BRITISH CHEMICAL ABSTRACTS

BRITISH CHEMICAL ABSTRACTSA.—PURE CHEMISTRY

JUNE, 1933.

General, Physical, andG low discharge in h ighly dried m olecular

g ases. A. G u n t h e r -S c h u l z e and F. K e l l e r (Z. Physik, 1933, 81, 528—538).—-When, dried with P 30 E, H 2 gave a new highly coloured discharge;N 2 and 0 2 became chemically very active, attacking even P t. A. B. D. C.

Spectrum of H 2. B ands ending on 2p2lJlevels. II. 0 . W . R i c h a r d s o n and P. M. D a v i d s o n (Proc. Roy. Soc., 1933, A, 140, 25—58).—The band systems coming from 3(P'S, 3cPTlab, and 3(PA„(, and ending on 2 p3ilaj levels, wliich have been p reviously described (A., 1931, 887), are reconstructed and extended. The properties of the levels arediscussed, and some of the principal consts. determined. L. L. B.

Theory of uncoupling and formulae for the Stark effect in hydrogen. J . K . L . M acD o n a l d (Proc. Roy. Soc., 1932, A, 138, 183—204).—M athematical. L. L. B.

Anode g low discharge. A. G u n t h e r -S c h u l z e and F. K e l l e r (Z. Physik, 1933, 81, 799—815).— Measurements of the anode fall in potential show th a t the fast electrons from the cathode move much farther from the cathode than has hitherto been assumed. The unperturbed anode fall is 20-5 volts in H 2, 30 volts in N2, and 14 volts in 0 2. Presence of dark spaces and" velocity distributions of electrons in the anode column are discussed. A. B. D. C.

Continuous electron affinity spectrum of hydrogen. C. K . J e n (Physical Rev., 1933, [ii], 43,540—547).—Mathematical. The intensity distribution in the continuous emission spectrum due to the capture of electrons by normal H atoms and the absorption coeff. in the corresponding absorption spectrum due to the neutralisation of negative H ions are calc, by wave mechanics. N. M. B.

Absolute probability of excitation of helium 2lP at zero angle. J . E . T a y l o r and R. W hid- d in g t o n (Proc. Leeds Phil. Soc., 1933, 2, 383— 385).—The im pact of 40—400-volt electrons with He atoms has been investigated, the inelastically scattered electrons a t zero angle being observed. The probability of 2XP excitation is approx. a linear function of the energy of the incident electrons. The excitation probability is lower than th a t predicted by recent theories. J . W, S.

Structure of the em ission line 6708 of lith ium .L. A l l e g r e t t i (A t t i R. A c c a d . Lincei, 1932, [v i] , 16,33—35).—In the arc spectrum of Li the above line

o o 547

Inorganic Chem istry.consists of two principal components with a separation of 0-155 Ä., and a third less intense line separated by 0-149 Ä. from the component of greater wave-length. 0 . J . W.

Stark effect. E. U. C o n d o n (Physical Rev., 1933, [ii], 43, 648—654).—Discussions on the Stark effect in at. spectra are illustrated by data on Ni, Li, C, and A. N. M. B.

Fine structure of the m etastable 2Jr>5/2l3,2 term s of n itrogen. V. T s c h u l a n o v s k y (Z. Physik" 1933, 82, 134—136). A. B. D. C.

Optical properties of the alkali m eta ls. R. W .W o o d (Nature, 1933, 131, 582).—New observations with th in films are described. L. S. T.

Anode spot in a neon tube. T . T a k a j h n e , T . S u g a , and A. Y a n a g ih a r a (Nature, 1933,1 3 1 ,584).— The anode spot in a discharge tube filled with Ne is interm ittent in its emission. L. S . T.

B and and line fluorescence in sod ium vapour excited by absorption. A. J a b e o n s k i , P. P r in g s - h e i m , and R . R o m p e (Z. Physik, 1932, 77, 26—34).— Fluorescence was excited in Na vapour a t 300— 400° by the continuous spectrum in the blue-green and re d ; a study of the relative intensities of the bands and lines on addition of He, A, and N2 revealed th a t the excited Na2 mol. is dissociated by collision.

A. B. D. C.Perturbed series of the spectrum of ionised

alum inium . L. P i n c h e r l e (Atti R. Accad. Lincei,1932, [vi], 16, 35—40).—Mathematical. The calc, divergence of certain series in the spectrum of A in from the R itz form agrees with the theory of Shen- stone and Russell (A., 1932, 439). 0 . J. W.

Arc spectra of chrom ium , m anganese, cobalt, and nickel in the red and near infra-red. H.S l e v o g t (Z. Physik, 1933, 82, 92—118).—The region studied was 6000—9000 Ä. A. B. D. C.

Isotope d isplacem ent and nuclear m om ent of zinc. H. S c h ü l e r and H. W e s t m e y e r (Z. Physik,1933, 81, 565—570).—Hyperfine structures of someZn n lines give isotopes 64, 6 6 , 67, and 6 8 , and the nuclear moment of 67 as 3/2. A. B. D. C.

N uclear m om ent of arsenic. M. F. Cr a w e o r d and A. M. Cr o o k e r (Nature, 1933,131, 655—656).— The nuclear moment of As is 1JxA/2tt. Details of the hyperfine structure of the spectrum of As rv are recorded. L. S. T.

548 BRITISH CHEMICAL ABSTRACTS.— A.

Intensity relations in the cadm ium spectrum .J. L. V e r h a e g h e (Proc. K. Akad. Wetensch. Amsterdam, 1933, 36, 71—73).—The intensity relations of certain Cd lines, exhibited by alloys of Ag and Cd containing 4% and 1% Cd, are discussed.

W. R. A.P aschen-B ack effect of hyperfine structure and

polarisation of resonance radiation. Cadm ium (6 1i >1—S1 ) . N. P . H e y d e n b u r g (Physical Rev., 1933, [ii], 43, 640—647).—Experimental data for the polarisation of Cd X 2288 A. resonance radiation, changing from 76-7% in zero field to 100% in a strong field || electric vector of the exciting light, are in good agreement with results calc, on the Goudsmit- Darwin theory of the Paschen-Back effect, and give1 2 -6 x lO "3 cm .-1 for the separation of the two levels into which the 6 1P 1 level of Cd (odd isotopes) is split.

N. M. BSignificance of H g A bands at 2365 and 2285 A.

and of the H g2 band at 1690 A. W. F i n k e l n b u r g (Z. Physik, 1933, 81, 781—784). A. B. D. C.

H igh-frequency d ischarge in gases. T. V.I o n e s o u and (Mme.) I . M ihttl (Compt. rend., 1933, 196, 1292— 1294; cf. A., 1932, 554; this vol., 9).— On applying a magnetic field parallel to the axis of a tube containing gas a t 0-001—0-1 mm. Hg and perpendicular to the field produced by a Mesny oscillator, if the la tter be moderately heated but little light is em itted and th a t mainly a t the electrode. This disappears a t the strength of field for which the free electrons are in resonance with the external electric field. A stronger magnetic field greatly increases the light, indicating th a t such a field reduces the potential required to m aintain the discharge, but i t again diminishes on further increase of the field. C. A. S.

Fine structure of the arc lines of lead and tin.S. B. L. Ma t h u r (Phil. M ag., 1932, [vii], 14 , 270— 275). N , M. B.

Uniform positive colum n. F. L. J o n e s (Phil. Mag., 1933, [vii], 15, 958—968).—Theoretical.

H. J . E.Evidence for a spinning photon. I. Intensity

relations in the Ram an spectrum of hydrogen.S. B h ag av an tam (Indian J . Physics, 1932, 7, 107— 138).-—The intensity and polarisation of the lines in the Ram an spectrum of H 2 are compared with the vals. calc, from wave mechanics (cf. Mannebaclc, A., 1931, 21). J . w . S.

V erification of Com pton’s arc theory by m ea surem ent of the arc gas tem perature at d ifierent p ressu res. L. S . O r n s t e i n , H. B r i n k m a n , and A. B e u n e s (Z. Physik, 1932, 77, 72—81).

A. B. D. C.D ischarge delay in hom ogeneous electric

fields and in air at atm ospheric pressure. R.S t r ig e l (Wiss. Veroff. Siemens-Konz., 1932,11, No. 2,52—74). A. J . M.

V isible part of the Northern L ight spectrum .L. V e g a r d (Z. Physik, 1933, 81, 556—559).— Correction of wave-lengths already given (A., 1932, 1187)- A. B. D. C.

Determ ination of Lande’s «/-factor by m eans of the E instein-de H aas effect w ith pyrrhotine.F. Co e t e r i e r (Naturwiss., 1933, 21, 251—252).— Pyrrhotine, a compound of Fe and S, containing a slight excess of S, is easily magnetised in one plane, b u t a t right angles to this is almost non-magnetic. The magnetism depends partly on orbital moment, and not alone on spin moment (cf. ferromagnetism). The relative presence of orbital and spin moments can be determined by finding the Lande (/-factor, which is 0 -6 , indicating both orbital and spin moments in the magnetism, the two being in opposite directions.

A. J . M.True and apparent intensity distribution in

spectral lines. II. H. C. B u r g e r and P. H. v a n

C i t t e r t (Z. Physik, 1933, 81, 428—434).—The in te gral equation of I (this vol., 2 0 1 ) is applied to p a rticular cases. A. B. D. C.

P ossib le variation in energy of atom ic processes occurring in a sm a ll interval of tim e.W. K u h n and H. M a r t in (Z. Physik, 1933, 81, 482— 490).—Association of spectral line width with life period leads to contradictions in the energy range of a predissociated mol. ; thermodynamics requires th a t this range be defined by the width of the illuminating line when this line is narrower th an the spectral line of the mol., b u t introduction of an in termediate level requires the range to be measured by the life period in the interm ediate level. The contradiction is not restricted to predissociation, but arises from the wave and corpuscular descriptions of nature being complementary. A. B. D. C.

Correspondence theory of line w idth . H.Ca s im ir (Z. Physik, 1933, 81, 496—506).—The relation of radiation damping to line width is treatedby Heisenberg’s method, and is applied to Ram anlines. A. B. D. C.

Structure of som e u ltra-soft X-ray lines. J . A.P r in s (Z. Physik, 1933,81, 507—515).—The structure of Ag M and W N lines are given, and C K lines are dependent on experimental conditions.

A. B. D. C.Scattering of hard X-rays by so lids. S.

Ci i y l i n s k i (Physical Rev., 1932, [ii], 42, 153— 166).N. M. B.

W eak lines in K spectra of rhodium and m olybdenum . H . H u l u b e i and (M l l e .) Y. Ca u - c h o is (Compt. rend., 1933, 196, 1294—1297).— Re-examined with the au thor’s spectrograph (cf. A., 1932, 902) the K spectra of R h and M o are slightly corrected and ex tended ; (30 a t 548-23 X for R h and 635-65 for M o are new (cf. Ross, Physical Rev., 1932, ii, 3 9 ,536,748). C. A. S.

L absorption d iscontinuities of gold . F. M. U b e r and C. G. P a t t e n (Physical Rev., 1932, [ii], 42, 229—232).—The vals. obtained agree with those obtained for Hg (cf. A., 1931,1105). N. M. B.

Fluorescence y ield from the Lux level of uranium . R . J . S t e p h e n s o n (Physical Rev., 1933, [ii], 43, 527—533).—The fluorescence yield for the Lm level, or the ratio , ho. of fluorescence quanta emitted/no. of incident quanta absorbed, gave the val. 0-67. The relative intensities of the a to the p lines

GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 549

in the K fluorescence spectra of Mo agree w ith the val. from the characteristic spectrum ; similar agreement is shown for the a and ¡3 lines in the fluorescence spectrum from the L U1 level of U. The ratio of the at. absorption eoeffs. on the short and long wave-length side of the L n i discontinuity is2-27. N. M. B.

Effect of chem ical com bination on the X-ray em ission spectrum of sulphur. J . V a l a s e k (Physical Rev., 1933, [ii], 43, 612—614).—W ith an improved method eliminating effects of chemical reaction with the target, the wave-lengths of S Ka and ¡1 lines were measured for S, FeS, CoS, NiS, Cu2S, andZnS. The iTp line in ZnS is a triplet. The Kfi lines of CoS and NiS are reported. N. M. B.

A bsorption coefficients for X -ra ys in the neighbourhood of the L edges for the elem ents gold, p latinum , and silver. M. W o le (Ann. Physik, 1933, [v], 16, 973—984; cf. this vol., 3).— From the absorption eoeffs. determined, the no. of dispersion electrons in the three L levels of Au, P t, and Ag were obtained. A. J . M.

D iffuse scattering of X-rays from sylvine. II.G. G. H a r v e y (Physical Rev., 1933, [iij, 43, 591— 595; cf. A., 1931, 1205).—The average at. structure factors of the K* and Cl' ions were calc., taking account of the incoherence of p a rt of the scattering, from abs. intensity measurements, of the diffuse scattering of X-rays of wave-length 0-71 A. for the angle range5—110°. Results are in good agreement w ith vals. for A, and with theoretical vals. N. M. B.

Absolute X-ray reflectivities of single crystals of calcite, rock-salt, R ochelle sa lt, and barite.P. K ir k p a t r ic k and P. A. R oss (Physical Rev,, 1933, [ii], 43, 596—600).— Using Ag Ko. radiation, the integrated reflexion, % reflexion, and rocking-curve width were derived for each crystal and wave-length. Scattering factors to show the variation with wavelength in the neighbourhood of the Ba K limit were found for barite. N. M. B.

Influence of oxygen and sulphur on the photoelectric effect of alkalis (K and N a). P . V. T im o f e e v a n d V. V. N a l i m o v (Z. P h y s ik , 1933, 81, 687—696).'—T h e m a x ' s e n s it iv i t y , I j l 0 , fo r p h o to -c e l ls i llu m in a te d w i t h t h e fu l l sp e c tr u m fr o p i a f i la m e n t la m p a t 2700° a b s . w a s o b ta in e d w it h 40 X10~5 g . p e r sq . cm . o f a d s o r b e d 0 2 fo r K , a n d w i t h 60 X10-8 fo r N a : T h e e ffe c t o f a d s o r b e d S a n d t h e s tr u c tu r e o f t h e s e n s it iv e su r fa c e a re d is c u s se d . A. B. D . C.

P ositive electrons. (M m e .) I. C u r i e and F. J o l io t (Compt. rend., 1933, 196, 1105—1107).— T hat positive electrons, and not negative ones brought to a focus by the chamber, are em itted when Pb is subjected to the neutrons and y-rays produced by P o + B e is rendered almost certain by placing the source behind a Pb plate closing an orifice in a cylindrical chamber and subjecting the em itted electrons to a magnetic field. W ith a field of 1100 gauss and considering only electrons of energy > 1 0 6 ev. there were for 1 0 negative electrons from the Pb 2-83 positive from the Pb and 1-76 positive or negative distributed on the walls of the chamber; with 640 gauss corresponding figures for electrons of

energy > 0-5 X'10.® ev. are 4-5 and 3-6; the positive electrons have a smaller energy than the negative. W ith an A1 plate the vals. are 0-53 and 1-3. In te rposition of 2 cm. of Pb between source and chamber reduces the no. of positive ¡electrons issuing from the Pb by 50%, implying th a t the emission of positive electrons is probably due to the y-rays (cf. this vol., 441). C. A. S.

Reflexion of electrons from standing light w aves. P. L. K a p i t s a (Proc. Camb. Phil. Soc., 1933, 29, 297—300).—Theoretical.

Variation w ith angle of em ission of the rad iation from m etals bom barded w ith slow electrons. C. B o e c k n e r (Bur. Stand. J . Res., 1932, 9, 583—591).—P t, W, and Ag cylinders were bombarded with electrons of energy 7 volts and the intensity of light emitted a t different angles 'was compared. The results indicate th a t the radiation is em itted uniformly in all directions from a layer beneath the surface of the metal. D. R. D.

Variation of secondary em ission w ith heat treatm ent. P. L. Co p e l a n d (J. Franklin Inst., 1933, 215, 435—443).—Targets contam inated with grease give high secondary emission on electron bombardment. When heated they recover to a val. characteristic of the metal. H. J . E.

Diffraction of very rapid electron s . M. K o s m a n and A. A l i c h a n ia n (Naturwiss., 1933, 21, 250).— Apparatus for producing very rapid electrons up to 520 kv., and for studying their diffraction a t Ag foil, is described. A. J . M.

Diffraction of low -speed electrons by a tungsten single crystal. W. T. S p r o u l l (Physical Rev., 1933, [ii], 43, 516—526).—Using a new magnetic deflexion method, the intensity of the secondary beams was measured when the (1—1—2 ) and (1-—0—0) planes of a W crystal were bombarded normally by prim ary electrons. Strong beams in the A A ' azimuth of the (1— I —2) plane were governed in every case by the vol. equation and not, as theoretically required, by the surface equation. Vals. obtained are Wa 5-52, and IF* 1 volt. N. M. B.

Electron affinity spectrum . 0 . O l d e n b e r g (Physical Rev., 1933, [ii], 43, 534—539).—A ttem pts to observe an electron affinity spectrum of at. I, em itted by the combination of neutral electronegative atoms and electrons, using three methods : hollow cathode, positive column with a rare gas added, and glowing filament, were unsuccessful. The failure is probably due to the capture of electrons by halogen atoms being unlikely as compared with the combination of positive ions and electrons.

N. M. B.Photo-electric investigation of the influence of

m atter on slow electrons. G. L a n g (Ann. Physik, 1933, [v], 16, 781—792).—Using monochromatic light of 2540 A. and a photo-electric cell, which incorporated a thin layer of P t sputtered on a quartz plate as cathode, the emission of slow electrons was investigated under various conditions of pressure and cathode thickness. W. R. A.

Scattering of electrons in th in f d m s . G . O . L a n g s t r o t h (Proc. Roy. Soc., 1933, A, 140, 159—


178).—Measurements have been made of the angle distribution of electrons scattered between 65° and 160° by celluloid and A1 films of varying thickness, and of the to ta l no. of electrons scattered back from various thicknesses of A1 film with >186 volts energy, for prim ary voltages of 8—24 kv. L. L. B.

E lastic and inelastic scattering w ith angle in helium . T. E m m e r s o n and R. W h i d d i n g t o n (Proc. Leeds Phil. Soc., 1933, 2, 386).—Preliminary results are reported from experiments on the electron scattering by He a t low pressure. At zero scattering angle and low electron speed the inelastic scattering is very small, bu t rises to a max. a t an angle < 1 0 °, in disagreement with theory. J. W . S.

Energy of the beam s in electron d iffraction.F. C. P o u l t n e y and R. W h id d i n g t o n (Proc. Leeds Phil. Soc., 1933, 2 , 387—390).—Investigation of the velocities of electrons diffracted by passage through a thin film has been repeated, greater resolution being obtained by deviating the rays through 90° in the field. The velocities are the same to ±0-3% and no trace of electrons the energy of which is < th a t of the main beam by the amount lost in X -ray excitation is found. J . W. S.

Q uantum theory of inelastic electron collisions.L. G o l d s t e in (Ann. Physique, 1933, [x], 19, 305— 420).—Mathematical. Following a general survey, calculations made for various series of levels are applied to ionisation stages, and compared with experimental results. N. M. B.

Scattering of electrons by ions and the m obility of electrons in a cæ sium discharge. C. B o e c k n e r and F. L. M o h l e r (Bur. Stand. J. Res., 1933, 10, 357—363).—From measurements of the electrical gradient and the electron temp, and concn. the mobilities of electrons in the positive column of a Cs discharge are calc. The cross-section of the Cs atom deduced from the mobilities a t low electronic concn. is 3-3 X10 ' 11 sq. cm. for electron energies of about 0-33 volt, and appears to increase linearly with ionic concn. in the discharge, the variation being due to scattering of electrons by ions. This variation gives a val. 75 X lO' 14 sq. cm. for the ionic cross-section of 0-33-volt electrons, a magnitude explicable by electrostatic interaction between ions and electrons.

J . W. S.Diffusion of electrons b y atom s. J . W i n t e r

(Compt. rend., 1933, 196, 1299—1301).—M athematical; The effect of a sphere of spherically symmetrical potential on a de Broglie wave is considered.

C. A. S.W idth of the discharge in the electron counter.

E. G r e i n e r (Z. Physik, 1933, 81, 543—555).—In the Geiger-Müller counter the discharge spreads through the whole tube by means of ultra-violet radiation.

A. B. D. C.Cathodic d isintegration of p latinum by m er

cury ions. J . E . H e n d e r s o n and (Miss) E. G i d e o n (Physical Rev., 1933, [ii], 43, 601—604).—Disintegration per positive ion increased linearly with the energy of the ion up to 2000 volts. Approx. two atoms of P t are ejected per incident ion of 1000 volts energy.

ÙST: M. B.

P olarisab ilities of ions from spectra. J . E .M a y e r and (Miss) M. G. M a y e r (Physical Rev., 1933, [ii], 43, 605—611).—D ata corrected for penetration effect and for higher order distortion of the ion are calc, for Li, Be++, Bt++, C++t +, Na+, Mg++, Al+t t , K +, Ca++, R b+, Sr++, and Cs+ from the corresponding spectra. N. M . B.

At; w t. of iodine. G u ic h a r d (Compt. rend., 1933,196, 1024— 1025).—Baxter and Butler’s doubts as to the purity of I 20 5 and its suitability for at. wt. determinations are criticised, and 126-91 is recommended as the at. wt. of I (cf. A., 1914, ii, 723;1931, 543; this vol., 203). C. A. S.

A t. w t. of lead from Bedford cyrtolite. G. P.B a x t e r and C. M. A l t e r (J. A m e r . Chem. Soc.. 1933, 55, 1445—1448).—The at. wt. is 205-92+ 0-02 from determinations of the ratio PbCl2 : 2 A g . The result is discussed. J . G. A. G.

A ttem pt to separate isotopes by reversible fractional d istillation . H. J . H e n r i q u e s and R. E. Co r n is h (J. Physical Chem., 1933, 37, 397—399).—Fractional distillation of CH2C12 in a column6-09 m. long gave no separation of C P5 and Cl37.

H. J . E.Photochem ical separation of isotopes. W.

K u h n and H. M a r t in (Z. physikal. Chem., 1933, B, 21, 93—137).—A more detailed account of the partial separation of the isotopes of Cl previously reported (A., 1932, 1186) is given. The fact th a t separation has been achieved indicates th a t the probability of decomp, of excited mols. which absorb strictly discontinuously in the region of sharp absorption bands m ay be finite. I t is estim ated th a t of mols. which have passed to the quantum state p '—i, q'— 1 by absorption of the line 2816-179 Ä. about one fifth decompose and the remainder return to the normal state. Since the photochemical method employed is purely chemical, the isotopes of an element cannot be identical in chemical properties. I t seems possible th a t there may be cases where, using such a method, practically complete separation can be achieved by a single irradiation. R. C.

Origin of the various kinds of lead. O. H a h n and L. M e i t n e r (Naturwiss., 1933, 21, 237—238).— Pb207 has the same origin as Pb206 and Pb208. The various forms arose a t different periods of the cosmic era. I t is doubtful whether the larger p a rt of ordinary Pb arose from U isotopes or from Th. A. J . M .

W ave m echanical m odel of the neutron. S.F l ü g g e (Z. Physik, 1933,8 1 ,491—495).—Theoretical.

A. B. D. C.O rbits of electrons released by neutron excit

ation. L. M e i t n e r and K. P h i l i p p (Naturwiss., 1933, 21, 286—287).—The no. and energy of electrons from a P o + B e source are much > those from a P o source alone. In a magnetic field, the m ajority of these electrons were deflected in a direction opposite to th a t expected of negatively-charged particles. They may be “ positive ” electrons (cf. this vol., 549).

A. J . M.N eutrons in the nucleus. I, II. A. L a n d jC:

(Physical Rev., 1933, [ii], 43, 620—623, 624—626).—I. Mass defects show th a t the isotopes of a n element


differ only by the no. of neutrons incorporated by them.

II . The no. of neutrons in the nuclei is illustrated by a model showing the building up of successive shells of neutrons. N. M. B.

Condensation cham ber photographs of atom ic disintegration by rapid protons. F. K i r c h n e r (Naturwiss., 1933, 21, 250—251).—The at. disintegration of B by rapid protons gives rise to a considerable no. of nuclear particles of range both > and< (1-5— 6 cm.) th a t noted by Cockcroft and Walton (3 cm.) (cf. this vol., 111). A. J . M.

A tom ic disintegration by ultra-radiation. W.M e s s e r s c h m id t (Naturwiss., 1933, 21, 285—286).— The at. nucleus of a substance absorbing u ltraradiation can be completely disintegrated by it. A bundle of very rapid corpuscular rays, having a range of 20 cm. in Pb, is then released. A. J . M.

Range of particles from atom ic disintegration at low voltages. R. D o p e l (Z. Physik, 1933, 81, 821—823).—Li and B disintegrated with 40-kv. canal rays gave particles of range in agreement with those observed on disintegration with several hundred kv.

A. B. D. C.C ollisions between neutrons and protons.

P. A u g e r and G. M o n o d -H e r z e n (Compt.rend., 1933, 196, 1102—1104; cf. this vol., 205).—The distribution of the rapid and slow protons ejected from H by neutrons produced by P o + B e as regards direction, and for the slow protons also length of path, determined by means of a Wilson expansion chamber, confirm the distinction between them. The probability of emission between 0 and O-fdO (0 being measured from the direction of incident neutron, assumed to be direct from the source) is, for the swift protons, a1 sin 0 cos 0 (¿0 , and for the slow ones approx. a2 sin 0 do (av a2 being consts.); the length of path of the la tter is 1— 14 mm., with a max. for about 5 mm. These results indicate as regards the swift protons elastic frictionless collisions between the neutrons and protons, as regards the slow ones the existence of slow neutrons diffused by the m aterial of the expansion chamber. C. A . S.

Diffusion of recoil atom s in air. (M l l e .) C. Ch a m ie (Compt. rend., 1933, 196, 1107— 1109).— A collecting plate was placed a t varying distances, x > 0T3 mm., from active deposit of Th (path in air a t 760 mm. and 15°, 0-13 mm.), and the intensity of ionisation measured. The intensity decreases exponentially, l==I0erkx for x > 0-13 < 0 -5 mm., and linearly for x > 0-5 mm., indicating diffusion of the recoil atoms in air. C. A. S.

Entry of the d isintegrating a-particle into the nitrogen nucleus and a general relation between heights of nuclear barriers and atom ic num ber.E. C. P o l l a r d (Proc. Leeds Phil. Soc., 1933, 2, 357—358).—Previous results (cf. A., 1932, 894) are amplified. The height of the barrier is, except for the lightest elements, approx. proportional to the at. no. N. M. B.

A tom ic radiations of short range from heavy elem ents. H. P e t t e r s s o n and J . J . S c h i n t l - m e is t e r (Naturwiss., 1933, 21, 222—223).—S u b -

stances in th in layers in the gaseous state werebombarded with a beam of a-rays from Po. W itha special apparatus the presence of short-range radiations from Xe mixed with He was shown, the proportion of new particles to to tal no. scattered being 0-66. The particles m ust be either scattered a-particles with greatly reduced range due to inelastic collisions, or else products of the disintegration of the Xe nucleus. A m ixture of 40% K r and 60% He yielded a similar group of particles with evensmaller range. A. J . M.

Fundam ental state of nuclear a-particles. G. G a m o w (Nature, 1933, 131, 618—619). L. S. T.

T heoretical decay curves for various ratios of ra d iu m -# to radium -C, and of thorium -U to thorium -C. J . A. Cr a n s t o n and C. B e n s o n (J. Roy. Tech. C o ll., 1933, 3, 47—51). A. R. P.

R adioactivity of sam arium and the form ation of h ibernium haloes. J . H. J . P o o l e (Nature, 1933,131, 654).—A discussion (cf. this vol., 442).

L. S..T.Chem ical detection of artificial transm utation

of elem ents. F. A. P a n e t h and P . L. G ü n t h e r (Nature, 1933, 131, 652—653).—In the bom bardment of 0 2 by a-rays such Ne as may be formed falls below the ratio 1 atom Ne to 105 a-particles, the present lim it of detection of Ne in He. Bombardm ent of N aF and K F also gave indefinite results. No formation of He has been observed after the bombardment of substances by ß-rays or by neutrons. When H 20 , C, K, Sn, or Hg is bombarded by the unfiltered rays of Tli-i? and -C, the He formed, within a 1 0 % limit of error, corresponds with the no. of a-particles shot into the substance; with compounds such as paraffin, palmitic acid, and P h 3, surpluses of up to 100% have been obtained. L. S. T.

Early h istory of the determ ination of atom ic charge. A n o n . (Nature, 1933, 131, 569—570).

L. S. T.Evaporation phenom ena w ith m ercury drop

lets and their influence on the m easurem ent of the elem entary quantum of electricity. R.N e s t l e , K. S c h ä f e r , and E. R e g e n e r (Z. Physik, 1933, 81, 700—702).—Polemical against Lustig and Reiss (this vol., 111). A. B. D. C.

T ransport phenom ena in E instein-B ose and F erm i-D irac gases. I . E. A. U e h l in g and G . E. U h l e n b e c k (Physical Rev., 1933, [ii], 43, 552—561). —Mathematical. N. M. B.

Significance of experim ental determ inations of the m ean specific ionisation by cosm ic rays from com parison m easurem ents w ith an ion isation cham ber and counter. W. K o l h ö r s t e r and L. T u w im (Z. Physik, 1933, 81, 435—439).—Recent applications of quantum mechanics explain the high sp. ionisation (135 ions per cm.) previously observed (ibid., 1931, 73, 130); the criticism of Locher (this vol., 556) is discounted. A. B. D. C.

O rigin of cosm ic radiation . H. A l f v ü n (Nature, 1933, 131, 619—620).—The origin of cosmic rays can be explained without new hypotheses by applying the kinetic theory of gases to the conditions of space.

L. S. T.


Absorption curves of u ltra-radiation and their explanation. E. R e g e n e r (Physikal. Z., 1933, 34, 306—323).—Results of determinations of the intensity of ultra-radiation in the sea and in the stratosphere are given, and the absorption curves arc analysed. The nature of ultra-radiation is discussed.

A. J . M.Dependence of ionisation by cosm ic radiation

on pressure. B. G r o sz (Z. Physik, 1932, 78, 271—278).—An equation is given. A. B. D. C.

The neutron, atom building, and a nuclear ex clusion principle. W. D. H a r k in s (Proc. Nat. Acad. Sei., 1933, 19, 307—318).—The neutron is held to constitute a new element of zero at. no. The emission of y-rays by nuclei excited by neutrons is discussed. The no. of neutrons (neutronic no.) is even for almost every known at. nucleus. A nuclear exclusion principle and pairing of neutrons are deduced. N. M. B.

Law of force betw een neutron and proton.E. C. P o l l a r d (Proc. Leeds Phil. Soc., 1933, 2, 397—400).—The relation between height of the nuclear barrier and tho nuclear charge is used to determine vals. for the polarisability of a neutron. J . W. S.

T etrahedral field of action of atom s. III. Probable cause. R. R e i n i c k e (Ann. Guebhard- Sevcrine, 1932, 8 , 217—244; cf. A., 1932, 563, 901).— The author’s theory is discussed from the viewpoint of electronic configurations. J , W. S.

T hree-dim ensional periodic orbits in the field of a non-neutral atom . M. A. E l -S h e r b i n i (Phil. Mag., 1932, [vii], 14, 304—310).—Mathematical.

N. M. B.Vector m odel and the P au li principle. M. H.

J o h n s o n , jun. (Physical Rev., 1933, [ii], 43, 627— 631; cf. A., 1932, 315).—M athematical. N. M. B.

A lm ost closed sh ells. M. H. J o h n s o n , jun- (Physical Rev., 1933, [ii], 43, 632—635).—M athematical. Shortley’s results (cf. A., 1932, 668) are extended, by a development of Heisenberg’s trea tment, to several almost closed shells with other electrons not in the shells. N. M. B.

Nuclear m agnetic m om ents. S. G o u d s m it (Physical Rev., 1933, [ii], 43, 636—639).—M athematical. Formulas for the calculation of nuclear magnetic moments from observed hyperfine structure separations are deduced. " N. M. B.

Theory of m eta ls. R. P e ie r l s (Z. Physik, 1933, 81, 697—699).—A theory different from th a t of Wilson (this vol., 116) is preferred. A. B. D. C.

Quantum m echanics of diatom ic system s.M. B o rn and S. F l ü g g e (Ami. Physik, 1933, [v], 16, 768—780).—Mathematical. W. R. A.

Evaporation of incandescent w ires in a vacuum . III. L. P r ä s n i k (Z. Physik, 1932, 77, 127—132; cf. A., 1932, 565).—■Theoretical: The effect of heat conductivity is taken into account.

. ; ' A. B. D. 0.Optics in the service of chem istry. B. K.

Singh (J. Indian Chem. Soc., 1933, 10, 7—26).— A lecture.

Optical properties of photographic layers.E. L axj and J . J o h a n n e s s o n (Z. Physik, 1933, 82, 37—47).—A study of the scattering of light by photographic plates revealed th a t for low intensity scattering by the gelatin predominates, Ag particle- scattering reaching a max. a t 50% image intensity. Microphotometer records are best obtained with diffuse light with dense images, and contrast can be increased by rubbing magnesia on the film surface Of the plate and examining with light incident on the glass surface. A. B . D . C.

L ight filter for the m iddle u ltra-violet. H . J . B a c k st r ö m (Naturwiss., 1933, 21, 251).—3 cm. thickness of a solution containing l-75.M-(pure)NiS04 and 0-5Jf-CoS04 is recommonded for transmission of light of wave-lengths in the neighbourhood of 300 mjx. Other filters are described’. A. J . M.

Investigations in the Schum ann region . H . H e s e , A. R o s e , and R . G r ä f i n zu D o h n a . I. Schum ann spectrograph for precision m easurem ents. H . H e s e . II. S im ple fluorite spectrograph and its application to absorption photographs. A. R o s e (Z. Physik, 1933, 81, 745—751, 751—-763).—I. The spectrograph is designed for absorption spectra of org. compounds.

II . The ultra-violet transmission of B20 3, andabsorption of 0 2, CH4, C2H 2, and CGH G were investigated between 2050 and 1250 Ä. A. B. D. C.

N ew band in the w ater vapour discharge. W . H. R o d e b u s h and M. H. W a h l (J . Amer. Chem. Soc., 1933, 55, 1742).—The spectrum of the electrodc- less discharge in H 2On vapour contains a band, with the head a t X 3564 A., which is attribu ted to the presence of OH+. J . G. A. G.

Band system of SrO in the near infra-red.K. M a h l a (Z. Physik, 1933, 81, 625—646).—R otational and band analyses of bands near 8000 Ä. arc recorded. A. B. D. C.

Band spectra of the m onoxides ScO , YO, and LaO. G. P i c c a r d i (Gazzetta, 1933, 63, 127— 138; cf. A., 1932, 1074).—Analysis of th e oscillation bands in the emission spectra of the vapour of the oxides shows th a t the bands are due in each case to the d iat. neutral mol. The fine structure of the bands could not be investigated. 0 . J. W .

R otation-vibration spectrum of w ater vapour.II. W . B a u m a n n and R. M e c k e . III. K. F r e u - d e n b e r g and R. M e c k e (Z. Physik, 1933, 81, 445— 404, 465—481).—II. Rotation lines in bands a t 9420, 9060, 8227, and 7227 A. are interpreted according to Mecke’s schcme (this vol., 445).

II I . R otation lines in bands a t 6994, 6524, 5952, 5924, and 5722 Ä. are interpreted according to Mecke’s scheme, and formulaj are given expressing the moments of inertia in term s of the vibrational quantum nos.

A .B .D . C.Optical investigation of perylene and its

derivatives. IV. U ltra-violet absorption spectrum of 1 : 12-derivatives and isom erides. C.H u a -c h ih and H . Co n r a d -B il l r o t h (Z. physikal. Chem., 1933, B, 20, 333—339; cf. A., 1932, 107).—1 : 12-Perylene peroxide has an absorption curve quite different from th a t of 1 : 1 2 -perylenequinone, and


seems to have a cyclic peroxide structure. The curves of 3 : 1 0 -dihydroxyperylene and -perylenequinone are similar, whilst the curve of 1 : 1 2 -dihydroxyperylene is unlike th a t of 1 : 1 2 -perylenequinone. The absoiption of hexahydroperylene supports Zinke and Schniderschitsch’s structure (A., 1929, 803), not Zinke and Benndorf’s (A,, 1932, 507).

R. C.Absorption of halogen derivatives of m ethane

in near ultra-violet, and their d issociation energies. T. I r e d a l e (Z. physikal. Chem., 1933,B, 20, 340—344).—A discussion of the absorption spectra of CH3I, CH2I 2, and CHT3 and the methods of determining the energy of the halogen-C linking shows th a t the spectroscopic vals. of this energy are as yet uncertain. R. C.

Absorption spectra [of the N a sa lt of tetra- iodophenolphthalein and phenoltetraiodophthal- ein]. E. H . H a r v e y (Amer, J . Pharm ., 1933, 105,199—200).—Curves are given for solutions in EtOH. The latter salt is more sensitive to p a changes.

R. S. C.Infra-red absorption spectra of halogen deriv

atives of m ethane. J . L e c o m t e (Compt. rend., 1933, 196, 1011—-1013).—-Using a special spectrograph with rotating prisms of NaCl or KOI the absorption spectra of the liquid halogen, X , derivatives of CH4 have been determined for X 6-9—20 |i. In most cases there are two max., in good agreement w ith the Ram an lines. X of both max. increases as X changes in the order Cl, Br, I ; increase in the no. of X atoms causes the X of the max. of greater X to increase, th a t of the max. of smaller X to decrease. Secondary zones of absorption are explicable by combination frequencies in the cases of CX4 and CHX3. C. A. S.

R otation-vibration spectrum of ethylene in the near infra-red. W. S c h e i b and P. L ü e g (Z. Physik, 1933, 81, 764—775).—The band a t 8715 Ä. was investigated, and gives the interm ediate moment of inertia as 28-85 X10*40 g.-cm .2 Taking the C-H distance as 1-08 Ä., the C-C distancb is 1-34 Ä. C-C separations arc 1-54, 1-34, and 1-19 A. for single, double, and triple linkings, respectively.

A. B. D. C.Interpretation of polyatom ic spectra. L. T isz a

(Z. Physik, 1933, 82, 48—72).—Selection rules for Raman and infra-red spectra arc deduced by the group theory for harmonic and combination tones, and for rotational structure. A. B. D. C.

R am an effect in X-ray region . II. W. K ast and F. WÜRSTLLN (Z. Physik, 1933, 81, 581—583).— Two examples of a supposed Ram an effect are due to known X-ray spectral lines. A. B. D. C.

R am an effect of glycerol. R. Bär (Z. Physik, 1933, 81, 785—789).— 15 lines were obtained in the Raman spectrum, bu t the continuous spectrum can be due only to fluorescence (cf. Carrelli and Went, this vol., 337). A. B. D. C.

R am an spectrum of silicon trichlorobrom ide.M . d e H e m p t i n n e , J . W o u t e r s , and (M l l e .) M . F a y t (Bull. Acad. roy. Belg., 1933, [v], 19, 318—324).— On excitation w ith the H g 4358-34 Ä. line SiBrCl3 shows Ram an frequencies of 410, 362, 325, 201, 183, and

123 cm.-1, the 362 cm .-1 frequency being very strong. The fundamental frequencies for this mol. are calc, and compared with the data for SiHCl3. J . W. S.

[Ram an effect and] ethylenic link ing : hexenes. (M l l e .) H. v a n R i s s e g h e m , (M l l e .) B. G r e d y , and L. P i a u x (Compt. rend., 1933,196, 938—940; cf. A.,1932, 897).—The Ram an spectra between 1250 and 1700 cm .-1 (omitting the band near 1450) of Au- and AP-(cis and ir<ms)hexene, S-(cis and trans)- and y-methyl-A^- and 8 -methyl-Av-pentene, and Py- d ¡methyl-A^-butene include lines a t 1252—1262, 1296—1306,1350—1416, and 1642—1676. Methods of prep., b.p., and some f .p. and d are given. C. A. S.

[Raman effect and] acetylenic link ing : d isubstituted acetylenes. (Ml l e . ) B. Gr e d y (Compt. rend., 1933, 196, 1119—1122; cf. A., 1931, 284).— T h e Ram an spectra of 11 hydrocarbons RC:CR', where R is Ph, C5H U, or C?H 13, and R ' M e, E t, Pr, Bu, or CjHj, are tabulated. All show two unequal lines between 2200 and 2300 cm r 1; Ph lowers the frequency. In its absence the strongest line is a t 2234 ; if R ' is M e there are strong lines a t 378 and 1380. All have a doublet a t 1300—1330. There is some ground for supposing the presence of two characteristic lines to indicate a new form of isomerism. C. A. S.

D epolarisation of ligh t by liquids holding crystalline particles in suspension in relation to the birefringence of these particles. S. P r o c o p iu (Ann. Sci. Univ. Jassy, 1933, 17, 111— 117).—The depolarisation is due to the magnetic birefringence of the particles. A proportionality relation between the depolarisation and the no. of particles and their birefringence has been developed theoretically and confirmed by experiment. This m ethod m ay be used for the determination of the magnetic birefringence of colloid particles. J . W. S.

Depolarisation of ligh t diffused by a uniaxial crysta l w ith optic ax is parallel to diffused light. J . Ca b a n n e s (Compt. rend., 1933, 196, 977—979).— If a uniaxial crystal be examined with its axis in the direction of the diffused ray all the Ram an lines are completely depolarised. This is inconsistent with the Langevin mol. model and the ellipsoid of refractivity. An explanation is based on the Kramers-Heisenberg theory (cf. A., 1932, 212; this vol., 113, 208).

C. A. S.Diffusion of light in h igh ly turbid m edia.

V. A. F a b r i k a n t , V. L. G i n s b u r g , and V. L. P u l v e r (Z. Physik, 1933, 81, 79i>—798).—Theoretical.

Theory of fluctuations and critical opalescence. Y. R o c a r d (J. Phys. Radium, 1933, [vii], 4, 165— 185).—Mathematical (cf. this vol., 113).

M echanism of photochem ical d issociation. L. G o l d s t e in (J. Phys. Radium, 1933, [vii], 4, 123— 131).—Mathematical. The nature of the intensity of continuous absorption bands for a mol. having .an electric moment in its fundamental electronic state, and the bands accompanying dissociation processes are calc. N. M. B.

Total reflexion of X-rays at liqu ids. H. S t e p s (Ann. Physik, 1933, [v], 16, 949— 972).— The reflexion of X-rays a t free liquid surfaces has been investigated. The properties of surfaces as regards

554 BRITISH ' CHEMICAL ABSTRACTS.— A.

image formation were compared. Those of glycerol and HoO were specially good. A. J . M.

P hysical proof of G urw itsch radiation. B. R a j e w s k y (Naturwfss., 1933, 21, 299).—Notes on the work of Siebert and Seifert (cf. th is vol., 335).

A. J . M.Intensity of fluorescence of sod ium salicylate.

P. D u b o u l o z (Compt. rend., 1933, 196, 1221— 1222; cf. A., 1932, 319).—Using the method previously described, save th a t dextrin was absent, curves re la ting intensity of fluorescence to wave-length of incident light have been obtained with a 0 arc and a W- filament lamp, confirming previous results (cf. A., 1927, 497). C. A. S.

Inhibitive action of organic substances on fluorescence of uranine. J . B o u c h a r d (Compt. rend., 1933, 196, 1317— 1318; cf. this; vol., 337).— For a giVen concn., s, of 14 org. substances (chiefly amines or phenols) the fluorescent power of uranine in O-lJV-NaOH decreases exponentially with its concn.; and similarly for a fixed concn. of uranine and variable concn. of org. substance. For 18 others (chiefly sugars, amines, or amides) the result is independent of s. C. A. S.

E m ission of phosphors. III. Behaviour of sam arium in the oxides of group II. R . Tom a- s c h e k and 0 . D e u t s c h b e in (Ann. Physilc, 1933, [v], 16, 930—948; cf. A., 1932, 1076).—The emission spectra of Sm phosphors with CaO, SrO, BaO, MgO, and BeO were obtained. The structures of these spectra depend on the previous history of the prep, and on the cryst. structure. A. J . M.

Spatial structure of phosphorescent m ixtu res.A. S c h l o e m e r (J. pr. Chem., 1933, [ii], 137, 40— 46),—The middle point of a phosphorescent centre is occupied by an active ion or an electrically differentiated group of atoms. I t is surrounded by mols. or groups thereof, the arrangement of which is either th a t of a crystal lattice in which the orientation is disturbed by the active middle point, or th a t which maintains within a solvate. The active ion plays the part of the dissolved substance and the fundamental mass th a t of the solvent. H. W.

Constitution of phosphorescence centres in fluorite. S. I im o r i (Sci. Pap. Inst. Phys. Chcm. Res., Tokyo, 1933, 20, 189—200; cf. A., 1931, 1 1 1 1 ).—The nature of the primary m atter, previously denoted P v in the lumino-transformation of fluorite is further discussed. J . W. S.

Lum inescence of alkaline-earth tungstates containing lead . F. E. S w i n d e l l s (J. Opt. Soc. Amer., 1933, 23, 129—132).—Pb is an activator for the phosphorescence of Ca and Sr tungstates, the optimum concn. being about 0-01 g.-mol. PbW 0 4 per g.-mol. of alkaline-earth tungstate. Higher concns. of Pb produce a very great increase in fluorescent and phosphorescent power of SrW 04, optimum Pb concn. being 0-2 and 0-4 g.-mol. for the respective effects, whereas high Pb concn. in CaW 04 decreases the luminescent power. N. M. B.

Transform ation of translational into vibrational energy in m olecular collision processes. J. F r a n c k and A. E u c k e n (Z. physikal. Cliem., 1933,

B, 20, 460-—466):—-In determining the frequency ofthis transform ation the m utual perturbation of the

-potential curves of the colliding individuals plays an im portant p a r t ; i t is probably th is effect, ra ther than the purely mechanical transfer of energy, which is the decisive factor. This affords a qual. explanation of the differences in yield. R. C.

Investigation of transform ation of translational into vibrational energy on collision of various m olecules by m eans of sound dispersion m easurem ents. A. E u c k e n and R . B e c k e r (Z. physikal. Chem., 1933, B, 20, 467—474).—Measurements of the velocity of sound of frequency 3.x 105 hertz have shown th a t He, H 2, HC1, and CH4 promote the transform ation of translational into intramol. vibrational energy of Cl2 and C02; A has no effect. These observations support the theory previously advocated (cf. preceding abstract). " R . C.

Inner photo-electric effect in cuprous oxide.D. N a s l e d o v and L . N e m e n o v (Z. Physik, 1933, 81, 584—604).—Conductivity measurements were made for Cu20 in the dark and when illum inated at room and a t liquid air tem p .; the inner photo-electric effcct is very small, being inappreciable for layers of resistance 1 0 4 ohms per cm., but giving a 600-fold increase in conductivity of layers of 1 0 7 ohms per cm. a t liquid air temp. A. B. D. C.

Photo-electric effect in single crystals of cuprite.R . D e a o l io (Compt. rend., 1933,196, 1303— 1305).— (a) When light falls perpendicularly on one gilt surface of a parallelepiped cut from a single crystal of cuprite two opposite surfaces of which are covered with a film of Au, a current passes externally from the illuminated to the dark surface—about 10~7 amp. for light of 25 candles, (b) If the light fall on two opposite ungilt surfaces a current still passes, the direction of which changes when the light falls close to the gilt surface which, except when it falls there, is the negative pole. If a current is passed through the cuprite arranged as (a), the photo-electric effect gradually disappears through deposition of Cu below the Au cutting off the light. These facts point to the cuprite becoming electrolytically conducting when exposed to light, and give a more satisfactory explanation of Dember’s effect (cf. A., 1931, 999; Physikal. Z., 1932, 33, 207). C. A. S.

N on-additive effect of radiations of different w ave-lengths on cuprous oxide photo-cells.C. L a p ic q u e (Compt. rend., 1933, 196, 1301—1303;cf. A., 1931, 1112). C. A. S.

Photo-effects in sem i-conductors. B . L a n g e

(Trans. Electrochem. Soc., 1933, 63, 69—81).— Current theories are critically reviewed and a new theory is advanced. The close parallelism between the spectral sensitivity of the photo-electric response of a Cu20 cell of the “ front wall ” type and th a t of the photo-electric change in its resistance indicates the identity of the electrons of the “ barrier ” film photo-effect and those of the internal photo-effect.

H. J . T. E.Proof of a lim itin g layer in the cuprous oxide

barrier layer cell. F. R o t h e r and H. B o m k e (Z. Physik, 1933, 81, 771—775).—Diffusion occurs

GENERAL, PHYSICAL, AND INORGANIC! CHEMISTRY. 555

in the thermal formation of Cu20 from Cu giving a reaction in the solid state. Several zones of different conductivity were observed, and it is suggested th a t the hypothetical barrier layer consists of a nonconducting layer of the purest oxide. A. B. D. C.

Relation of characteristic vibrations and the external photo-electric effect. III. Coal-tardyes in the ultra-violet. F. H l u ô k a (Z. Physik,1933, 81, 521—527).—Measurements in the u ltraviolet confirm relations already given (this vol., 447).

A. B. D. C.N ew detector. J . Ca y r e l (Compt. rend., 1933,

196, 1216—1218).—If aq. H 2S is electrolysed with a crystal of galena as anode the crystal becomcs covered with a brown powder consisting of finely-divided S in a more or less colloidal condition. Galena so treated gives with Cu greatly improved B rectification, due to formation of CuS a t the point of contact (cf. A., 1920, ii, 526). C. A. S.

C æ sium -oxygen-silver photo-electric cell.C. H. P r e s c o t t , jun., and M. J . K e l l y (Trans. Elcc troc hem. Soc., 1932, 62, 207—232).—The cell consists of a Ni wire anode and an oxidised Ag foil cathode on which Cs is deposited by heating a mixture of Cs2CrO,1, Cr20 3, and Al. The active cathode surface appears to he a film of free Cs of at. dimensions adsorbed on a m atrix of Cs20 and Ag containing free Cs and small amounts of Ag20 . The characteristics of the cell are described.

N ew photo-electric phenom enon. A. E t z r o d t (Physikal. Z., 1933, 24, 338—340).—The effect noted by M ajorana (A., 1932, 898, 1189) is no t primarily photo-electric, but is due to the effect of heat rays on the resistance of the conducting metal. A. J . M.

N ew photo-electric phenom enon. Q. M a jo r a n a (Physikal. Z., 1933, 34, 340).—A reply to E tzrodt (preceding abstract). I t is m aintained th a t the effect is photo-electric. A. J . M.

Photo-electric conductivity and absorption of Lenard phosphors in the red and infra-red spectral region. L. W e b e r (Ann. Physik, 1933, [v], 16, 821—843).—Photo-electric conductivity of a phosphor was produced by means of the superposition of a photo-electric effect on the centre (especially for short waves) and on the main constituent, e.g., CaS, for long waves. Two experimental methods indicate that absorption of the phosphor in the red and infrared consists of a superposition of absorption bands from the fundamental constituent and the selective absorption bands of the phosphorescence centres.

W. R. A.Dependence of breakdown strength on thick

ness for very thin layers of T a2Os. G. J u s t (Z. Physik, 1933, 82, 119—133).—The breakdown potential is proportional to layer thickness for layers between 15 and 250 m;x, the factor of proportionality being 2-0 X106 volts per cm. A. B. D. C.

Calculation of electric m om ents. G . A l l a r d (Compt. rend., 1933, 196, 1095—1097; cf. A ., 1931, 894).—The correctness of the method of calculating the electric moment of a mol. by vectorial addition of the partial moment of each of the linkings in the mol.,

considered as directed along th a t linking, is dem onstrated by wave mechanics. C. A. S.

D ielectric constant and conductivity of ionised gases. T. V. I o n e s c u and C. M i h u l (Ann. Sci. Univ. Jassy, 1933, 17, 78—110).—The dielectric const, and conductivity of ionised air have been measured by a resonance method a t wave-lengths of200—2090 cm. a t different accelerating potentials. The changes with wave-length exceed those an ticipated theoretically, and lead to the conclusion th a t ionised air possesses a characteristic frequency3-16 X107 independent of the electronic density. I t is suggested th a t some of the electrons are attached to mols. of gas, whilst the others are free, and th a t these two categories exert different influences on the variation of dielectric const, and conductivity with frequency. The large proportion of ionised gas in the higher s tra ta of the atm. may account for the great penetrating power of short electric waves.

J. W. S.D ielectric polarisation. VI, VII. E. C. E.

H u n t e r and J . R. P a r t in g t o n (J.C.S., 1933, 309— 313).—VI. The dipole moments ( X1018) of E t2N20 2, Bz2N20 2, and s-Me2S03 in CGH 6 are 1-5, 0-4, and 2-9, respectively, and th a t of N H 2N 0 2 in dioxan is 3-75. The parachors obtained for E t, P r , and «-Bu hypo- nitrites agree with the formula HO-NIN-OH for the acid. The constitutions of NH 2N 0 2 and N20 arc discussed.

VII. The dipole moments (x lO 18) of M cN02, E tN 0 2, and B uN 02 in C„H6 solution are 3-02, 3-19, and 3-29, respectively. Induction apparently occurs in the hydrocarbon chain, the effect of the N 0 2 group extending a t least as far as the th ird C atom. Since the val. for PhNO, is 3-9, the moment of N 0 2 is smaller in the aliphatic than in the aromatic series.

M; S. B.Dipole m om ents of som e benzene derivatives.

H. P o i .tz (Z. physikal. Chem., 1933, B, 20, 351— 356).—The measured dipole moments of the nitro- and iodo-toluenes agree with the vals. calc, from group moments by vectorial addition. W ith m- C6H 4I-N 02 the agreement is also good, bu t with the o- and ^-compounds there arc divergences, which largely disappear when Smallwood and Herzfeld’s method of calculation (A., 1930, 841) is used.

R. C.D ielectric constant of liquids. IX. Aqueous

solutions of carbam ide. G. D e v o t o (Gazzetta, 1933, 63, 119—121; cf. A., 1932, 794).—Vals. of e are given for solutions of carbamide a t 15°. O. J . W.

Dipole m om ents and structures of the organic azides and aliphatic diazo-com pounds. N. V.S id g w ic k , L. E. S u t t o n , and W. T h o m a s (J.C.S., 1933, 406—412).—The electrical dipole moments of the following compounds have been determined a t 25°: PhN3 l-SS^-CgHjMe-Ng l-96,i>-C6H4Cl-N3 0-33, P h 2CN2 1-42, (?j-C6H.1Me)2CN2 1-94, (p-C6H 4Cl)2CN2 0-62, Ph-NCO 2-23, and ^-C 6H 4Cl-NCO 0-82. "The negative end of the dipole is directed away from the C6H 6 ring. The data for the azides and diazo- compounds are in favour of the ring structure (I)R—N < a| rather than either of the open-chain

5 56 BRITISH CHEMICAL ABSTRACTS.— A.

structures (II) R —N = N —N or (III) R—N-^-N=N, but the possibility of a state of continuous and rapid oscillation between the forms (II) and (III) is not ruled out. The la tter view also receives some support from the val. of the heat of formation of the azides.

M. S: B.Nature of electrical conductivity of a-silver

sulphide. C. W a g n e r (Z. physikal. Chem., 1933,B, 21, 42—47).—Transport, conductivity, and diffusion data are m utually reconcilable if conduction is preponderatingjy electronic and the share of Ag ions in it is comparatively small. The proportion of electrolytic conduction has been approx. determined by e.m.f. measurements with the cell Pt(S)|Ag,S|Ag.

R. C.Conductivity of a-silver sulphide. II. W.

J o s t and'H . R ih ’ER (Z. physikal. Chem., 1933, B, 21, 48—52; cf. A., 1932, 446).—Transport experiments with Ag2S-Cu2S mixed crystals reveal certain anomalies, and Faraday’s law is not valid for conduction in Ag2S a t 220° a t high c.d. These observations are explained by W agner’s theory, of the formation of Ag2S films on Ag (this vol., 564) and of conduction in a-Ag2S (cf. preceding abstract). R . C.

D rude’s theory of optical activity. W . K u h n (Z. physikal. Chem., 1933, B, 20, 325—332).—The mol. model on which Drude based his theory is incapable of optical activity. He incorrectly eal: culated the interaction with the incident light.

R. C.Refractive index of a liquid. S. C. G l a d d e n

(Rev. Sci. Instr., 1933, [ii], 4, 231—232).—A simple watch-glass method was u sed ; results are given for H 20, PhMe, C6H 8, and CC14. : N. M. B.

Spectrochem istry of pyridone and pyridine derivatives. K . v o n A ijw e r s (Z. physikal. Chem., 1933, 164, 33— 43).—The sp. depression of C5H 5N is reduced by halogens, I having the most marked effect. By formation of active conjugations the groups -C 0 2R, -C O R , and —CHO cause exaltation, the effect increasing in th is order. The sp. exaltation of a CgH-N derivative with an activo conjugation is reduced by entrance of Cl into the nucleus. E t2 chelidamate has m.p. 125°. R. C.

M agnetic birefringence of liquid oxygen. P.L a in S (Compt.rend., 1933,1 9 6 ,1218—1220,1594).— The magnetic birefringence of 0 2 a t 90-6° abs. forX 5460 is—1-96 (that of PKN02 a t 17° being 1 ), giving Cm— •—■5-33 X 10~12. This is incompatible w ith the mol. 0 2 possessing symmetry of revolution around an axis uniting the centres of the constituent atoms unless this axis be a direction of low and not of high refractivity.

C, A. S.M agneto-optical d ispersion of organic liquids

in the u ltra-violet region of the spectrum . V. «-Propyl propionate, isobutyl acetate, ethyl acetoacetate, and ethyl oxalate. A. d e M, B e a n l a n d and E . J . E v a n s (Phil. Mag., 1933, [vii],15, 905—929; cf. A., 1932, 323).—The magnetooptical and ordinary dispersion of each liquid, measured in the visible and ultra-violet spectrum, are represented by formulae. The wave-length,s of the absorption bands of the four liquids are 0-1088,0-1080, 0-1089, and 0-1105 ¡x, and the calc. vals.

X 10~7 of e /m are 0-99, 1-015, 0-873, and 0-91 e.m.u., respectively. H . J. E.

M agnetic susceptib ilities of hydrochloric acid and lith ium chloride solutions. A. F. S c o tt andC. M. B l a ir , jun. (J. Physical Chem., 1933, 37, 475—482).—D ata for aq. HC1 agree with those of H ocart (A., 1929, 628), bu t not w ith those of Farqu- harson (A., 1931, 1118). The /-concn. curve is linear when c < 19%, after which x decreases suddenly, the data above 22% LiCl falling on a different straight line (cf. A., 1929, 247 ; 1932,678). D. R. D.

M agnetic susceptib ility of com plex com pounds. II. L‘; Ca m b i and L. S z eg ô (Ber., 1933, 6 6 , [B], 656—661 ; cf. A., 1932, 10).—The magnetic susceptibility of dithio-compoundsFe(CS2,N H R )3 [R = Me or E t] is th a t typical of Eem salts and follows the Weiss-Curie law. Compounds Fe(CS2-OR)3 [R = E t] and Fe(CS2R )3 [R = P h or p-CGH,Br] behave analogously to K 3Fe(GN)6, whereas those of the type Fe(CS2-NR'R " ) 3 [R '= R " = M e , E t, Pr, Bu, C5H n , CeH 13, C7H 15, C8H 17, C12H 25, or C1GH:!3] exhibit a susceptibility varying according to the temp, between the limits calc, for Fenr. The simultaneous existence of magnetic-isomeric forms is thus recognised, the equihbrium of which depends on the temp, and the more or less polar nature of the acid radical.

H .W .Param agnetic saturation of potassium chrom e

alum . C. J. G o r t e r , W. J. d e H a a s , and J. v a n d e n H a n d e l (Proc. K. Akad. Wetensch. Amsterdam, 1933, 36, 158—167).—Measurements have been made with a new apparatus down to 1-34° abs. and a field strength of 21 oersteds. The results agrée with the Bose-Stoner theory (A., 1927, 805 ; 1929,1371). Ko influence of orbital magnetism could be detected.

M. S. B.M agnetic behaviour of som e chrom ium com

pounds at low tem peratures. , C. J. G o r t e r , W. J. d e H a a s , and J. v a n d e n H a n d e r (Proc. K. Akad. Wetensch. Amsterdam, 1933, 36, 168—173).— The magnetic susceptibilities of samples of basic Cr2(S04)3, Cr20 3, and [CrCl2(H20)4]Cl,2H20 (I) have been determined between 14° and 290° abs. The val. for (I) alone follows approx. the theoretical law for Cr compounds^ The reasons for the deviations are discussed. M. S. B.

Param agnetic properties of crystals of the rare earths. II. H. A. K r a m e r s (Proc. K . Akad. Wetensch. Amsterdam, 1933, 36, 17—26; cf. this vol., 340).—The paramagnetism of a cryst. powder, particularly th a t of CcF3, and the paramagnetic rotation in the crystals, particularly in tysonite, are deduced mathematically. W. R. A.

Law of discontinuous distribution of ferrom agnetic Curie points. I. Influence of distance betw een m agnetic atom s. R. F o r r e r (J. Phys. Radium, 1933, [vii], 4 ,109—117 ; cf, A., 1932, 452).— A necessary condition for ferromagnetism is th a t the distance between magnetic atoms should lie between definite limits, the; “ effective distance.” The limits for Fe and Mn are 2-7—-3, and for Co and Ni 2-4—2-5 Â., the former applying also to Fe-M n combinations. Distances greater and less th an the effective


distance lead to variable paramagnetism and const, paramagnetism, respectively. N .M . B.

M agnetisation of ferrom agnetic crystals. F.B it t e r (Physical Rev., 1933, [n], 43, 655—660; cf. this vol., 2 1 2 ).—Photographs are given of models representing a function for the energy of a crystal as a function of the direction of magnetisation in the case of undistorted crystals of Ni and Fe, and Fe distorted by compression and extension. For the last-named, magnetisation curves are calc, and illustrated.

N. M. B.F errom agnetism of ferric oxide. H . S a c h s e

(Natunviss., 1933, 21, 299).—The conclusion of Danilow et al. (cf. this vol., 340) th a t trigonal Fe20 3 can exist in para- and ferro-magnetic forms according to heat treatm ent is contrary to the fact th a t ferromagnetic Fe20 3 is cubic and th a t when heated it affords the trigonal paramagnetic form. I t is usual to ascribe the ferromagnetism of trigonal Fe20 3 to the presence of small quantities of Fe30 4. A. J. M.

Interatom ic distances and ferrom agnetism .E. C. S t o n e r (Proc. Leeds Phil. Soc., 1933, 2, 391— 396).—The relative interaction energy J 0 associated with ferromagnetism of electron pairs in neighbouring atoms in Fe, Co, and Ni is calc. For Fe d JJd V is positive and for Ni negative,: indicating th a t interaction is a max. for R vals. between those of Co and Ni. R vals. (ratio of interat. distance to sum of effective radii) are calc, for a no. of unlike at. pairs with incomplete d shells and the results are discussed.

J . W. S.A tom ic m om ents in ferrom agnetic m eta ls and

alloys w ith non-ferrom agnetic elem ents. E. C.S t o n e r (Phil. Mag., 1933, [vii], 15, 1018—1034).— Theoretical. From Sadron’s results for alloys (A., 1932,112, 679) the decrease in magnetic moment of Ni (in Bohr units) per atom of alloyed Cu, Zn, Al, or S n is shown to equal the valency of the substituted atom.

H. J . E.Photo-stationary states of som e geom etrically

isom eric acids. A. R . O l s o n and F. L. H u d s o n (J. Arner. Chem. Soc., 1933, 55, 1410—1424).—Photo- stationary concns. of maleic and fumaric, citracdnic and mesaconic, and cis- and ira?us-cinnamic acids have been determined conductometrically in aq. solution a t 0—90° in monochromatic light of wavelengths 2536 and 3130 A. Photo-decomp, was negligible. Previous consideration of potential energy curves for photo-stationary states (A., 1931, 578) is extended to these cases in which the isomerides have different absorption coeffs. The importance of using monochromatic light is emphasised. J . G. A. G.

R egularities am ong hydrides. A. K r e b s (Z. Physik, 1933, 81, 776—780).—Nuclear separation plotted against a t. no. gives two smooth curves for hydrides between Li and F. A. B. D. C.

Three-electron link ing in chlorine dioxide.L. 0 . B r o c k w a y (Proc. N at. Acad. Sci., 1933, 19, 303—307).—Energies of possible electronic structures are discussed. Electron diffraction photographs of the gas lead to the val. l-58±0-03 A. for the Cl— 0 distance, in close agreement with the theoretical val.

1-57 A., and giving definite evidence for the three- electron linking. N. M. B.

Form and vibrational frequencies of the N O a m olecule. L. H a r r is , W. S. B e n e d i c t , and G. W . K in g (Nature, 1933,131, 621).—Critical (cf. this vol., 336). Evidence is advanced for the view th a t the atoms in the N 0 2 mol. form an obtuse-angled triangle.

L. S. T.Pseudo-atom s. A. E r l e n m e y e r and M. Leo

(Helv. Chim. Acta, 1932, 15, 1171— 1186).—Measurement of the mol. extinction coeff. of azo-dyes made by coupling (3-naphthol with diazotised p-amino- diphenyl ether, -diphenylmethane, and -benzophenone, respectively, reveals a close resemblance between the first two, which is not shared by the third. This supports the conception of •CH2- as pseudo-oxygen. Solubilities of the sulphate, chloride, bromide, and iodide of HgMe decrease in the order named ; the halides are sol. in aq. NH3, KCN, or Na2S20 3, and the sulphate forms no double salt with Al sulphate. The radical is therefore regarded as pseudo-silver and not, as formerly held, as a pseudo-alkali metal. The subject is discussed theoretically. F . L. U.

V olum es of alkyl groups and their orienting pow ers. R. J . W. L e F è v r e (Nature, 1933, 131, 655).—Reasons for expecting an orientation contrary to electronic theories for certain types of compound arc given and are supported by the nitration and halogénation of cyme ne. Me appears to possess agreater o-directive influence than Pr^. L. S. T.

O rientations of m olecules in the p-benzoquinone crystal. K . S. K r i s h n a n and S. B a n e r - j e e (Nature, 1933,131, 653—654; cf. th is vol., 682). —Magnetic susceptibility measurements show th a t the mol. planes in the ^-benzoquinone crystal are almost coincident w ith the (201) plane. Optical properties support this view. L. S. T.

M osaic structure of crysta ls. F. B l a n k (Physi- kal. Z., 1933, 34, 353—368).—A summary.

Specially suitable standard substance for the accurate determ inations of lattice constants by the D ebye-Scherrer m ethod. K. M o e l l e r (Natur- wiss., 1933, 21, 223).—T1C1 is recommended.

A. J . M.M ovem ent of liquid drops on grow ing crystals.

L. K o w a r s k i (Compt. rend., 1933,196, 1091— 1093; cf. A., 1932, 796).—When ^p-toluidine is slowly sublimed and deposited pn a razor edge, superfused droplets appear under certain temp, conditions on the crystals although the tem p, is below the m.p., indicating indirect contact between crystal and liquid. The appearances are figured. C. A. S.

Effect of etching on the relative intensities of the com ponents of double Laue spots obtained from a quartz crystal. M. Y. C olby and S. H a r r is (Physical Rev., 1933, [ii], 43, 562—563).— The investigations of Cork (cf. this vol., 213) are extended. * ■ N. M. B .

Interatom ic electrons in crystal la ttices. R. F o r r e r (Compt. rend., 1933, 196, 1097—1099; cf.A., 1932, 449, 452).—The author’s theory of effective contacts and interat. electronic orbits applies satis-

558 BRITISH CHEMICAL ABSTRACTS.----A.

faetorily to the Curie points of Fe20 3, Fe30 4 and 8 -Fe, and to the m.p. of Bi and Sb, indicating the presence of such electrons in a crystal lattice. C. A. S.

Influence of the in itial grain size on the final grain size of crystals during recrystallisation. R. A l e x a n d r u (Bull. Sci. Polytsch. Timisoara, 1933,4, 122— 129).—Samples of electrolytic Fe with grain sizes between 200 and 24 grains per sq. mm. were deformed by rolling, and allowed to recrystallise a t 650—750°. An initial grain size of approx. 157.grains per sq. mm. gave a max. grain size in the product.

H. J . E.Scattering of A-rays from powdered crystals.

G. E. M. J a ix n c e y and F. P e n n e l l (Physical Rev., 1933, [ii], 43, 505—515; cf. this vol., 115).—The “ average scattering ” from powdered crystals of KOI, CaS, NaF, and MgO was determined for a wide band of X-rays entering a wide window of an ionisation chamber (cf. Coven, A., 1932, 1072); the spectral distribution of the intensity was obtained by reflexion from rock-salt, and the scattered intensities were compared w ith those from paraffin. D ata are in good agreement with vals. calc, from the theory of diffuse scattering. N. M. B.

Dependence of crystallisation velocity on m olecular structure. M. E. K r a h l (J. Amer. Chem. Soc., 1933, 55, 1425—1429; cf. A., 1932, 450).—The linear velocity of crystallisation increases to a const, max. val. with increased supercooling. D ata for 32 substitution derivatives of C6H 6, CH4, C2H 8, C2H4, and C10H 8 support the hypothesis that, of a series of isomerides, the most symmetrical compound crystallises fastest. The velocity is independent of temp, and time of melting, the no. of remeltings, and the time of ageing of the melt. J . G. A. G.

N ickel carbide and its relation to other carbides of elem ents from scandium to nickel. B. J a c o b s o n and A. W e s t g r e n (Z. physikal. Chem., 1933, B, 20, 361—367).—In Ni3C, prepared by heating Ni a t 270—300° in CO, the Ni atoms have hexagonal closest spherical packing, and the un it cell has a 2-646 and c 4-329 A. The C atoms occupy the largest in terstices in the Ni lattice, and seem to form a definite array. Ni3C is probably so unstable th a t i t falls ou tside the scope of Hagg’s rule (A., 1931, 414), to which it would otherwise be an exception. R. C.

M etals and alloys. X II. N ature and structure of lattices of binary m agnesium com pounds.E. Z i n t l and E. H u s e m a n n (Z . physikal. Chem., 1933,B, 21, 138—155).—The following lattice consts. have been obtained : Mg3P„, a 12-03; Mg3As2, a 12-33; Mg3Sb2, a 4-573, c 7-22~9; Mg3Bi2, a 4-671' c 7-403 A. The lattices are co-ordinated and anti-isomorphous w ith those of oxides M20 3. R. C.

Crystal structure of the com pound LaAl4.A. R o s s i (Atti R . Accad. Lincei, 1933, [vi], 17, 182—-185; cf. A., 1932, 575).—Cleavage takes place along the (0 0 1 ) pinacoid faces, and the lattice distance between cleavage planes is 5-1 A. or an integral multiple thereof. The unit cell has a 13-2 A., c/a 0-77; cW . 3-69, d0b8. 3-86. 0 . J . W .

Crystal structure of yttrium vanadate. E.B r o c h (Z. physikal. Chem., 1933, B, 20, 345—350).—

Yt vanadate, prepared by heating Y t earths with NH 4V 03, has the space-group The unit cellhas a 7-126 andc 6-179 A., and contains 4 Y tV 0 4 mols.

R. C.P ossib le form of S i3Og groups in silicates.

T. I to (Proc. Imp. Acad. Tokyo, 1933, 9 , 53—55).—A chain arrangement of the Si and 0 in Si30 8 groups is suggested, and used to account for the cleavage properties of certain silicates with1 S i : 0 = 3 : 8 .

H. J . E.Crystal structure of cancrinite from Dodo,

Korea,. I . S. K 6 zu and K. T a k a n e (Proc. Imp. Acad. Tokyo, 1933, 9 , 56;—59; cf. this vol., 252).— The mineral crystal belongs to the hexagonal pyram idal hemihedral hemimorphic class [a 12-72, c 5-18 A.;1 mol. of 3(Na2A104-Si20 4),2CaC03 in un it ce ll; space-group C§]. H. J . E.

Crystal structure of cancrinite from Dodo,Korea. II. S. K 6 zu and K . T a k a n e (Proc. Imp. Acad. Tokyo, 1933, 9 , 105—108).—A model of the arrangement of atoms in the unit cell of the crystalis suggested. H. J . E.

Crystal structure of diaspore. K . T a k a n e (Proc, Imp. Acad. Tokyo, 1933, 9, 113— 116).—The unit cell has a 4-43, b 9-36, c 2-80 A., and contains2 mols. of H 2A120 4; space-group H . J . E.

Diaspore from Shokozan. B. Y o s h i k i (Proc. Imp. Acad. Tokyo, 1933, 9 , 109— 112).— The mineral forms prism atic crystals, of the approx. formula A120 3,H20 . Facial angles and optical properties are recorded. H. J . E.

Crystal structure of tenorite (cupric oxide). G. T u n e l l , E. P o s n j a k , and C. J . K s a n d a (J. W ashington Acad. Sci., 1933, 23, 195— 198).—The unit monoclinic cell has ag 4-66, b0 3-40, c0 5-09 A., all ¿ 0 -0 2 A . ; (3 99° 3 0 '± 30 '. C. W. G.

Crystal structure of o-iodobenzoic acid. H. P. K l u g (J. Amer. Chem. Soc., 1933, 55, 1430—1436).— The monoclinic crystals have 4 mols. in the unit cell, with a : b : c = 0-745 : 1 : 0-2863, (3=90° 43' 47", and a0 11-30, b0 15-17, c0 4-336 A .; space-group CV The closest distances of approach between I atoms of adjacent mols. are 3-99 and 4-34 A. J . G. A. G.

Crystal structure of anthracene. Quantitative X-ray investigation. J . M. R o b e r t s o n (Proc. R o y . Soc., 1933, A, 140, 79—98).—A detailed account of work already noted (this vol., 216).

L. L. B.Hi-defined fibre-diagram s of cellu lose deriv

atives. C. T r o g u s and K. H e s s (Z. physikal. Chem., 1933, B, 21, 7— 17).—The lack of sharpness in such diagrams is entirely a consequence of the conditions of separation of the cellulose derivative, and has no relation to the structure of the cellulose mol. Cellulose n itrate separates from solution in an org. solvent as a cryst. solvate, from which the normal ester lattice is formed by topochemical decomp. R . C.

X-Ray fibre-diagram of glucom annan. I.SA K U R A D A andK .H uT iN O (Z. p h y s ik a l . C h em ., 1933, B,21, 18—24).—K o n n ja k u m a n n a n (A., 1928, 873) e x is t s in a n a m o r p h o u s fo r m , so l. in H 20 , a n d a c r y s t . i n ® , fo r m . W h e n t h e g e l i s s t r e tc h e d , t h e m ic e lle s o r ie n t t h e m s e lv e s in th e d ir e c t io n o f s t r e t c h in g ; o r ie n ta t io n


has also been observed in dried films and frozen discs of the gel. On swelling in HjO the lattice of the cryst. form is distended, the effect being most marked across the fibre-axis. The unit cell contains three , hexose residues. R. C.

Alternations in the properties of A7-m ono- alkylm alonic acids. M alkin's view s concerning the alternation phenom ena. P. E. V e r k a d e and J . Co o p s (Proc. K. Akad. Wetensch. Amsterdam, 1933, 36, 76—87).—A crit. examination of X-ray work on alternation phenomena in crystals.

W. R. A.Structure of cyanuric triazide (C;!N ;i)(N3);1,

T. C. S u t t o n (Phil. Mag., 1933, [vii], 15, 1001— 1018). —(C3N 3)(N3)3 forms holohedral hexagonal prisms, term inated by a single hexagonal pyramid (axial ratio 0-684; d 1-71; a = b = c—8 -6 6 A., d 5-94 A.; 2 mols. in un it cell). A model of the unit cell has been constructed, which represents the observed properties of the crystal. The azide group is a short chain of3 N atoms, linked to the (C3N3) group by the middle N. C3N3 forms a hexagonal ring resembling CflH 6.

H. J . E.Effect of tension on the electrical resistance

of single antim ony crystals. (Miss) M. A l l e n (Physical Rev., 1933, [ii], 43, 569—576; cf. this vol., 217).—The adiabatic tension coeff. of resistance was determined for various orientations. The coeff.- oriehtation curves resemble those of Bi. The six coeffs. defining the resistance behaviour under deforming forces are found with and w ithout strain corrections.

N. M. B.Change in m agnetic induction under constant

field strength during cold w orking and the recovery on heating. G. T a m m a n n and H. J . R o c h a (Ann. Physik, 1933, [v], 16, 861—864).— Curves showing the recovery of magnetic induction of Fe, Ni, and mixed crystals of Fe and Ni are given.

W. R. A.Change of resistance of a sem i-conductor in

a m agnetic field. J. W. H a r d i n g (Proc. Roy. Soc., 1933, A, 140, 205—222).—Mathematical. W ilson’s theory of semi-conductors (ibid., 1931, A, 134, 277) gives the correct form of the curve required to explain the experimental results both for low and high fields, and the correct order of magnitude for the resistance change. L. L. B.

Effect of w ater on the p lasticity of rock-salt.A. Sm e k a l (Naturwiss., 1933, 21, 268).—The view is expressed th a t recent work on the taking up of H 20 by rock-salt does not necessarily establish a direct causal connexion between the entrance of H 20 and plasticity of the crystal. ” A. J . M.

Strength and elastic lim it of th in rods of rock- salt, single crystals of zinc, and g la sses . E.J e n c k e l (Z. Elektrochem., 1932, 38, 569—578).

M echanism of p lastic deform ation. A. V.S t e p a n o v (Z. Physik, 1933, 81, 560—564).—During plastic deformation the deformation energy is transformed into heat in the small zones bordering slip, and this localisation of heat causes a tem porary dissociation of the lattice around the zones.

A. B. D. C.

Polym orphic transform ations of iron at the A3 and A 4 poin ts. A. V. S v e t c h n ik o v (Rev. Met., 1932, 29, 583—587).-—Calculations based on lattice measurements show th a t the sp. vol. of Fe is decreased by 3-4% a t the A3 transform ation and increased by 0-9% a t the A4 point. On plotting the sp. vol. of a-, y-, and 8 -Fe against the temp, the vals. for a- and 8 -Fe lie almost on a straight line and those for y-Fe on a smooth curve concave to the vol. axis and meeting the a- 8 line a t the m.p. of Fe. I t is concluded therefore th a t a- and 8 -Fe are the same phase. A. R. P.

Superconductivity. L. B r il l o u i n (Compt. rend., 1933, 196, 1088— 1090).—Theoretical. Superconductivity can occur if a certain relation (illustrated by curves) holds between the energy and momentum of the electron in a crystal lattice. This is very improbable except in a face-centred cubic lattice in which the electrons are almost bound, as is the case in superconductors. The explanation is consistent with the effect of a magnetic field on superconductivity, and its appearance a t a definite temp. (cf. A., 1930, 1082). C. A. S.

Therm o-electric pow ers of nickel and n ickel- chrom ium alloys near the Curie point. A. W.F o s t e r (Proc. Leeds Phil. Soc., 1933, 2, 401—405).— The thermo-electric powers of Ni (99-5%) and Ni-Cr alloys (Ni 98-5, Cr 1%, and Ni, 97-5, Cr 2%) have been measured against Cu. The change in the sp. heat of electrons a t the Curie point is lowered very rapidly by the addition of Cr. J . W. S.

Theory of heat conduction at low tem peratures. W. K r o l l (Z. Physik, 1933, 81, 425— 427).

Effect of m agnetic field on the heat conductivity of gases. I. H. S e n f t l e b e n and J . P i e t z n e r (Ann. Physik, 1933, [v], 16, 907—929).—-The conductivity of paramagnetic gases is decreased by the application of a magnetic field. The effect is in dependent of field strength (J?) for the higher vals. of II, and alteration of temp, has no influence beyond a certain limit. The effect is independent of pressure for low pressures. A. J . M.

Jum p in the expansion coefficient of liquid helium in p a s s i n g the X -p o in t . W. H. K e e s o m (Proc. K. Akad. Wetensch. Amsterdam, 1933, 36, 147—152).—Theoretical. A relation is deduced between the inclination of the X -curve in the p -T diagram of He, the jum p in sp. heat, and the jum p in the expansion coeff. a t 2-19° abs. Aa= —0-0648. This val. is in harmony with the results of Onnes and Boks for the density of liquid He between 1-8° and 2-5° abs. M. S. B.

Specific heats of tungsten , m olybdenum , and copper. H. L. B r o n s o n , H. M. C h is h o l m , and S. M. D o c k e r t y (Canad. J . Res., 1933, 8 , 282— 303).—The vals. of Cp a t 0—500° for Cu, Mo, and W are determined by the method of mixture, and for Cu by electrical heating also. They are given by : Cu, C,p==0-09292+0-0000136T-452/T2; Mo, C'p= 0-06069+0-00001227—361/212; W, Gp=0-03199+ 0-0000032821—129/T2. H. A. P.

560 BRITISH CHEMCAL ABSTRACTS.----A.

Active oxides. LXIII. Specific heats oi crystalline zinc hydroxide and the calculation of the affinity between zinc oxide and w ater. G. F.H ü t t ig and H . M ô l d n e r (Z. anorg. Chem., 1933,211, 368— 378; cf., A., 1932, 1211).—The mean sp. heat of cryst. Zn(OH )2 a t —185° to 10-6°, —79° to 17-5°, and 16-9— 49-8° was measured. The total heat (U) and the affinity (A ) for the formation of stable cryst. Zn(OH), from ZnO and H^O were calc, for different vais, of T. The equilibrium diagram of the system ZnO-HaO was plotted, and the effect of activation of ZnO on the equilibrium discussed.

H. J . E.Heat of vaporisation of hydrogen fluoride.

J. H . S im o n s and J . W. B o u k n ig h t (J . Amer. Chem. Soc., 1933, 55, 1458— 1460).—The heat of vaporisation a t 748 mm. is 97-5 g.-cal. per g. The agreement with the val. calc, from v.-d. and v.-p. data shows th a t the heat of vaporisation does not involve the heat of dissociation of H 6F 6. J . G. A. G.

Calculation of specific heats of so lids. K.H o n n e f e l d e r (Z. phvsikal. Chem., 1933, B , 21, 53—64).—The sp. heats a t not too low temp, of Cu, Cd, Zn, W, Sn, Zn blende, fluorspar, quartz, rock- salt, and syl vine calc. from the Debye-Born-von Karm an theory agree more or less satisfactorily with the observed vais. Below about 15—25° abs., however, for W, Zn, and Cd the calc: vals.\are 70% below the observed vais. R. C.

Isom orphism and alternation in the m .p . of the norm al alcohols, acetates, brom ides, acids, and ethyl esters from C 10 to C 18. J . D. M e y e r andE. E. R e i d (J. Amer. Chem. Soc., 1933, 55, 1574— 1584).—The m.p. of w-decyl to n-octadecyl alcohol do not show detectable alternation, whilst those of the corresponding bromides do so. The m.p. of the acetates and the isomeric E t acylates both show alternation. Decided arrests are found in the curves of the alcohols from C12 to C18. Cetyl and octadecyl acetates exhibit two f.p. (a- and [3-forms), bu t hepta- decyl acetate shows only one ; below cetyl, the acetates of tho odd alcohols exhibit two f.p., whilst those of the even alcohols show one. Many of the acetates and E t acylates exhibit dimorphism.

H. B.T herm al properties of halides. V. Influence

of constitution on m .p ., b .p ., heats of vaporisation, and volum es of halides. W. F i s c h e r . V I. Vapour pressures and vapour densities of berylliu m and zirconium halides. 0 . R a h l f s and W. F i s c h e r (Z. anorg. Chem., 1933, 211, 321—348, 349— 367; cf. A., 1932, 1195).—V. The b.p. and m.p. of the halides in the main groups of the periodic table are plotted as functions of valency, and their b.p. as functions of the cation radius. Vais, for X/T^ and o/Ts are tabulated (x= heat of vaporisation a t abs. b.p., T n ;o—heat of sublimation a t the abs. sublimation temp., T s). The ratio of the mol. vol. a t m.p. and b.p. to the mol. vol. of cryst. state a t 0 ° abs. for the halides is plotted against T p/T ^ (2 V = abs. m.p.).

VI. The v.p., v.d., and m.p. of BeCl2, BeBr2, B ela, ZrCl4, ZrBr4, and Z rl4 were measured. BeCl2 and BeBr2 a t their b.p. are approx. 50% associated to Be2Cl4 and Be2Br4. The Zr compounds are

unimol. Z rlj dissociates a t 1000° in to Z rl2 and I,. Be halides and ZrCl4 a ttack S i02, forming SiCl4. No oxychloride of Si is formed from SiO, and SiCl. a t 630°. ••H. J . E.

E bulliom etric and tonom etric researches on chem ically pure liquids. I. A. Z m a c z y n s k i (Rocz. Chem., 1933, 13, 181—192).—'The vals. of A , B, and C in the equation t=±A-\-Btlw -\-Ct\lti) (t is the b.p. of the liquid, and tlU0 th a t of H 20) have been determined a t 330—2000 mm. pressure, for EtBr, CS2, COMe2, CHCI3, CgH 0, PhMe, PliCl, and PhBr, using a differential ebullioscope fitted with a rectifying column. R . T.

Revision of isotherm m easurem ents of Kohn- stam m and W alstra. A. M ic h e l s and A. J . J . G e r v e r (Ann. Physik, 1933, [v], 16, 745—750; cf. Kohnstamm and W alstra, A., 1914, ii, 800).—A table of jpv vals. for EL, is given. W. R. A.

Vapour pressure of liquid and solid carbon dioxides. C. H. M e y e r s and M . S. v a n D u s e n (Bur. Stand. J . Res., 1933, 10, 381—412).—The v.p. of C02 has been redetermined over the temp, range —56-60° to 31-0°. Empirical equations which represent the v.p. for the liquid and solid states, respectively, have been developed. The results accord with those of other investigators. J . W. S.

P hysical properties of d ivinyl ether. F. T.M i l e s and A. W. C. M e n z ie s (J. Physical Chem., 1933, 37, 425—430).— Over the range —30° to +60°, the v.p. of (CH3:CH)20 is given by log ;pmm. = 21-73592 —2085-11/2’—4-81530 log T. Between 0° and 25°, ¿=0-79601—l-1.4582ix 10-3-2-5706<2x l0 -8± 2 x 10'"4. The orthobaric v.d. is 0 002994 a t the b.p., 28-35°±0-04. The laten t heat of vaporisation a t the b.p. is S9-4 g.-cal. per g. T routon’s const, is 20-8 and Hildebrand’s is 14-2 a t —21°. D . R. D .

Vapour pressure of tra>is-di-iodoethylene.L . F . B r o a d w a y and R. G . J . F r a s e r (J.C.S., 1933, 429—430).—The v.p. has been determined between —S° and 2 0 ° by the mol. effusion method and m ay be expressed by the equation log p mm = —2130/T+5-86. The calc, laten t heat of sublimation is 9720 g.-cal. per mol. M. S. B .

Equation of state of real fluid. S. C. B r a d f o r d (Engineering, 1933, 135, 439).—Work previously reported (cf. A., 1930, 1119) leads to a new definition of te m p .: the mean kinetic energy of a particle of a perfect gas, or the temp, of a therm om eter filled with a perfect gas in equilibrium with the substance under observation. From this definition, with the help ofX, the ratio of the most probable particle speed in the liquid to th a t in a perfect gas, and A an association factor, the kinetic relations and an equation of state for a real fluid, in agreement with experimental data, are deduced. N. M. B . '

Values of b and y '« for the alkali m etals, halogens, and m olten alkali halides. D eterm ination of the critical tem perature and pressure from various independent data. J . J . v a n L a a r (Chem. Weekblad, 1933, 30, 294—304).—The calculations (from published data) are given in detail.

H. F . G.


V iscosity , therm al conductivity, and diffusion in gaseous m ixtu res. XXII. Tem perature coefficient of m olecular d iam eter and its relation to M axw ell diam eter, la ttice size , and nuclear separation. M. T r a u t z (Ann. Physik, 1933, [v],16, 751—767).—Vais, of mol. diameters deduced from physical data are compared and the temp, coeff. is derived for a large no. of gases and vapours.

W. R. A.D em onstration apparatus for liquefaction of

helium . F. S im o n and J . E . A i il b e r g (Z. Physik, 1933,81,816—820). A . B. D. C.

P ossib ility of attain ing any low tem perature.F. S im o n (Z. Physik, 1933, 81, 824— 831, 838—839).

A. B. D. G.A ttainm ent of low est tem perature by com

pression of liquid helium . W . M e i s s n e r (Z. Physik, 1933, 81, 832—837).—Compression cools liquid H e; the possibility of attaining lower temp, is indicated. A. B. D. C.

T herm odynam ic functions of hydrocarbon gases from spectroscopic data. L. S. K a s s e l (J. Amer. Chem. Soc., 1933, 55, 1351— 1362).— Approx. methods of evaluating the free energies and entropies of polyat. mols. are applied to CH4, C2H ,, and C2H 2 between 250° and 5000° abs. J . G. A. G.

D eterm ination of the constant a of the Ste- fan-B oltzm ann radiation law . C. M ü l l e r (Z . Physik, 1933, 82, 1—36).—An accurate determ ination of a gave the val. 5-774(±0-02) x 10~12 w a ttx cm.-2x degree-4. A. B. D. C.

V iscosity, heat conductivity, and diffusion of gaseous m ixtu res. XXIII. A bsolute E n sk og- Chapman diam eter of gas. m olecules and their tem perature coefficients. M. T r a u t z (Aim. Physik, 1933, [v], 16, 865—886; cf. A., 1932, 14).— The calculation of mol. diameters from viscosity is discussed, with special reference to the various types of mol. models. The temp, coeffs. of the diameters are calc., and the physical interpretation of these numbers is discussed. A. J . M.

D eterm ination of com position of certain azeotropic m ix tu res, u sin g a universal fractional distillation apparatus. I . R a b c e w ic z -Z u b k o w s k i (Rocz. Chem., 1933, 13, 193—200).—A fractionating apparatus' adapted for use a t increased or reduced pressures is described. The composition of the azeotropes of E tO H and C6H 6 varies with the pressure: b.p. 0°, 4-5%; b.p. 35-5°, 12% ; b.p. 76-5°, 21% ;b.p. 160°, 45% EtOH . A m ixture of E tO H and C6Hg can hence be separated by successive distillation at high and low pressures. The H 20 content of the azeotrope of E t20 and H 20 of b.p. 34-15° is 1 -3 %, and of b.p. 114° 4-5%; by distillation a t 114° (11 atm.) H 20 is distilled off in the azeotropes, leaving anhyd. E t20 . The composition of E t0 H -H 20 azeotropes does not vary with pressure; for this reason Lewis’ method for the prep, of anhyd. E tO H by fractionation under pressure is no t possible. R . T.

Azeotropic hydrobrom ic acid solutions at pressures of 100—1200 m m . W. D. B o n n e r , L. G . B o n n e r , and F. J . G u r n e y : (J. Amer. Chem.

Soc., 1933, 55, 1406—1409).—The composition, d, v.p., and b.p. of “ const.-boiling ” solutions are recorded. J . G. A. G.

H eat of m ix in g of norm al liqu ids. V. K i r e j e v (Z. anorg. Chem., 1933, 211, 423-426).—An expression for the heat of mixing, developed from th a t of van Laar and Lorenz (A., 1925, ii, 870), agrees with experimental vals. for CS2-C GH c and CS2- Me20 mixtures. H. J . E.

S ystem w ater-phenol. III. E lectrical conductivities. O. R. H o w e l l and C. H a n d f o r d (Trans. Faraday Soc., 1933,29, 640—653).—Electrical conductivities of mixtures of PhOH and H 20 have been determined a t 20—70°. The form of the conductivity (ic)-concn. curves, which show a max. is attribu ted to the formation of the compound, (PhOH2’)(OH') and its subsequent dissociation. The acidity of dil. aq. PhOH affords evidence for the alternative dissociation: P h 0 H + H 20 = ^ :P h 0 '- |-OH3‘. The K-temp. curve for each concn. is smooth and is represented by the equation k,.—<c20.-|- a(t—20°)-:j-(3(£—20°)2. The curves obtained by p lo tting a and ß against the concn. exhibit an inflexion for the equimolar mixture. M. S. B.

Rate of diffusion of m eta ls in gold and silver.W. J o s t (Z. physikal. Chem., 1933, B, 21,158-—160).— The rates of diffusion of Pd, P t, and Cu in An and of Pd in Ag have been determined over a wide temp, range by an X -ray method. R. C.

D iffusion of m ercury on rolled tin foils. F. W.S p i e r s (Phil. Mag., 1933, [vii], 15, 1048— 1061; cf.A., 1932, 906).—From X -ray analysis, the amalgam has a hexagonal structure (a 3-23, c 3-00 Ä .; 1 atom in unit cell). I t is shown by resistance measurements to be a secondary solid solution. H. J . E.

Are liquid sod ium am algam s colloidal? H. E.B e n t (J. Physical Chem., 1933,37,431— 436).—Polemical against Paranjpe and Joshi (this vol., 118) Liquid N a amalgams are true solutions with properties independent of the mode of prep. D. R. D.

E lastic properties of single crysta ls of s ilv er- gold alloys. H. R ö hl (Ann. Physik, 1933, [v], 16, 887—906).—The Young’s and torsion moduli of single crystals of the mixed crystal system Ag-Au have been determined. The elastic properties of the system are quite as anisotropic as those of the pure components. The system does not obey the mixture rule for any given direction. The velocity of sound, and its dependence on direction, have been calc, for Au and Ag. A. J . M.

R elation betw een m ean atom ic volum e and com position in copper-zinc alloys. E. A. O w e n and L. P i c k u p (Proc. Roy. Soc., 1933, A, 140, 179— 191).—-In the Cu-Zn series the mean at. vol. of both phases present in a mixed region remains const., bu t the const, at. vol. of one phase depends on the second phase. The increase in at. vol. when a Cu atom is replaced by a Zn atom is attributed to the fact th a t the Zn atom is no t “ spherical ” and packs differently in the various phases. A detailed analysis is made of the e- and -/¡-phases. For pure Zn a=.2*659 A.., c =1-856 a t room temp. L. L . B.


Variation of m ean atom ic volum e w ith tem perature in copper-zinc alloys, w ith observations on the ^-transform ation. E. A. O w e n and L. P i c k u p (Proc. Roy. Soc., 1933, A, 140, 191—204).— The changes in mean at. vol. with temp. (350— 800°), for the a-, (3-, and y-phases of Cu-Zn alloys, have been studied by X -ray precision analysis. The mean at. vol. of both the constituents in a mixed region shows a change (probably owing to a change in solid solubility), whereas the mean at. vol. in the pure phases remains const. Both the p- and y-phases in the P + y region show a min. mean at. vol. a t about 500°, whilst the a-phase in the a + p region shows a max. val. a t the same temp. The P-transformation which occurs a t about 470° is discussed in the light of the experimental data. L. L. B.

A-Ray analysis of iron -tin alloys. W. P.E h r e t and A. F. W e s t g r e n (J. Amer. Chem. Soc., 1933, 55, 1339—1351).—The solubility of Sn in a-Fe increases from 9-8% a t 680° to 18-8% a t 900°, and the edge of the body-centred a-Fe lattice increases linearly with concn. of Sn from 2-896 to 2-925 A. The cell consts. of the hexagonal p-phase are ax 5-292, a , 4-440, and the unit cell contains three FeSn mols. The p'-phase is present in alloys containing27—59% Sn annealed a t 680°, whilst the p"-phase in alloys containing 27—48% Sn and annealed a t 860° is hexagonal and contains two Fe2Sn per unit cell for which a 1=5-449 A., a2 =4-353 A. A y-phase is present in certain alloys quenched from 750—900°. The un it cell of the FeSn2 phase contains 1 2 atoms, and is hexagonal, with a 1 5-317, a3 9-236. The results are discussed in relation to previous work (B., 1931,1053).

J . G. A. G.M etals and alloys. X . Valency electron rule

and atom ic radii of base m eta ls in alloys. E. Z i n t l and G. B r a u e r . XI. Lattice structure of N aln and deform ation of atom s in alloys. E.Z in t l and S. N e u m a y r (Z. physikal. Chem., 1933,B, 20, 245—271, 272—275).—X. X -Ray examination of binary alloys of alkali and alkaline-earth metals with other metals in equi-at. proportions has shown the existence of numerous phases with the structure of p-brass and NaTl. The no. of valency electrons per atom varies, however, from 1 to 2 i , so th a t the rule th a t in body-centred alloy phases there are always three valency electrons for each two atoms is not valid for alloys of very electronegative metals. In such alloys the interat. distance is < corresponds with additivity, an effect which is ascribed to diminution in the at. radius of the base component. I t is inferred th a t the concn. of valency electrons does not determine the structure if the components of an alloy differ greatly in polari’sability. The miscibility of oonc. Li alloys has been investigated.

X I. The alloy N aln has the NaTl structure with a 7-297 A. In this the radii of Na and T 1 are both1-58 A. The at. radii deduced from NaTl structures show th a t the contraction of base metals in alloys is the greater the larger are their atoms and the smaller the atoms of the more electropositive component. R. C.

Non-substituted m ixed crysta ls of iron. E.(Scheil JZ . anorg. Chem., 1933, 211, 249—256).—

Crystals of a- or y-iron in which atoms such as C or N can be inserted in virtue of their small at. radius are chemically reactive a t a temp. 200—300° lower than are those in which Fe atoms are substituted. Spacial considerations lead to the conclusion, supported by observation, th a t y-iron will accommodate a larger proportion of C or N than will a-iron, bu t th a t the foreign atoms will become mobile a t a lower temp, in the latter. F. L. U.

F orm ation of layers in the sy stem s alkali h ydroxide-w ater-am m onia. E. W e it z and U. H e u b a u m (Ber., 1933, 6 6 , [5], 790—792).—The behaviour of aq. NaOH or KOH towards NH 3 under high pressure shows th a t the solubility of each substance in H ,0 is depressed by the presence of the other. H. W .

P hysica l properties of heterogeneous ternary m ixtu res. P. M . M o n v a l (J. Chim. pliys:, 1933, 30, 195—197; cf. A., 1928, 1084).—A reply to Bruii (A., 1932, 1091). F. L. U.

Solubility of silver in m ercury. II. R. E.D e r ig h t (J. Physical Chem., 1933, 37, 405—416).— Between 20° and 80°, the solubility of Ag in Hg is given by log AT= —1105-8/2'-{-0-5894. D. R. D.

T ransform ations of sa lts of tervalent m eta ls in solution. V. Solubility of chrom ic sulphate and of potassium and sod ium chrom e a lu m s . C. M o n t e m a r t in i and E. V e r n a z z a (L’lnd . Chimiea, 1933, 8 , 445—446; cf. A., 1932, 708, 827, 912, 996).—Saturated aq. solutions a t 18° contain K 2S 04,Cr,(S04)3,24H20 28-2, Cr„(S04)3,17H20 84-8, and Na2S 04,Cr?(S04)3,24H20 94-8%. The % of violet fraction is 51-75, 51-68, and 51-70, respectively. Thus the equilibrium violet—green form of Cr2(S04)3 is not affected by alkali sulphate, and is almost independent of the concn. T. H. P.

D istribution of radium in fractional precipitation of radiferous barium chloride. (M m e . ) B. E. M a r q u e s (Compt. rend., 1933, 196, 1309—1311).— Steadily increasing proportions of the Ba and Ra contained in equal amounts of a BaCl2+ R aC l2 solution were pptd. by aq. IIC1. The proportion of R a which is pptd. decreases steadily as the total am ount of the ppt. increases. C. A. S.

Influence of tem perature and pressure on adsorption of hydrogen by nickel. II. J. S m it- t e n b e r g (Rec. trav. chim., 1933, 52, 339—351; cf. this vol., 346).—Two further preps, of Ni have been used in the determ ination of adsorption isotherm s a t 18°, 122°, 208°, and 300°, and of isobars at 760 mm. The adsorption capacity of Ni is diminished not only by rise in the temp, of reduction, bu t also by calcination of the oxide prior to reduction. Adsorption of H 2 by Ni is a complex process consisting of a t least two superposed phenomena which, for the isotherm a t 300°, can be satisfactorily expressed by a combination of two formulaj. F . L. U.

E nergy exchange at p latinum -hydrogen interface. H. H. R o w l e y and K. F. B o n h o e f f e r (Z. physikal. Chem., 1933, B , 21, 84—92).—The coeff. of accommodation, a, of H 2 on bright P t is 0-22 a t room temp, and increases as the temp, falls, reaching at 110° abs. the val. 0-37; the coeff. is independent of


the pressure between 0-03 and 0-3 mm. This high val. of a is ascribed to reflexion occurring on an adsorbed film of II, and the negative temp. eoefT. is possibly due to a for rotational energy having a large negative temp, coeff. For an approx. 50% mixture of ortho- and para-H 2 a a t 140° abs. is about 10% < and a t 180° about 15% < for ordinary H2, which shows th a t a is smaller for rotational than for translational energy, a is considerably increased by the presence of adsorbed 0 on the P t. R. 0.

A dsorption of sulphur dioxide and carbon dioxide at sm a ll equilibrium pressures. A. M a g n u s and H. G i e b e n h a i n (Z. physikal. Chem., 1933, 1 6 4 , 209—222).—Various forms of wood charcoal have been used as adsorbents and measurements made w ith S 0 2 a t 0—300° and C 02 a t 0° and pressures of about 0-001—5 mm. None of the isotherms for S02 has the double point of inflexion reported by Polanyi and Welke (A., 1928, 580) for Aussig C, and the differential heat of adsorption calc, from the isotherms diminishes continuously with the amount adsorbed, w ithout passing through a min. a t low pressures. For C 02 m any of the isotherms are markedly concave to the pressure axis a t low pressures, hut become linear a t higher pressures, which is taken to mean th a t the active centres of highest adsorption potential are first occupied, after which only physical adsorption occurs, corresponding with the linear part of the isotherms. By treatm ent of the C with small amounts of 0 2 a t 380:—700° p art of the active centres could be burned away. For a given form of C the isotherm for CO„ a t 0° is very similar to th a t for S 0 2 a t 100°. R. C.

Gas adsorption on electrically conducting films during their condensation from m olecular rays. M. .C. J o h n s o n and T. V. S t a r k e y (Proc. Roy. Soc., 1933, A, 140, 126—140).—A const, stream of Hg vapour, with or w ithout the addition of H2, 0 2, A, C 02, or various ionised gases, is condensed into an electrically conducting film on a target cooled w ith liquid air. The curves obtained are in accord with microscopical observations relating to the growth of loosely-aggregated structures from Hg vapour in presence of a gas. L. L. B.

Influence of com bined oxygen on the adsorption of vapours by porous so lids. I. L. J . B u r - Rage (J. Physical Chem., 1933,3 7 , 505—510).—Charcoal which had been heated in vac. a t 800° for 80 hr. still contained traces of CO and C 02. A method for removing these by flushing with CC1, is described. With this 0-free 0, reversible isothermals, consisting of a series of rectangular steps, were obtained for CC14 by the static method, equilibrium being instantaneous. D. R. D.

Desorption of u-butylam ine from charcoal. H. J . P h e l p s and R. B. V a l l en d e r (Biochem. J ., 1933, 2 7 , 435—441).—Desorption (I) of NH 2Bua from charcoal in H 20 or an equi-vol. m ixture of H 20 and EtO H occurs as a two-stage process. In the primary rapid stage up to 50% (I) occurs within 10 min. The second stage is slow and is inhibited a t 0°.

H. D.Mode of retention of sulphur by carbon. J . P.

W i b a u t (Z . a n o r g . Chem., 1 9 3 3 , 2 1 1 , 3 9 8 —4 0 0 : p p

cf. this vol., 221).—P art of the S adsorbed by C can be removed (as CS2) only by heating to 1000°. A chemisorption, resembling th a t of 0 2 by C, is suggested. H. J . E.

A dsorption of Congo-red by an im al charcoal.G. R ossi and A. M a r e s c o t t i (Annali Chim. Appl., 1933, 23, 62—66).—The degree of dispersion of Congo-red solutions varies appreciably w ith the dilution. The fact th a t the adsorption by animal charcoal in solutions of different concn. does not follow Boedecker’s law is probably due to this change in the degree of dispersion. T. H. P.

Adsorption of electrolytes from neutral so lu tions by calcium carbonate. J . J e b a v y (Z. Zuckerind. Czechoslov., 1933, 57, 264—268, 269— 272).—The adsorption of CaS04, Ca citrate, and Ca aspartate from neutral solution by twelve different varieties of calcite and qf aragonite has been-determined; the concns. of the solutions used correspond with the concns. of the salts in diffusion juice. The adsorption falls in the o rder: citrate, sulphate, aspartate, and for all forms of calcite is > for aragonite; i t varies with the temp, and method of prep, of the adsorbent. The presence of free CaO increases the adsorption. H. F . G.

Inner adsorption in crystalline sa lts . VI.D. B a l a r e v (Kolloid-Beih., 1933, 37, 324—341; cf. this vol., 1 2 2 ).—The theory of the mosaic structure of crystals and the consequent inner adsorption at the surface of the elementary crystal blocks has been applied to the formation of solid solutions. The elementary blocks of colloidal dimensions are considered to be slightly disoriented w ith respect to one another, so th a t the unoriented ions or atoms constitu te variable linkings between the individual blocks. The following main types are distinguished : (a)typical mixed crystals (e.<;.,KCl-KBr), (b) typical solid solutions [e.g., C0H ri and I), (c) typicalInner adsorption (e.g., K 2S04 and H 20), bu t it is emphasised th a t progression from one type to another is continuous.

E. S. H.Influence of foreign substances on the adsorp

tion of liquid by n on-sw elling pow ders. H.F re u n d lic h , O. E n s lin , and G. L tn d au (Kolloid- Beih., 1933, 37, 242—280).—The max. amount of H 20 , lv„, taken up by homodisperse powders of different chemical nature (SiO,, A120 3, Fe20 3, MgO, T i0 2, As2S3, PbS, ZnS, FeSo, and Cu2S,Fe2S3) is almost const., although differences appear when the powder is heterodisperse or when the particles are very small or rough. W ith homodisperse S i02, increases rapidly as the particle size is increased from 8 to 45 ¡j., but varies little further up to 150 (x. A marked increase of wm is observed in A120 3 particles between 7 and 32 ¡x. Similar results are obtained when the hydrophilic, S i02 particles are made hydrophobic by adsorption of dyes and when the hydrophobic As2S3 particles are made hydrophilic by adsorption of gelatin or casein. Addition of 0-lJli-BaCl2 does not change wm unless the particle size is > 30 p., when wm is increased and a looser packing is observed. The rate of imbibition of H20 by S i0 2 is high, bu t is decreased greatly by adding small amounts of a basic, strongly adsorbable dye (crystal-violet); the acid dye Me-


orange has no effect. The velocity of imbibition of H 20 by hydrophobic As2S3is correspondingly increased by adsorption of gelatin, casein, e tc .; ovalbumin has little effect. E. S. H.

Adsorption of radon by silica gel. R . L i v i n g s t o n and L . H. R e y e r s o n (J. Physical Chem., 1933, 37, 534—535).—The distribution eoeff. for Rn between S i02 gel containing 5% H 20 and free space (Rn per g. of gel/Rn per c.c. of space) is 144 (cf. A., 1932, 803). The adsorptive capacity of Pyrex glass is much < th a t of S i0 2 gel. D. R. D.

A dsorption by colloidal clay. E. U n g e r e r (Z. Pflanz. Diing., 1933, 29, A, 38—50).—Adsorption of basic dyes by clay colloids ( < 0 -2 ¡¿) conforms to the general adsorption isotherm. The adsorption of methylene-blue (and of cinchonine) is related to the adsorption capacity determined by the BaCl2 method. Sparingly sol. compounds (e.g. B aS04, CaC03; Li, Ba, Ca, and Mg phosphates) are decomposed by the clay in aq. suspension, liberating free anions. The bearing of this on the mobility of anions in soil and on the formation of alkali soils is discussed. A. G. P.

H ygroscopic m oisture of cellu lose. X I. M echa n ism of adsorption of w ater vapour by cellu lose.S. O g u r i (J. Soc. Chem. Ind., Japan, 1933, 36, 67b). —The absorption of H20 by cotton cellulose is not an effect of simple dissolution and chemical reaction. From the therm al viewpoint there is scarcely any difference between absorption and condensation of H 20 vapour in the case of standard cotton cellulose. Theories of the mechanism of H 20 absorption are discussed. I t is probable th a t this is due to the attraction of OH groups in the mol. Almost half the OH groups in the cellulose mol. arc unsuitably oriented to a ttrac t H 20 . V. E. Y.

A dsorption of various am m onium com pounds in so ils. K . N e i i r i n g and A. K e l l e r (Kolloid- Beih., 1933, 37, 293—323).—The adsorption of NH4‘ by soils is in accordance w ith the Freundlich isotherm, and the amount adsorbed is influenced by the lyotropic character of the anion present. The adsorbent power of acid soils is increased when the H* is replaced by Ca” , and particularly by N a'. Adsorption of NH4* by acid soils is very marked in (NH4)2H P 0 4 and (NH4)2C20 4, but is reduced considerably when CaC03 is added to the soil. In acid soils the effects of concn. and nature of the anion are more marked th an in neutral soils. E. S. H.

M echanism of precipitation p rocesses. XII. P rocesses in w hich cadm ium sa lts participate.Z. K a r a o g l a n o v and B. S a g o r t s c h e v (Z. anorg. Chem., 1933, 211, 227—232; cf. A., 1932, 584).— CdS pptd. from CdBr2 by Na2S contains a proportion of CdBi'2 which increases with time, and depends on the concn. of CdBr2, bu t not on the presence of acids. W ith K 2C03, a much smaller proportion of precipitant is retained. CdCl, behaves similarly. When CdS04 is used, this is also contained in the ppt. with Na2S or K 2C03, bu t the am ount does no t change w ith time. Na,C20 4 in all cases gives a ppt. free from secondary products. The results are referred to the fact th a t CdS is the least and CdC20 4 the m ost sol. of the ppts. examined. ” F. L. IJ.

Co-precipitation. IV. Co-precipitation of alkali ions w ith calcium oxalate. A dsorbent properties of the latter. V. Co-precipitation of anions w ith calcium oxalate. I. M. K o l t h o f e and E. B. S a n d e l l (J. Physical Chem., 1933, 37, 443—458, 459—473).—The order of adsorption of alkali metal ions by CaC20 4,H20 (I) is the same as th a t for co-pptn., viz., N a > K > N H 4. These effects are diminished by an excess of Ca” in the solution and increased by excess of C20 4", except in very conc. solutions, where irregularities are observed. Under the conditions used in the analytical pptn. of (I), contamination is slight. The purest (I) is obtained by pptn. a t room temp, from fairly conc. solutions a t

4—6, the mixture being then heated for 24 hr. on the steam-bath. Co-pptn. decreases with rising temp. The am ount of alkali metal co-pptd. is an exponential function of its concn.

V. The order of co-pptn. of anions w ith (I) is : I 0 3'> C r0 4" = S 0 4" > B r 0 3'> C r = B r '= r . OH' is also strongly adsorbed by, and co-pptd. with, (I), recrystallisation failing to remove i t unless acid is present. The amount of I 0 3', C r04", S 04", and OH' pptd. m ay be sufficient to affect analytical work, whereas only traces of Cl', B r', or I ' are pptd. under the conditions most favourable to co-pptn. Co-pptn. is favoured by high temp, and excess of Ca” , and suppressed by excess of C20 4". . In the case of I 0 3', which has been investigated in most detail, the amount co-pptd. is an exponential function of [I0 3'].

D. R. D.Interrelation of electrokinetic behaviour and

cation exchange of iron phosphate. J. B. H e s t e r (J. Amer. Chem. Soc., 1933, 55, 1442—1445).—The cation exchange capacity of Fe phosphate pptd. a t Pu 3—9 is a min. for p a 4-4. Thus high base exchange accompanies high electrokinetic potential of the colloid. J . G. A. G.

Theory of form ation of surface film s on m etals.C. W a g n e r (Z. physikal. Chem., 1933, B, 21, 25— 41).—The ra te of formation of surface films on metals by reaction with 0 2, S, or halogens is in m any instances determined by the rate of diffusion in the film. Assuming th a t diffusion occurs almost exclusively by migration of ions and electrons, the rate of formation of the film m ay be calc, from affinity, conductivity, and transport nos. of ions and electrons. The results for the systems Ag-S and C u-0 agree with experiment. In the system Ag-halogen the mechanism is possibly similar. R. C.

Structure of unim olecular film s. I. Surface potentials of film s of long-chain com pounds.R. J . F o s b i n d e r and A. E. L e s s ig (J . Franklin Inst., 1933, 215, 425—433).—The method of Schulman and Rideal (A., 1931, 299) was modified, and their results with m yristic and palmitic acids were confirmed. A liquid condensed film of stearolactone has a limiting mol. area of 31 sq. A., agreeing with the val. calc, for the lactone ring. H. J . E.

Structure of surface film s. XVII. y-Hydr- oxystearic acid and its lactone. N . K . A d a m (Proc. Roy. Soc., 1933, A, 140, 223—226).—y-Hydroxystearolactone forms a condensed film of area about 29 sq. A. a t zero compression on H 20 , dil. acid,


and dil. alkali. On iV-NaOH the lactone films undergo rapid expansion, due to hydrolysis to the acid. The acid forms a liquid expanded film a t arid above room temp, on slightly acid solutions, and a condensed film near 0°. The OH group has a tendency to approach the C02H group and the underlying H 30 . " L. L. B.

Behaviour of surface film s of unsaturated com pounds. A. H . H u g h e s (J.C.S., 1933, 338—344).— Unimol. films of long-chain aliphatic compounds on aq. solutions have been examined by surface pressure and surface potential methods. In the series oleic, petroselic, and A'M.sooleic acids, the dipole system of the double linking has a marked adhesion for the H 20 surface as compared •with a saturated hydrocarbon chain. Proxim ity to a C 02H group greatly increases the dipole moment of a double linking. A double linking in a five-membered ring, as in chaulmoogric acid, also has a dipole moment > th a t of a double linking, in a straight chain. A triple linking has a dipole moment > th a t of a double linking, thus causing greater adhesion to the H ,0 surface. The behaviour of a conjugated double-linking system has been studied in a- and (3-elseostearic acid and their additive compounds with maleic anhydride. Both acids undergo autoxidation in the unimol. film, but this is completely inhibited by the presence of 0 -1 2 % of quinol in the underlying solution. M. S. B.

M olecular phenom ena at an oil-w ater surface : application to testing [lubricating oils], J . J .Tr il l a t and L. L e p r i n c e -R i n g u e t (Coinpt. rend., 1933, 196, 1214— 1216).—The change of the intcr- facial tension produced by the addition of a foreign substance depends on the electric moment of the latter. In the case of a paralfin-H 20 surface cyclo- hexanol produces a marked decrease in interfacial tension, whereas cycfohexane has no effect; th is is due to orientation of the mols. of the former. Measurements of interfacial tension indicate changes in lubricating oils due to heat, ultra-violet light, use, e tc .; a decrease implies acid formation. C. A. S.

Interfacial phenom ena in the form ation of crystals w ith continuous or discontinuous d istribution of m icroscopic com ponents. L. I m r e (Z. Elektrochem., 1932, 38, 535—543).—The analogy between crystal growth and adsorption of ions on heteropolar crystal surfaces is discussed a t length. The relative ease of adsorption of two kinds of ion is not const, over the whole cryst. surface; a const, difference of adsorption, potential occurs only when the ions are similar, and in these cases the difference is independent of temp. H. F . G.

W etting velocity and flotation. H. F r e u n d - licit , 0 . E n s l i n , and G. E i n d a u (Kolloid-Beih., 1933, 37, 281—286).—PbS and FeS2 are wetted very rapidly and ZnS and Cu2S,Fe2S3 slowly by H 20 . After treatm ent with oleic acid all are wetted slowly, whilst S i02 is wetted rapidly. Rapid wetting by aq. NaOH or KCN occurs a t a definite concn., which varies w ith the particular sulphide, thus offering a means of separation. E . S. H.

D iffusion of m onatom ic gases through fused silica. T. A l t y (Phil. Mag., 1933, [vii], 15, 1035—

1048).—The assumption th a t atom s of inert gases diffuse along narrow cracks of mol. dimensions in the >Si02 agrees with experimental data. Atoms enter the cracks directly from the gas phase, and not from an adsorbed surface layer. H . J . E.

Copper m em brane gas-m olecu le sieve. Calen d a r 's theory of o sm osis . D. L. W a r r ic k andE. M a c k , jun. (J. Amer. Chem. Soc., 1933, 55, 1324— 1332).—The porosity of a Cu membrane made by vac. distillation of the Zn from th in sheet brass a t 400—900° increases with rise of temp, and duration of heating. Membranes prepared a t low temp, have about 1 0 12 pores (diam. 6 —2 0 A.) per sq. cm., and the transpiration of gases through the membrane is a mol. process ra ther than one of viscous flow. The separation of CGH G or E t20 from gases of smaller mol. diam. is only partly possible owing to clogging of the pores. Callendar’s theory of osmosis is supported by approx. agreement between calc, and observed rates of osmotic flow through a Cu membrane separating H 00 and aq. sugar solutions.

J . G. A. G.A bsorption and osm o sis . I. F. A. H. S c h r e i n e -

m a k e r s and C. L. d e V r ie s (Proc. K. Akad. Wetensch. Amsterdam, 1933, 36, 180—189).—A membrane absorbs substances to which it is permeable and changes its character in the process. These changes have been studied for pig’s bladder in aq, Na2C03, aq. (CHo-C02H)3, and aq. ta rta ric acid (I), and for cellophane in aq. (I). M. S . B.

Perm eability of protein -cellu lose m em branes.G. F l o r e n c e and J . L o i s e l e u r (Bull. Soc. Chim. biol., 1933, 15, 395—401).—Clear membranes can be obtained only when the protein-cellulose solutions are allowed to dry completely a t room temp., and these become permeable only on im bibition of solutions such as dil. aq. H C 02H or EtOH. The permeability increases with the % protein, and is greatest for casein (cf. A., 1931, 167). H. D.

Cryoscopic effects in m ixtu res of solvents and their relation to solub ility of solute. O. A n d e r s (Z. physikal. Chem., 1933, 164, 145— 175).—The solubilities of I, S, and Na2Cr04 in C0H c, AcOH, and mixtures of these a t 0°, 20°, and 30° and of AgC104 in AcOH and C6H 6 a t 20° have been measured. The f.-p. depression of the eutectic and other mixtures of CgH g and AcOH by the above solutes and by Cr03 and the composition of all the phases in equilibrium a t the f.p. of these solutions have been determined. Addition of a small amount of a solute to the CgH g-AcOH m ixture having the eutectic composition causes enrichment of the solid phase separating on freezing in the component in which the solute has the smaller solubility. The f.-p. depression data exhibit abnormalities which are due partly to salting- out effects and partly to polymerisation. N a,C r04 is largely dissociated, whilst AgC104 is associated and somewhat miscible Witli CGH e in the solid state.

R. C.Solvent action. VI. Optical rotatory p o w ers

of (3-octanol, d-am yl alcohol, and their derivatives. H . G. R u l e , (M i s s ) E. B. S m i t h , and J . H a r r o w e r (J.C.S., 1933, 376— 387).— The ro tatory powers in solution of the 15 sec.-p-octyl and (Z-amyl

566 BRITISH CTIEMICAL ABSTRACTS.— A.

compounds examined are closely related to the dipole moment of the solvent, provided th a t mono-substitu ted derivatives of the same hydrocarbon arc employed for comparison. For 11 compounds the ro tatory powers tend to vary inversely as the polarity of the solvent, b u t for the more highly polar substances the reverse relation tends to hold. The explanation is discussed in terms of the theory of dipoles. The graph for the ro tato ry ' power of ¡3- octanol on progressive dilution with CGH 14 is irregular, probably owing to variations in the degree and mode of association of the alcohol mols. in solution. Other alcohols display similar changes in polarisation. Other octyl derivatives, however, yield smooth curves without max. and min., which behaviour is also normal. M. S. B.

Solubilities, conductivities, an db .-p . elevations of solutions of organic and inorganic com pounds in liquid hydrogen fluoride. K. F r e d e n h a g e n [with G. Ca d e n b a c h and W. Iv l a t t ] (Z. physikal. Chem., 1933, 164, 176—200).—In its ability to dissolve org. and inorg. compounds and form highly conducting solutions, H F surpasses all other solvents, even H 20 . H F and H 20 are as solvents almost entirely dissimilar, in spite of the small difference in their dielectric consts. HC1, HBr, and H I are not measurably sol. in H F and do not affect its conductivity. The only anion which can exist in H F solution is F ', and the ion pptn. reactions which occur in aq. solution are not observed. W hilst fluorides ionise in the same way as in H ,0 , other electrolytes ionise according to such schemes as A cO H + H F = A cO H ,H '+ F ', and K N 0 3+ 2 H F = K -+ H N 0 3>H ;+ 2F', as is shown by b.-p. elevation and conductivity data. H F dissolves numerous neutral org. compounds, including carbohydrates, ethers, and ketones, yielding solutions often with conductivities > those of the most highly conducting aq. solutions. Here the ions are formed by dissociation of solvates, e.g., M eO H +H F=M oO H ,H ‘+ F '. I t is suggested th a t in a solution in a binary solvent an atom or group of a solute can form an ion only if its affinities for the cationic and anionic constituents of the solvent are unequal. R. C.

D eterm ination of m olecular b .-p . elevations in hydrogen fluoride. K. F r e d e n h a g e n and G. Ca d e n b a c h (Z. physikal. Chem., 1933, 164, 201— 208).—The mol. b.-p. elevation is 1-90°. R. C.

D iffusion of electrolytes. B. W. C l a c k (Phil. Mag., 1933, [vii], 15, 1061—1062; cf. Davies, this vol., 347).—A correction. H. J . E.

Cryoscopic determ ination of hydration of ions of p otassium chloride. G. B o u r io n and E. R o u y e r (Compt. rend., 1933, 196, 1111—1113; cf. this vol., 460).—On the assumption previously made, the hydration for il/-KCl is represented by KC1,8-62H„0, and for 0-5M-KC1 by KC1.10-2H,6 (cf. A., 1908, ii, 1009; 1928, 954). C. A. S.‘

Lowering of eutectic points : a ternary eutectic. H. M u l l e r (Compt. rend., 1933, 196, 1109— 1111; cf. A., 1932, 913).—The mol. lowering for the eutectic (100 H ,0 , 10-3 K N 0 3, 4-7 K ,S 0 4; —3 -0 2 °) is 16-5. ‘ " C. A. S.

P artia l m ola l vo lum es of cobalt sulphate and of cadm ium iodide [at 25°]. R . C. C a n te lo and H. E. P h i f e r (J. Amer. Chem. Soc., 1933, 55, 1333— 1338).—The d a ta refer to 0-005—2-29jTJ aq. solutions. F o r CoS04, F = 14-06^—3-514, for KC1, 7 =3-652^+26-23, and for Cdl2, F=67-16, where V is thepartial molal vol. and c is mol. concn. The results are discussed in relation to the theory of complete ionisation. J . G. A. G.

Colorim etry of titan ium . III. H. G i n s b e r g (Z. anorg. Chem., 1933, 211, 401—411; cf. this vol., 43).—Coloured solutions obtained by adding H 20 2 to Ti solutions containing H 3P 0 4, H 2S 04, K H S 04, and A12(S04)3 obey the Lam bert-Beer law a t concns.4—0-2 mg. of Ti per 100 c.c. The determination of Ti with the abs. colorimeter (A., 1932, 1225) is described.

H. J . E.A lkali tartrates and chrom ium . J . P. M a t h i e u

(Compt. rend., 1933, 196, 1222—1224; cf. this vol., 26).—Measurements of optical activity, a, circular dichroism, 8 , and absorption for solutions containing varying proportions of Cr111, NaOH, and Na ta rtra te indicate the existence, besides the chrom itartrate, of one or more intermediate compounds, and also of a compound, for which a is negative for blue, and positive for red light, and for which 8 is positive.

C. A. S.B irefringence of cerium sa lts in aqueous and

non-aqueous solution. C. H a e n n y (Compt. rend., 1933, 196, 1297— 1298; cf. A., 1932, 677, 909).— Magnetic birefringence-concn. curves of aq. solutions of Ce(N03)3, Ce2(S04)3, and CeCl3 are convex to the axis of concn. The birefringence of the n itrate is much the strongest; i t is diminished by excess H N 03, and the magnitude of this effect increases more rapidly than the H N 0 3 concn. EtOH solutions o f . Ce(JSf03)3 and CeCl3 are also strongly birefringent; CeTV salts are only slightly so. These facts indicate a connexion between birefringence and magnetic moment.

C. A. S.Subsidence of starch m ilk . S p r o c k h o f f and

H o n s c h (Z. Spiritusind., 1933, 56, 59).—Potato starch suspensions of d 1-07— 1-15 were allowed to subside in a vertical glass tube 1 m. long and of 45 mm. bore; deposition was regarded as complete as soon as the upper surface of the deposit offered a firm resistance to a glass rod with flattened end. For suspensions of equal concn. the time required for deposition is proportional to the height of the liquid, and for a given height the time required is proportional to the original concn. In practice moderately tall vats and low concn. are recommended as most favourable to the separation of fibrous m atters from the starch.

J . H. L.A pplication of W iener’s general m ixture for

m ula to colloid-disperse sy stem s. II. F r e u n d - l ic h and F . R o g o w s r i (Kolloid-Beih., 1933, 37, 215—222).—The variation of n w ith concn. in sols of A120 3, S i02, TiOa, ThOa, mercurisulphosalicylic acid, gelatin, ovalbumin, and cellulose acetate and nitrate is not consistent with W iener’s theory. E. S. H .

Influence of saline im purities on osm otic pressure of colloidal so lutions. A. B o u t a r ic (J. Chim. phys., 1933, 30, 181— 185).—Expressions

GENERAL, p h y s i c a l , a n d in o r g a n ic c h e m is t r y . 567

for the osmotic pressure of a colloidal electrolyte against its ultra-filtrate are derived for cases where the non-diffusible ion is n-valent, and where the salt im purity is uni-uni- and uni-bi-valent. F. L. U.

Dependence of the ultra-filtrate from a so l of1 ‘ ferric hydroxide ' ’ on rate of u ltra-filtration ; Donnan equilibrium and ]>n of so ls . J . W. M cB a i n and W. L. M cCl a t c h ie (J. Amer. Chem. Soc., 1933, 55, 1315— 1323; cf. A., 1932, 994).— The concn. of the filtrate from fairly conc., well- dialysed Fe(OH )3 sol decreases many-fold with increasing ra te of ultra-filtration through cellophane membranes a t pressures between 1 , and 1 0 0 atm. That the jhi of a rapidly obtained ultra-filtrate is < th a t of a sol of a positive colloid (with very slow ultra-filtration, the p n is much greater) supports the view th a t in the slow process the ultra-filtrate approaches the Donnan membrane distribution due to the presence of charged colloids, whereas in the rapid process the regions immediately surrounding the particles are sampled. The importance of these results in relation to previous work is emphasised.

J . G. A. G.R eversal of lyotropic series in flocculation

experim ents. A. V o e t and F. B a l k e m a (Rec. trav. chim., 1933, 52, 371—377).—The coagulating power of univalent anions for Au sols which have had their charge reversed by A l"‘ or T h‘“ ‘ is in the order C N S '> r> N 0 3 '>C 10 3 '> B r '> C r , showing an in version of the usual order. Peculiarities in the coagulation of hydrated and non-liydrated sols are explained by the reduction of the dielectric const, of H„ 0 by accumulation of ions in the double layer.

F. L. U.Coagulation of colloidal sulphur solutions by

gelatin. G. R o s s i and G. S c a n d e l l a r i (Annali Chim. Appl., 1933, 23, 67—71).—Coagulation of highly-dialysed colloidal sulphur solutions by gelatin yields large flocks, which are formed only within very narrow limits of gelatin concn. and redissolve with excess. The coagulation thus differs essentially from th a t caused by KC1. T. H. P.

Depolarisation of ligh t on p assing through colloidal solutions. V. P e t r e s c u (Ann. Sci. Univ. Jassy, 1933, 17, 15—69).— Of 14 colloids examined none shows any light depolarisation in the sol state, either fresh or after ageing. The corresponding gels, however, exhibit the property to a degree which depends on the age of the sols from which they are formed. For suspensions of V20 5 and CaC03 the angle of depolarisation varies as the square of the radius of the particles. A modified form of Pokrovski’s formula agrees well with experiment.

J . W. S.Stability of lith ium urate so ls . S . P r a k a sh (J.

Indian Chem. Soc., 1933, 10, 35—39).—The ageing of sols has been followed by measurement of electrical conductivity. The sol is hydrophobic and gels formed from it have little stability. A. S. C. L.

Influence of non-electrolytes on the coagulation of Ce(OH)4 so l d ialysed to different extent.M. P r a s a d and M. V. N a b a r (J. Indian Chem. Soc., 1933, 10, 53—56).—Alcohols sensitise the sol to coagulation, ■ their efficiency increasing with chain-

length. Sugars protect, sucrose being more officient than glucose. These effects become more marked when the stabilising ions are removed. A. S. C. L.

Double layer of silver iodide sol. E. K. W.V e r w e y (Proc. K . Akad. Wetensch. Amsterdam, 1933, 36, 225—233).—The adsorption of AgN03 and K I by undialysed Agi sols has been determined potentiometrically and colorimetrically. The ageing of dialysed and undialysed sols has been studied quantita tively by changes in adsorptive power. I t may take place rapidly without increase in size of particles or slowly with increase. Adsorption of the peptising ion appears to take place a t edges or irregularities on the surface of the submicroscopic crystals. These active points decrease in no. as the crystals gradually assume a more regular and perfect form.

M. S. B.Variation of the electrical charge of colloidal

particles. V. Effect of the m anner of preparation of A s2S 3 sol on cataphoresis in presence of electrolytes. J . M u k h e r j e e , S. R o y c h o u d h u r y , and S. G. R a j k u m a r (J. Indian Cliem. Soc., 1933,1 0 , 27—32).—The influence of various electrolytes oncataphoretic velocity has been studied ; the mechanism of their action is discussed. A. S. C. L.

Electrokinetic phenom ena. X I. Action of univalent electrolytes on electric m obility of proteins. H. A . A b r a m s o n (J. Gen. Physiol., 1933,16, 593—603).—The velocities (I) of natural and heat-denatured ovalbumin and of gelatin in various conens. of acetate buffer were determined. The decrease in (I) due to increased concn. suggests a simple relation between (I) and the effective reciprocal thickness of the electric double layer. Such a relation may be derived theoretically from the assumption th a t the electric charge of proteins is primarily determined by the [H‘] of the medium (cf. A ., 1932, 695).

F. O. H.Colloid chem ical studies on rosin sizin g . I,

11. K . K a n a m a r u and T. T s u c h i d a (J. Soc. Chem. Ind. Japan, 1933, 36, 102— 110b).—The influence of KC1, NaCl, MgCl2, K 2S04, IiCl, H 2S04, NaOH, A1C13, A12(S04)3, and Th(N 03)4 on the Ç potential and turbidity of sols of abietic acid and its N a salt is in accordance w ith the valency rule. A1C13 and Th(N 03)4 cause a reversal in the sign of charge of the particles, and a sharp min. is observed in the turbidity-concn. curve where the Ç potential-concn. curve intercepts the concn. axis. Changes in the concn. of electrolyte affect the potential and the turbidity in the same manner. AUSOJo does not reverse the sign of charge.

E. S. H.Influence of lyotropic substances on the m u ta

rotation and gélatin isation of gelatin -w ater m ixtu res. II. Substances w ith two hydrophilic groups. J . R. K a tz and J . F. W i e n h o v e n (Rec. trav. chim., 1933, 52, 385—388; cf. this vol., 226).—Comparison of substances containing two hydrophilic groups with those containing only one shows parallelism between the influence on surface tension and th a t on the m utarotation and gélatinisation of 3% gelatin. Substances with several S 03H groups, and o-CrjH ,(OH)-CO.,H form an exception to this rule. “ F. L. U.

taÜTÏSH CÏIlîMIOAL ABSTRACTS.----A.

T ransform ations of gelatin . I. Scattering of light. II. U ltra-filtration . J . D u c la u x and F. H ir a ta (J. Chim. phys., 1933, 30, 213—231).— Scattering of light by gelatin sols and gels has been measured a t concns. 0-—2-1%, temp. 5—40°, and p a3-5—9. Gelatin exists in two forms, one of which ( < 2 %) scatters white light strongly with max. a t p a 5 , whilst the other scatters blue light feebly, the scattering increasing continuously with the p B: Gélatinisation does not involve an increase in the vol. of the particles, but is due to formation of a network. The fraction of gelatin which can pass an ultra-filter increases continuously with rise in temp, between 0 ° and 70°. . F . L. U.

Influence of sm a ll quantities of electrolytes on the course of gélatin isation of potato starch by heat. E. W i e g e l (Z. Spiritusind., 1933, 56, 62— 63).—The changes in viscosity of 1% suspensions of air-dried potato starch in H 20 or electrolyte solutions, in the course of heating from 20° to 95° and maintaining a t 95° for several hr., were measured by W o . Ostwald’s method (“ Kleine Praktikum der Kolloidchem.,” 7th Ed., 1930, 41) and arc represented by graphs. In most cases a pronounced max. was obtained i — 1 hr. after 95° had been attained. The max. val. is greatly influenced by the ra te of heating to 95°. For a standard ra te of heating the max. val. is lowered considerably by small quantities of electrolytes.

J . H. L.Rliythm ic precipitates. II. Influence of ligh t

and ageing. T. Isem u ra (Bull. Chem. Soc. Japan, 1933, 8 , 108—112).—The rhythm ic bands formed by the action of AgNOs solution on a gelatin jelly containing K 2Cr20 7 do not become irregular when the system is exposed to light, even direct sunlight, but they become closer and their number increases. Previous reports to the contrary are ascribed to irregular irradiation. U ltra-violet radiation retards band formation and causes the bands to become finer and closer together; this effect does not occur with CuCr04 bands in S i0 2 gel. The Ag2Cr04 bands produced in an aged gelatin gel and "in a gel of the same age, but warmed and allowed to re-set before the AgN03 is added, are identical; the influence of ageing is thus related to a reaction between the K 2Cr20 7 and the gelatin and no t to the gel structure. The effect of ageing is less pronounced with CuCr04 bands in S i0 2 gel. H. F. G.

D istribution of cations and anions in sw ellin g gelatin . W. von Moraczewski (Biochem. Z., 1933, 259, 3S7—397).—In Ca salt solutions a t p a below the isoelectric point the gelatin is richer in anions (Cl', I ', CNS') and poorer in cations than the outer fluid ; a t p K above the isoelectric point the gelatin is richer in cations but has the same anion content as the outer fluid. For K and NH 4 salts the results are much less definite. P. W. C.

Sw elling of gels in presence of denaturing agents. N. J e r m o l e n k o and A. L o b a n o v it s c h (Biochem. Z., 1933, 259, 374—3S0).—Denaturing substances (CH20 , PhOH, EtO H, MeOH) decrease the swelling. The effects of these substances and those of hydrating substances (KCNS, K I, carbamide) in mixtures are additive. The characteristic >u-swclling

curve is still given in presence of denaturing substances. The latter retard the liquefaction of gelatin by certain salts (KCNS, KI) a t room temp.

P. W. C.Dénaturation of proteins. X . Acid and alkali

titration curves of crystalline ovalbum in. XI. Effect of dénaturation on capillary activity of solutions of certain proteins. W. J . L o u g h l in (Biochem. J ., 1933, 27, 99—105, 106—111).—X. T itration curves for undenatured cryst. ovalbumin (I) with the glass electrodo (A., 1930, 1151) agree with those given by the H 2 (A., 1932, 996) or quinhydrone electrodes (A., J.932, 181). The curves for(I) are identical with those for the denatured protein for p a 2-5—6 ; the agreement on the alkaline side is no t so satisfactory (cf. A., 1930, 628; 1931, 316). The method of coagulating the protein may influence the titration on the alkalino side.

X I. The dynamic surface tension (s) of solutions of natural and of denatured but unflocculatcd (I) and oxyhæmoglobin (II) has been determined. W ith natural (I), s has a min. val. a t the isoelectric point (cf. A., 1928, 121). Both natural proteins lower the s of H 20 , bu t the 2}u~s curves for (II) are more regular than those for (I). In both cases dénaturation lowers s to an extent which depends on p a. The increased capillar}' activity on dénaturation is due to the increased size of the micelles. F. 0 . H.

Effect of u ltrasonic w aves on g e ls , especially th ixotropic je llies. H . F r e u n d L ie n , F . R o g o w s k i , and K. S ô l ln e r (Kolloid-Beih., 1933, 37, 223—241). —Apparatus for producing intense ultrasonic weaves is described. The waves have the effect of liquefying those gels th a t can be liquefied normally by shaking, bu t no permanent change is brought about, as the subsequent solidification time is not altered. Liquefaction occurs first a t the air boundary. Non-thixo- tropic gels do not exhibit the phenomenon. The swelling and peptisation of caoutchouc in various org. media and of gelatin in H 20 are accelerated by ultrasonic waves, apparently by reason of local heating a t the gel-liquid boundary. S i0 2 gels do not liquefy under the influence of ultrasonic waves, but lose their elasticity and become slightly turbid after long exposure ; the original elasticity is regained on keeping the gel. E. S. H.

Study of sy n eresis . G. R ossi and A. M a r e s c o t t i (Gazzetta, 1933, 63, 121— 127).—The concn, of salt in the liquid obtained by the syneresis of agar-agar dissolved in aq. gelatin solutions containing Na and K halides is in general > (but for some KI solutions < ) tho concn. in the original gelatin solution. This sp. influence of the salt ions on syneresis is probably of importance in certain biological processes. O. J . W.

Com plex coacervation. XVII. Specific effects in the m ixed coacervation type 4 —1 ofgum -arabic so l. H . G. B. d e J o n g , J . H . v a n d e rH o r s t , and A. L a f l e u r (Biochem. Z., 1933,2 6 0 ,161— 169).—The auto-complex coacervation of gum-arabic sol has been examined in respect to (a) the effects of cations and anions of neutral salts of the types 2 — 1 and 1— 1 , and (6 ) the effects of various alcohols as desolvation agents. H . W. D.


Com plex coacervation. XV. Coacervation and precipitation of types 4 and 4— 1 by sod ium arabate sol. H. G. B. d e J o n g and K . C. W i n k l e r . XVI. M echanism of the union of oppositely-charged ions. H. G. B. d e J o n g (Biocliem. Z., 1933, 259, 436—441, 442—452).—XV. Previous experiments (A., 1931, 908; 1932, 693) with gum- arabic sol arc repeated using Na arabate sol, with similar results, quant, differences being chiefly duo to the substitution of Ca" by Na'.

XVI. Further experiments with Na nucleate sol are discussed in relation to the attachm ent of oppositely-charged ions a t the inner surface of the double layer. P. W. C.

Change of state of v iscous system s. VII. E xtension of theory to solid substances. H.U m s t a t t e r (Kolloid-Beih., 1933, 37, 287—292; cf. ibid., 1932, 34, 1).—Theoretical. E. S. H.

Chem ical equilibrium in vapour of a m ixtu re of hydrocarbons. H. A. W i l s o n (Proc. Boy. Soc., 1933, A, 140, 1—8).—The author’s theory (A., 1927, 1139; B., 1929, 503) is applied to mixtures containing naphthenes and cycZoparaffins as well as paraffins and unsaturated hydrocarbons. W ith liquid and vapour both present, the naphthene fraction increases with rise of temp., bu t falls with the pressure; when vapour only is present, i t falls w ith the temp, but rises with the pressure. The variation of the C6H 6 fraction with temp, and pressure is also considered.

L. L. B.Role of the solvent in electrolytic dissociation.

A. R. Ma r t i n (Nature, 1933, 131, 584—585).—A criticism (cf. this vol., 354). L. S. T.

Equilibrium law of electrolytes. K. J a b l - c z y n s k i and J . W o j c ie c h o w s k a (Rocz. Chem., 1933, 13, 167— 175).—The expression nm lii^= K (where n0 is the concn. of undissociated salt, and n th a t of one of its ions) is verified cryoscopically for various concns. of H, Li, Na, K, N IL , and Ag n itrate, H, Na, NH 4, and K perchlorate, K B r0 3, N aB r03, K I0 3, and H I0 3. A const, val. is obtained for K on the assumption th a t certain ions are hydrated (H‘ 9, L i' 11, N a' 3, It ', NH4', Ag', N 0 3', BrCV, and I 0 3' 0, and C104'4 mols. H 20), and th a t Na, K, NH4, and Ag nitrates are associated. Since LiN 03 and H N 0 3 do not exhibit association, the same m ust apply to N 0 3' ions, whence it follows th a t complexes of the type [M(N03)2]' m ust be formed. The vals. of K for acids diminish in the order H I> H B r> H C l> H N 0 3> HC104 > H I 0 3, and a similar series is obtained for K salts of certain of these acids. R. T.

D issociation constants of acids. G. N. B u r k - h a r d t (Chem. and Ind., 1933, 330).—A reply to Wynne-Jones (cf. this vol., 464). E. S. H.

Ionisation of sulphuric acid. H. M. D a w s o n (Proc. Leeds Phil. Soc., 1933, 2, 359—364).—The hydrolysis of EtOAc in solutions of H 2S04 is due to the joint catalytic effects of the H ’ and H S 04' ions. Since the first-stage ionisation is practically complete, it is possible to derive the [H*] for dil. solutions ofH ,S0 4 from the measured reaction velocities and the catalytic coeffs. for the two reactive ions. The second-stage ionisation const. A7, = 0 -0 1 0 ; this val.

affords a satisfactory account of the reaction velocity data for a wide range of H 2S04 solutions.

N. M. B.E xtent of d issociation of zinc su lphate. I. A.

Co w p e r t h w a it e (Trans. Faraday Soc., 1933, 29, 593—596).—The conclusion reached from e.m.f. data (A., 1932, 126), th a t ZnSO.j is completely ionised up to 0-01ilf, is supported by the Debye-Hiickel theory as extended by La Mer and his colleagues. M. S. B.

One-third basic alum inium acetate solution.I . C. R o h m a n n (Arch. Pharm., 1933, 271, 219— 247).—The degree of hydrolysis of A1 diacetate (I) increases from 14-4 for l-15iV to 32% for 0-060IV solution. The jhi is only slightly affected by the temp, of prep, or by dilution. The solution is shown by electrometric titrations to have excellent buffer capacity with max. a t pn 3-6, 4-7, and 10-5. Conductivity measurements indicate th a t (I) behaves as a salt of a univalent cation and univalent anion.F.-p. measurements support the view th a t (I) is associated in solution. The sediment formed during various methods of prep, always gives the same X-ray diagram and appears to consist of (I) with a slight excess of OAc. R . S. C.

P hase changes in the ordinary and extended sense classified according to the corresponding singularities of the therm odynam ic potential. P. E h r e n f e s t (Proc. K . Akad. Wetensch. Am sterdam, 1933, 36, 153—157).—Discontinuities in curves of both first and second order, due to phase change, are discussed. M. S. B.

A lkaline-earth hydrides. P. REM Y-GENNETf; (Ann. Cliim., 1933, [x], 19, 263—352).—A crit. review of data relating to the dissociation of CaH2 and experimental details of results previously published (Bull. Soc. chim., 1929, [iv], 45, 699; Compt. rend.,1929, 189, 579). The chief difficulty in the determination of the dissociation pressure of CaH2 is the volatility of Ca. This has been overcome by enclosing the heated CaH2 in an Fe tube with a th in wall which, when hot, is permeable to H a, but not to Ca vapour. The H 2 pressure has thus been determined for the temp, range 815—965°. The results are satisfactorily represented by the equation log £>=0-00917997'— 8-503. There is no indication of the existence of a subhydride CaH. These results are in good agreem ent with those of H urd and Walker (A., 1931, 800). The heat of formation calc, from Nernst’s theorem is approx. 41,000 g.-cal. M. S. B.

Transition points of sa lt hydrates in various non-aqueous solvents. W. W. L u c a s s e and H. J. A b r a h a m s (J. Physical Chem., 1933, 37, 511—519).— The method previously described (A ., 1926, 799) has been extended by using different solvents (MeOH, EtO H, Pi-OH, mo-C5H u -OH, C5H sN, COMe2, and glycol). The transition temp, is in general independent of the solvent and identical -with th a t obtained by other methods. Mean vals. are : L iN 03,3H20 — >- 2LiN03,H20 , 29-5°; CaCl2,6H20 — > |3-CaCl2,4H20,

28-7°; CdBr2,4H20 — ^ .CdBr2,H„0, 35-5°;Zn(N03)2,6H20 — ^ Zn(N03)2,3H;0, 35-3°;

ZnBr2,2H20 — > ZnBr„ 35-3°; CoCl2,6H„0 — > CoCl2,H20 (?), 31-3° in “C5H 5N or MeOH: and 29-7° in glycol. D. R. D.

570 BRITISH CHEMICAL ABSTRACTS.-— A.

Change in the transform ation tem perature of copper sulphate at 56° w ith the solvent m edium .H. J . A b r a h a m s and W. W. L u c a s s e (J. Physical Chem., 1933, 37, 521—524).—The transition point of CuS04 a t about 56° (probably g-CuS04,5H20 ■ ■ > (J-CuS04,5H20) has been determined by the authors’ method (cf. preceding abstract), using glycerol-EtOH mixtures as solvent. The transition temp, falls from53-1° with 10% glycerol to 49-6° with 80%.

D. 11. D.Chem ical system s of Lenard phosphors. I.

R. S c h e n c k and H. P a r d u n . II. R. S c h e n c k (Z. anorg. Chem., 1933, 211, 209—221, 303—320).—I. The systems MS-Bi2S3 (M =Ca, Sr, Ba) have been studied with reference to the chemical changes occurring during absorption and emission of light by phosphors. From the determ ination of equilibria in the reaction Bi2S3-p3H2—2B i+ 3H 2S a t 507° in presence of varying amounts of MS it appears th a t BaS and SrS, bu t not CaS, combine with Bi2S3 thus : S " + B i2S3— >(Bi2S4)". H eats of formation of the thiobismuthites from the respective sulphides arc calc, by two independent methods, th a t of CaBi2S4 being assumed = 0 .

II . The phosphor system is regarded as analogous to a storage battery, electrons being transferred from cation to anion during absorption of light energy, which is em itted during the reverse change. This view receives support in the agreement of the differences between the heats of formation of Ca, Sr, and Ba thiobismuthites with those between the energies of electron transference in the corresponding phosphors calc, from the wave-length of their a-emission bands. The reaction wliich gives rise to the bands is therefore M '+ (B i2S4)'— ^M ” + (B i,S 4)".

F. L. U.Phloridzin crysta ls. P. G a u b e r t (Compt. rend.,

1933,196, 554—556).—Addition of a dye (0-1—0-5%) to hydrated phloridzin, C21H 24O20,2H2O, leads to the formation of larger crystals, probabh7 rhombic. The hydrated crystals, d 1-431, heated in vaseline a t about 105° give off H 20 and w ithout melting pass into the anhyd. substance, d 1-452, m.p. about 150°. The behaviour on heating the crystals in air is described in detail (cf. A., 1932, 101). C. A. S.

Foreign m atter in solid solution and stability of crystals. P. G a u b e r t (Compt. rend., 1933, 196, 942—944; cf. this vol., 451, and preceding abstract).— The influence of the presence of > 1 % of various dyes on the dehydration, cleavage, and refractivity of crystals of hydrated phloridzin is described. I t is suggested th a t the presence of minute quantities of foreign substances may explain the varying behaviour of m any minerals, e.g., laumontite, of different origins. C. A. S.

S ystem (NH4)2S 0 4-H 2S 0 4-H 20 . P. LocuTYand P. L a f f i t t e (Compt. rend., 1933, 196, 1311— 1314; cf. A., 1921, ii, 45).—The system has been examined a t 30°, 50°, and 70°; the resu ltan t curves are similar and indicate the compounds (NH4)2S 0 4,H>S04, 3(NH4)2S04,H2S04, and 4(NH4)2S 0 4 ,H2S 04.

C. A. S.System H gB r,-K B r-E tO H . (M l l e .) M . P e r n o t

(Compt. rend., 1933, 196, 1314—1316; cf. A., 1931,

695).— With pure EtOH, HgBr2,KBr,EtOH is formed as colourless crystals, in which E tO H is rapidly replaced by H 20 on exposure to the atm . W ith 95 vol.-% EtO H the crystals are HgBr„,KBr,H,,0.

C. A". S.Ternary system palm itic, m argaric, and

stearic acids. R. L. S h r i n e r , J . M. F u l t o n , andD. B u r k s , jun. (J. Amer. Chem. Soc., 1933, 55, 1494—1499).—F.p. for the ternary system of palmitic, m.p. 62-2—62-4°, margaric, m.p. 59-9—60°, and stearic, m.p. 69-6—69-8°, acids are recorded.

H. B.Reciprocal system in absence of the solvent.

A. P . P a l k in (Acta Univ. Asia; Media;, Chem., 1930,6 , No. 4, 1— 10).—I. A gC l+K B r === A gBr+K Cl. The reaction -<— shows a small heat effect, 0-3 kg.- cal., b u t the equilibrium tends to the AgBr side owing to the slight solubility or slight dissociation of the salt. The cutectoid line is characteristic. I ts projection on a vertical plane is convex with a max. near AgBr. The binary systems AgBr-AgCl and K B r- KC1 form an unbroken series of solid solutions, whilst AgBr-K Br and AgCl-KCl each have a eutectic.

II . A g B r+ K I Agl-j-KBr. The system is similar to the previous one. The reaction — >- is accompanied by a positive heat effect of 8 -8 kg.-cal. In the binary system A g l-K I an unstable compound, Id ,4A gI, decomp. 267°, is formed. B oth systems represent a link between the purely reciprocal and the irreversible types. M. S. B.

G aseous therm al diffusion—the principal cause of discrepancies am ong equilibrium m easurem ents on the system s F e30 4-H ,-F e -H 20 , F e30 4-H 2-F e 0 -H 20 , and F e 0 -H 2-F e -H 20 . P .H . E m m e t t and J . F. S h u l t z (J. Amer. Ciiem. S o c ., 1933,55,1376—1389; cf.A ., 1932, 1090).—By means of a static method incorporating special precautions the following equilibrium ratios, Pn,olPu„ have been found : 0-334, 0-419, 0-501, 0-603, and 0-678 a t 600°, 700°, 800°, 900°, and 1000° for the Fe-FeO system, 0-107, 0-214, and 0-283 a t 400°, 500°, and 550° for the Fc-Fe30 4 system, and 2-35, 1-16, and 0-461 a t 800°, 700°, and 600° for the F e0 -F e 30 4 system. Thermal diffusion accounts for previous static vals. being as much as 40% too high (cf. A., 1931, 41), and the degree of therm al separation in H 20 -H 2 m ixtures at 400—500° in a tube with a temp, gradient has been determined. I t is calc, th a t therm al diffusion may lead to errors > 8 % in the CO„/CO ratio for the systemF e-C 0 2-F e0 -C 0 . " J . G. A. G.

Equilibrium in the system S n 0 2-H 2-S n -H ,0 . Indirect calculation of the values of "the"water-gas equilibrium constants. P. H. E m m e t t and J. F. S h u l t z (J. Amer. Cliem. Soc., 1933, 55, 1390—1395). —By means of the technique previously described (preceding abstract), the statically determined equilibrium ratio, P u,0 /Ph„ for the reaction 0‘5Sn02+ H 2= 0-5Sn+H 20 is 1 -6 6 , 2-22, 2-84, and 3-53, a t 650°, 700°, 750°, and 800°, respectively. T hat previous results (cf. A., 1928, 594) are about 25% too high is attributed to therm al diffusion. The new vals. combined with data for the S n-C -0 system give consts. for the water-gas equilibrium in accord with direct determinations. J . G. A. G.


Field of saturation of p otassium and sodium chlorides in quinary sea-salt system s. II. D.L a n g a u e r (R ocz. Chem., 1933, 13, 201—212).—The solubility of KC1 and NaCl in solutions of a const, concn. of MgCl2 and a variable concn. of MgS04, and vice versa, has been determined a t 83°, 90°, and 100°.

R. T.Value of the determ ination of free energy

change for organic com pounds. D. B. K e y e s (Science, 1933, 77, 202—204). L. S. T.

H eat of form ation of silicon tetrafluoride, carbon tetrafluoride, and silicon carbide. H.v o n W a r t e n b e r g and R . S c h ü t t e (Z . anorg. Chem., 19 3 3 , 211, 2 2 2 — 2 2 6 ).— The vals. obtained in kg.-cal. are : Si(cryst.) + 2 F .2= S i F 4 4 - 3 6 0 ^ 3 ; C(graphite) +2F2= CF4-j-162 ¿ 2 ; and (by fluorination of SiC) Si(cryst.)-f C (graphite)=S iC +31±6. F . Lv U.

M oving boundary m ethod for the determ ination of transport num bers. G. S. H a r t l e y and J . L. M o il l ie t (Proc. Roy. Soe., 1933, A, 140, 141— 158).—Theoretical. The fundamental relations between the transport no., mobility, and equiv. conductivity of a radical are worked out, and the equations for the displacement of concns. in conducting solutions are derived. If there is a moving boundary between two electrolyte solutions with a common ion, and if the leading non-common ion is faster than the following non-common ion, the two solutions become separated up to a lim it determined by diffusion, the leading ion remains a t const, concn., and the following (or indicator) solution autom atically attains a const, concn. Experimental work on both rising and falling boundaries is discussed. The independence of the boundary velocity of the initial concn. of the indicator solution is limited by the effects of temp, and concn. correction. L. L. B.

Change of transport num bers in a m em brane due to the concentration of electrolyte, and a theory of transport num ber in the pores of a m em brane. S. O k a (J. Soc. Chem. Ind. Japan, 1933, 36,93—98b).—Experim entsw ithhardened filter paper, two kinds of collodion, collodion impregnated with haemoglobin, parchm ent paper, cellophane, and parchment paper dyed with Congo-red show th a t the transport nos. depend on the concn. of the solution and th a t the relative effects of the membranes arc small a t high concn. and become more marked at lower concns. In explanation it is suggested th a t the capillary pores of a membrane contain (a) the membrane ion, (6 ) the ions in the outer double layer, (c) free anions, (d) free cations. E. S. H.

L udw ig-Soret effect and ionic m obilities in cuprous b rom ide-silver brom ide m ixed crystals.H. R e in h o l d and R. S c h u l z (Z. physikal. Chem., 1933, 164, 241—276).—The equilibrium diagram for the system CuBr-AgBr has been determined. The Ludwig-Soret effect changes in sign on passing through a concn. of 50 mol.-% and also on passing through 200°. Transport nos. have been measured a t 170—290° w ith mixed crystals containing 30—90 mol.-% A gB r; their temp, coeffs. change in sign in the same temp, and concn. region as the Ludwig- Soret effect. In the region of stability of the high -

temp, form of AgBr the sp. conductivity of mixed crystals containing 65, 80, and 90 mol.-% AgBr may be represented by K=K1-{-K2==A1e~E,,tlT-\-A2e~E''Kli’, the consts. of which can be evaluated from transport data. (E1—E 2) has the same val. as the difference of the heats of transport. A relation between the Ludwig-Soret effect and relative ionic mobilities in mixed crystals, deduced from W agner’s theory (Ann. Physik, 1929, [v], 3, 629), agrees with the above results. Diffusion coeffs. have been measured in mixed crystals containing 50, 65, and 80 mol.-% AgBr, and the results in conjunction with Einstein’s equation give vals. for the ionic conductivities of the same order as the observed vals. R. C.

E lectrical conductivities of solutions of w ater in sulphur dioxide. M. d e K. T h o m p s o n and F. C. J e l e n (Trans. Electrochem. Soc., 1933, 63, 91— 105).—The sp. conductance of anhyd. S 0 2, measured by a d.c. method immediately after distillation into a Pyrex cell w ith smooth P t electrodes, decreases notably with successive distillations, but becomes nearly const, after 5—10 distillations. The vals. increase on keeping for periods up to I hr., and Ohm’s law is no t obeyed, the apparent sp. conductance decreasing with increase of applied voltage between 44 and 990 volts per cm. The lowest immediate val. obtained a t —2 0 ° to 0 ° was approx. 10~9 mho per cm. Cooling from 20° to —60° causes a marked increase in conductivity. The sp. conductance of S 0 2 containing up to 0-004% of H aO does not differ appreciably from th a t of anhyd. S 0 2 measured under the same conditions, bu t with higher concns. of H 20 the sp. conductance increases rapidly, reaching 0-77X10-6 a t 0-1% H 20 and 3-4x10-« a t 1% H 20 a t 0 °, the la tter concn. being near the saturation val. The temp, coeff. of conductivity changes sign between0-064 and 0-15% H 20 . Sp. conductances >10"® mho per cm. were measured by the a.c. method.

H. J . T. E.Conductivity of Grignard reagents in ether

solutions. W. V. E v a n s and F. H. L e e (J. Amer. Chem. Soc., 1933, 55, 1474—1477).—1The order of conductivity a t —10° to 20° is : MgEtBr (max.), MgBuaBr, CH2Ph-MgBr, MgPhBr, MgBr2 (m in.); all have negative temp, coeffs. Except with 2 M- MgPhBr, fall in temp, causes increase in the conductivity. The mol. conductivity of M gEtBr decreases with dilution. H. B.

Interpretation of electrolytic part of conduction in am algam s and other alloys. II. C.W a g n e r (Z. physikal. Chem., 1933, 164, 231—233; cf. A., 1932, 230).—Comments on Schwarz’ paper (cf. following abstract). An approx. expression for transport no. in a solid alloy is deduced. R . C.

Theory of electrolysis phenom ena in m etallic solutions. K. S c h w a r z (Z. physikal. Chem., 1933, 164, 223—230).—Skaupy’s theory (A., 1907, ii,327) th a t in a molten metallic solution the force opposing tho action of the applied field on tho ions is the friction of the electrons on the ions is irreconcilable with experimental data, bu t the assumption th a t the migration of the ions is determined only by the resultant of the electrostatic force and electro- hydrostatic buoyancy leads to a relation between


transport no., density of charge, p, and mobility which agrees with available data, and indicates th a t th a t component of the solution having the greater p will migrate to the cathode. Hg is apparently completely dissociated into clcctrons and H g' or Hg2". B .C .

Standard battery. R. B. E l l io t t arid G. A. H u l e t t (J. Physical Chem., 1933, 37, 4S9—493):— Details are given for the construction and maintenance of a Weston coll battery. On closing the circuit, the c.m.f. falls about 0 - 2 0 0 mv. during the first 30 sec. and then remains const, a t 1017-489^0-003 mv., independent of temp. D. R . D.

H aber’s g la ss cell. J . Zi r k l e r (Z. Physik,1932,: 77, 126; cf. A., 1931, 914).—The c.m.f. of a cell symmetrical with respect to a glass membrane is probably a piezo-electric effect duo to strains ill the glass. This cell m ay bo adapted to measure e.m.f. without diffusion, and thus verifies Nernst’s views on the association of strong electrolytes.

A.'B. D. C.U se of the tungsten -n ickel electrode system in

neutralisations. N. H. F u r m a n and G. W. Low, jun. (J. Amer. Chem. Soc., 1933, 55, 1310—1315).— The W -H g2Cl2 and the N i-Hg2Cl2 electrodes are most sensitive in the p n regions in which phenol- phthalehi and Me-orange, respectively, changc colour. The W -N i system is satisfactory in th e . titra tion of a weak or a strong base with a strong acid.

J . G. A. G.M echanism of hydrogen-oxygen electrode,

K, B e n n e w i t z and W. N e u m a n n (Z. physikal. Chem., 1933, 164, 277—294).—The potential, s, of a P t electrode in contact with a m ixture of H 2 and 0 2 has been measured. A platinised electrode reacts so rapidly compared with the ra te of diffusion th a t if H 2 is in excess above the stoicheiometric ratio it behaves as a H 2 electrode, whilst if the 0 2 is in excess it acts as an 0 2 electrode, although in the latter caso the reversible potential is not reached, which m ay be accounted for by the oxide theory (A., 1932,24). W ith a bright P t electrode the relation between s and the composition of the gas mixture is most satisfactorily accounted for on the lines of Erdey-Gruz and Yolmer’s theory (A ., 1930, 1376).

R. C.O xidation-reduction potential of the system

th ioglycollic acid-d ithioglycollic acid. E. L a r s - s o n (Svensk Kem. Tidskr., 1933, 45, 65—72).—This system gives reproducible potentials with a P t electrode in a N 2 atm ., and these are unaffected by traces of 0 2. The presence of 1 0 _c equiv. Fe per litre causes non-reproducible potentials, and renders the system sensitive to 0 2. R. P. B.

D eterm ination of the isoelectric point [of aqueous lead m onoxide]. L. Y. A n d r e w s andD. J . B r o w n (J. Physical Chem., 1933, 37, 417— 424).—The e.m.f. of cells of the type Hg, HgO, aq. K0H1H 20 , PbO, HgO, Hg indicates th a t the activity of OH' in saturated aq. PbO is 1-S4X10"4 for red PbO and 2-82 x lO "4 for 3P b0 ,H 20 . Hence K for the dissociation Pb0 ,xH 20 === P bO H '-f OH' is 2-7 x 10-4. The isoelectric point, given by the concn. of KOH a t which E==0 for the coll Hg, HgO, aq.

KOH|aq. KOH, PbO, HgO, Hg, is 5-6 x K H . The basic character of HgO is too weak to affect the results. D. R. D.

E lectrochem ical phenom ena in the catalytic decom position of hydrogen peroxide by platinum . R. W o l f e (Compt. rend., 1933, 196, 1113—1116).— The p.d. a t a P t electrode in J i-H 20 2 is a linear function of the jhi of the solution over the range p n1-25— 11-3. The potential is supposed to be connected with the catalytic dccomp. of the H 20 2.

C. A. S.A nalysis of chem ical reaction s . G. G r ig e r c s ik

(Aim. Sei. Univ. Jassy, 1933, 17, 195—198).— Mathematical. J . W . S.

O ptim um tem peratures in exotherm ic gaseous reactions. (M l l e .) A. E. K o r v e z e e and F . E . C. S c h e f f e r (Rec. trav. chim., 1933, 52, 321—326).— Theoretical. Expressions giving the temp, a t which the max. quantity of the, product of a reversible gaseous reaction is formed are derived, having regard to the rate of flow of the gas through a heated tube. Tho two cases A ~ B and 2A~B~{-C are considered.

F. L. U.Photographic analysis of explosion flam es.

W . A. B o n e (Proc. Roy. Inst., 1933, 27, 698—730).— A lecturo.

M inim al critical pressure of exp losions.K . S. G. Doss (J. Indian Chem. Soc., 1933, 10, 57— 59).—Theoretical and polemical against Semenov (A., 1928, 847). A. S. C. L.

H ydrogen-oxygen reaction. A dsorption of hydrogen on P yrex and quartz. A. T. W il l ia m s o n (J. Amer. Chem. Soc., 1933, 55, 1437—1441).— Tho ra te of adsorption of H 2 a t 760 mm. on Si02 and Pyrex in the range 400—542° has been determined. True adsorption equilibrium vals. have been obtained for Pyrex only after prolonged. contact. Alyea’s theory of the upper explosion lim it of tho H 2- 0 2 reaction is inconsistent w ith tho results (cf. A., 1931, 6 8 8 ). J . G. A. G.

M echanism of the upper lim it of inflam m ation of electrolytic gas m ixtu res. N. S e m e n o v , A. N a l b a n d j a n , and D u b o w iz k y (Trans. Faraday Soc., 1933, 29, 606— 611).—Experiments on the inflammation of electrolytic gas in presence of at. H show th a t the upper lim it of inflammation still exists, contrary to the observation of Haber and Oppenheimer (A., 1932, 576). The presence of at. H enlarges the region of inflammation, bu t does not alter its form. The extinction curve has also a similar form. Tho inflammation limits depend in somo way on the no. of initial centres, and tho chain theory of inflammation m ust be restricted, i.e., the interaction of chains m ust ho included in the theory. At. 0 has a much stronger action th an a t. H, and extremely small concns. lower the inflammation temp. 80— 100°. This supports Semenov’s theory of the mechanism of chain development in tho inflammation region (A., 1930, 299). M. S. B.

Effect of n itrogen in com bustion processes. H . H. G r a y (Chem. and Ind., 1933, 351—352).— The work of Bone and his co-workers is discussed. The inactivity of N 2 is questioned, and it is suggested


th a t tho retardation by N 2 of combustion in gaseous mixtures, particularly those containing CO, is due to a reaction between C and N2. H. F. G.

Reaction regions. XXIV. E xplosion regions of gas m ixtures in w hich an oxygen com pound is used in place of oxygen. N itrous oxide as oxygen provider. III. E xplosion regions C H ,- N 20 - A and CH4-(N „ + 0 -5 0 2)-A . W. I5. J o r i s s e n and A. A. v a n d e r D u s s e n (Rec. trav. clum., 1933,52, 327—332; cf. A., 1930, 708).—The lower and upper explosion limits in the m ixture CH4+ N 20 are respectively 2 -2 and 36-6% CH4, whilst the corresponding vals. for CH4+ (N 2+0-5O2) mixtures arc 4-3 and22-9. The quenching action of A does not differ greatly in the two cases. F. L. U.

Reaction betw een sod ium vapour and cyanogen halides. J . C u r ry and M. P 6 la n y i (Z. physikal. Chem., 1933, B, 20, 27G—282).—In the homogeneous reactions w ith CNC1 and CNBr a t 300—400° the’ratio of NaCN : N aX (X=C1 or Br) formed in the primary reaction varies from about 1 : 50 to 1 ; 150, falling as the temp, rises. I t is concluded th a t two prim ary reactions occur simultaneously : Na-f-CNX— >N aX +C N , N a+ C N X — -> N aC N + X . R. C.

Oxidation of am m onium sulphite and preparation of am m onium sulphate from gaseous sulphur dioxide, am m onia, and w ater vapour.S. I. VOLFKOYiTSCH and D. L. Z ir l in (Z. anorg. Chem., 1933, 211, 257—271).—The ra te of oxidation of aq. (NH4)2S 0 3 by air increases with rise of temp. Owing to simultaneous decomp., the optimum temp, is 70°. Cu and M n02 have a weak catalytic influence. The best results were obtained with a large surface of Si02 gel. Oxidation of solid (NH4)2S03 was very incomplete under all conditions. The product obtained by electrostatic pptn. from a mixturo of S 02,NH3, H 20 vapour, and air a t 18° contained > 9-2cJ?0of ('NH4)2S04. F. L. U.

Organic therm o chem ical m easurem ents. Velocities and h eats of saponification of am ides.III. G eneral resu lts and their interpretation.E. Ca l v e t (J. Chirn. phys., 1933, 30, 198—212).— The results of tho work previously described (A.,1932, 344; this vol., 353) are summarised and discussed. F . L. U.

Kinetics of reactions of iodine w ith ferrous salts. II. D iscussion of resu lts . A . B e r t h o u d and S. V. A l l m e n (J. Chim. phys., 1933, 30, 186— 194; cf. this vol., 469).—When K F is used to suppress the reverse change, the velocity of the reaction between I and FeS04 in aq. solution at first decreases to a min. •with increasing [I'J, then increases to a max., and finally attains a limiting val. The velocity increases with [Fe"j and cc [Ij except in the region between the min. and max. I t cc 1/[H’]. The effect of other ions has also been studied. The thermal coeff. is about 3 a t 20—30°. F . L. U.

Energy of activation. V. K . L a M e r (J. Amer. Chem. Soc., 1933, 55, 1739—1741; cf. A., 1931, 1132).—The energy of activation, E, of the reaction between CH„Br-C02Na and Na2S20 3 decreases, whilst th a t of the reaction between Na (3-bromopropionate and Na2S20 3 increases, with rise of temp. T , and

added salts have marked offects on E. The dependence of the relation between E and T on the heat capacity, free energy, and entropy of activation is considered. J . G. A. G.

Kinetics of the addition of iodine to p-phenyl- propiolic acid. E. A. M o e l w y n - H u g h e s and A. R. L e g a e d (J.C.S., 1933, 424—429).—The addition of I to CPh:C,C02H in aq. solution is bimol. In moderate concns., reaction is between the anions CPh:C'C02' and I3'. Comparison with the velocity. coeff. calc, from the collision theory indicates th a t oidy ternary collisions involving H 20 mols. are effective. Below2 - 5 x 1 0 k rises rapidly, duo to preponderance of addition of HIO to CPhlC-CO,', proceeding a t 100 times tho velocity calc, from tho collision theory.

J . S. A.Effect of the solvent on reaction velocity. III.

Interaction of persulphate and iodide ions.F. G. S o p e r and E. W il l ia m s (Proc. Roy. Soc., 1933,A, 140, 59—70).—The equationk = P x Z e r E'ltT is proposed for reaction velocity in solution. P is a probability factor varying with temp, and connected with the polar nature of reagents and products. ZerERT is the collision frequency of mols. having the necessary activation energy. Alternative ideas for the physical nature of P are proposed : (a) the solvent exerts its effect on tho breakdown of the intermediate crit. complex, causing a resolution into those substances, resultants, or reactants for which it has a greater affinity; and (6 ) the solvent exerts its effect in aiding or hindering the articulation of the reactant mols. to form the crit. complex. In both cases the effect of polar, as compared with non-polar, solvents will bo to favour the formation of polar mols., and thus to accelerate or retard the reaction velocity, according as the resultants or the reactants are the more polar. A study of the kinetics of the oxidation of iodide by S 20 8" ions over the range of ionic strength from (1= 0 -0 0 1 to 0-025 and where the product ions are of dissimilar charge favours alternative (a), but this explanation may bo obscured by disturbances duo to the high charge of the crit. complex. L. L. B.

Verification of a m echanism involving a reactive interm ediate com pound. Rate of oxidation of oxalate by hypobrom ous acid. B.M a k o w e r and H. A. L i e b h a f s k y (Trans. Faraday Soc., 1933, 29, 597—606).—Tho ra te of the reactionH 0 B r+ H C 20 4' — H 20 + 2 C 0 2+ B r ', measured in the absence of Br2, is virtually independent of Br' over the concn. range 1 0 _0 to 10~GJ f . The val. of k1 (2-7x 1 0 3 a t 0 °) is in close agreement with th a t deduced by Griffith and others (A., 1932, 344) and is thus direct evidence for the theory th a t halogens in H 20 solution are oxidising agents only through the intermediary of the hypohalous acids or their ions. Agreement is also obtained for the measured and calc. vals. of the activation energy of the reaction, 15,700 g.-cal. In alkaline solution there is an increase in rate which is independent of H ' and is accounted for by a sccondrate-determining step : 0 B r '+ H C 20 4' ----’-> H C 03'- rC02+ B r '. Assuming 10~9 as the dissociation const, of HOBr a t 0°,, ¿2=3X.105. The val. of lc1 is not affected by diffused daylight. M. S. B.


Therm al reactions of phosphorous acid w ith brom ine and chlorine. R. 0 . G r if f i t h and A. M cK e o w n (Trans. Faraday Soc., 1933, 29, 611—618). —The reaction between H 3P 0 3 and X 2 in presence of H X and the corresponding neutral salt, where X is Cl or Br, is bimol., but is retarded by H ' or X '. The data aro interpreted in terms of two simultaneous processes of the typo X 2+ H 2P 0 3'- fH 20 — > H„PO,' + 2 H X and X 2+ H P 0 3" + H 20 — > H P 0 4" + 2 IIX .

M. S. B.M echanism of sim ple substitution processes

and W alden inversion. I. E. B e r g m a n n , M. P ô l â n y i , and A. S za bo (Z. physikal. Chem., 1933,B , 20, 161— 174).—The rates of reaction of N al with d-CHIMePr and with (Z-CHlMoBu in C0Me2 solution a t 30°, leading to racémisation (cf. this vol., 31), have been measured. The reactions of I ' with the corresponding chlorides (A., 1925, i, 494) and with the bromides are apparently of this same type. CHClPhMe dissolved in SO., gradually racemises owing to the configurative lability of the positive carbonium ion formed by ionisation. R. C.

Theory of explosive reactions. H. M u r a o u r (Chim. et Ind., 1933, 29, 507—514).—The vais, of A and B in the Arrhenius formula K = B erA'RT recently calc, by Roginski (A., 1932, 1003) for numerous explosives aro criticised on the ground th a t the formula is applicable only when rise in temp, produces an increase in the reaction velocity without modifying the nature of the reaction. In numerous cases considerable changes in the nature and amount of the reaction products occur with rise in temp., and in some cases products formed a t low temp, act as catalysts in the further decomp, of the substance. According to the manner in which the necessary energy is supplied to the explosive, decomp, m ay take place in one or other of the following ways : thermal decomp, below the explosion temp., decomp, by inflammation which m ay or m ay not be followed by detonation according to the rate of decomp., and true detonation. The mechanism of these processes is explained theoretically. Bombardment of N I3 with electrons, ultra-violet rays, X-rays, or the a-rays from polonium fails to produce detonation.

A. R. P.Reaction between a gas and a so lid . Absorption

of carbon dioxide by calcium oxide and by calcium hydroxide. H. W. B. R y a n (Fae. Sci. [London], Spec. Bull., No. 2, 15 pp.).—The ra te of absorption of dry C02 by dry CaO is very small, and a surface film of CaC03 causes almost complete cessation of the réaction; in presence of H 20 vapour, however, the CaC03 crust falls away from the surface. The curve showing the increase with tim e of the wt. of Ca(OH) 2 placed in a dry C02 atm . passes through a max., and subsequently becomes parallel to the time axis; its form agrees closely with a theoretical equation, of general applicability, based on the rate of absorption of the COo and the ra te of evaporation of the liberated H 20. Ail equation is derived also for the absorption of moist C02 by moist Ca(OH),. H . F. G.

“ T ransition points ” of b ism uth and copper.J . A . H e d v a l l , R . H e d i n , a n d E. A n d e r s s o n (Z. anorg. Chcm., 1933, 212, S4—90).—The rates of

attack of Bi by 1-84IV-HN03 or 0T3iV'-I in aq. K I and of Cu by l-84Ar-H N 03 showed discontinuities a t approx. 75° and 70°, respectively, these being the transition temp, of Bi and Cu observed dilato- metrically by Cohen (cf. A., 1914, ii, 206; 1915, ii, 471). H. J . E.

Laws of com bustion of (a) colloidal [explosive] pow ders, (b ) nitrocellulose colloidal pow ders. H. M u r a o u r and G. A u n i s .— See B., 1933, 365.

Corrosion of m eta ls. P. F. T h o m p s o n .—See B., 1933, 392.

T herm al decom position of crystals of barium azide. F. E. H a r v e y (Trans. Faraday Soc., 1933, 29, 653—658).—In the thermal decomp, of single crystals of dehydrated BaNfi for the temp, range 100— 130°, an induction period is observed similar to th a t in the case of Hg fulminate (this vol., 470). The reaction accclorates a t a rate which increases as the tenth power of the time and the acceleration obeys the law, log (fZ /(fi—-iZ 0/di)=fc1<-f const., previously found to hold for fulminate and Pb styphnatc. Towards the end the reaction is unimol. A black cryst. residue is left. During decomp, nuclei of Ba are produced. M. S. B.

Reactions in the solid state. J . A. H e d v a l l (Svensk Kem. Tidskr., 1933, 45, 80—106).—Reactions between solids are greatly influenced by cryst. form, particle size, and thermal history. The presence of liquid or gas is in most cases a secondary effect, reaction taking place by the motion of atoms or ions in the solid lattice. Melting does not always increase the reaction velocity. The loosening of the lattice by thermal vibration m ay be greatly affected by the presence of other solids oven in very small amounts. Abnormal activity is often shown a t the transition temp, between two cryst. forms. Experiments on the effect of ultra-violet and X-rays on three reactions gave negative results. R. P. B.

H om ogeneous catalysis of the para-ortho- hydrogen transform ation by param agnetic substances. L. F a r k a s and H. S a c h s s e (Sitz. Preuss. Akad. Wiss. Phys.-Math. Klasse, 1933, 6 , 14 pp.).— In the gaseous phase the transformation is a first- order reaction in presence of 0 2, NO, or N 0 2. The collision efficiency is approx. equal (1 : 1 0 12) in each case, is independent of temp., and is the same when0 2 is used in aq. solution. The gaseous catalyst undergoes no chemical change. The paramagnetic ions Cu", N i", Co", Fe", and Mn" (as sulphates in0-5ilf aq. solution) aid the transformation, the velocity increasing in the order of ions given. For a const, amount of a given salt the velocity of the transformation increases with dilution. E. S . H.

Intensification by alkali carbonate or hydrogen carbonate of catalytic oxidation by traces of m ineral substances. G. Ca r p e n t i e r (Union pharm., 1932, 72, 65—67; Chem. Zentr., 1932, ii, 3761).—St. Nectaise H 20 (6 g. H C 03' per li tre ; traces of C u, Co, Mn, and Fe) gives reactions with Meyer’s, Escalch’s, and the benzidine reagents. The reactions are not given by H ,0 from which insol. carbonates, co-pptg. the active metals, have separated.

A. A. E.


Com plex form ation and catalysis. I. Increase of the rate of reduction of m olybdic acid by com plex form ation. P. K r u m h o l z (Z. anorg. Chem., 1933, 212 , 97— 108; cf. this vol., 580).— The rate of reduction of Mo03 to Mov compounds by N aI+0-05—0-2Ar-HCl is accelerated by addition of H 3P 0 4, H 4Si04, or H 4Ge04, duo to formation of the complexes H 3P 0 4,12Mo03, IT4Si04,12Mo03, and H 4G c0 4,12M o0 3. Addition of H 2S 0 4 to Mo03 reduces the catalytic activity of H3P 0 4, the I i 2S04 itself forming complexes. The catalytic action of the above complexes is discussed in relation to their stability. H. J . E.

Effect of various com pounds on the stab ility of hydriodic acid. W. J . H us a and L. M ac; i d (J. Amer. Pharm. Assoc., 1933, 22, 279—289).—The accelerating effect of 0-5N solutions of iodides on the ra te of decomp. of 0-liV-HI decreases in the following o rd e r: Fe11, Mn, Sr, Na, K, Li, Mg, Ca, NH4. Ba and Hg iodides have strong retarding effects and Zn and Cd iodides slight effect. W ith const. p n increase in iodide concn. increases the rate of decomp. of H I, and with const, iodide concn. increase of p„ increases the rate. HC1 has a. greater effect than H 2S 04. Ni", Fe", and Co” have sp. catalytic cffects in increasing the ra te of decomp. NiCl2, FeCl2, and CoS04 markedly accelerate, A12(S04)3 and CdCl2 markedly retard, and MnS04, MgCl2, SrCl2, BaClo, ZnCl2, CaCl2, and KC1 slightly retard decomp. NH 4C1, LiCl, and NaCl have no effect.

E. H. S.Peroxidative and catalytic action of ferrous

salts. II. S. G o l d s c h m id t and S. P a u n c z (Anna- len, 1933,5 0 2 ,1— 19; cf. A., 1928,251).—Comparison of the absorption curves of mixtures of FeS04, OH-CH^COjH (I), and 0H-CH 2-C02Na with those of FeS04-)-H2S04 indicates th a t complex F e" salts of(I) are not produced in any appreciable quantity. Max. oxidation of E tO H (to MeCHO and AcOH) with H 20 2 in presence of FeCl2 or FeS04 and mineral acid occurs independently of the anion of the Fe” salt a t p n about 0-7; the no. of equivs. of H 20 2 activated by 1 equiv. of F e“ is affected by the anion. No consumption of H 20 2 occurs with K 4Fe(CN)G or Na pentacyanoaquofcrroate [which, contrary to Kuhn (A., 1926, 1215), possesses catalytic activity]. When EtOH is added to a m ixture of H 20 2 and FeCl2, a renewed consumption of H 20 2 occurs and the EtOH is oxidised, thus showing th a t all the F e" is not oxidised to F e" ' by the H 20 2. Catalytic decomp. of H20 2 by Fe" salts proceeds in two stages (first rap id ; second slowly), is influenced by the anion (max. with Cl'), and decreases with rise in [H‘] (independently of the anion). Catalytic decomp. with FeCl2 and HC1 can occur more readily in presence of EtOH than in its absence. Both types of reaction are considered to be chain reactions. H. B.

Prim ary sa lt effects in reactions in which the substrate is neutral. N. N. T. S a m a r a s (J. Physical Chem., 1933, 37, 437—441).—Theoretical.

D. R. D.Catalysts for production of hydrogen by m eans

of the w ater-gas reaction. IX. Reduction of ferric oxide catalyst during cata lysis . X . Activ

ity of triferric tetroxide catalyst. R. Y o s h i -m u r a .—Sec B., 1933, 426.

Are traces of w ater really necessary for the occurrence of m any reactions? M. B o d e n s t e i n (Z. physikal. Chem., 1933, B, 20, 451—459).—The inhibition of reactions necessitating the penetration of solid surfaces by intensive drying may be due to blocking of the interfaces by films of resultants, the mols. of which w'ould diffuse away in adsorbed H 20 films and form discrete crystals. Those gas reactions which are inhibited are chain reactions or are delimited by chain reactions under the experimental conditions. The drying either introduces impurities which te rminate the chains or prevents chains starting.

R. C.Catalytic oxidation of carbon m onoxide.

(M m e .) L . S. M a t h i e u -L k v y (Compt. rend., 1933, 196, 1319—1321; cf. A., 1927, 407; 1931, 904).— The catalytic activity of Mn dioxide (measured by the rise of temp, caused by the oxidation of CO) immediately after stoving is < th a t of a sample which has adsorbed Fe, and this is < one th a t has adsorbed Mn11, but as regards resistance to ageing the order is reversed, and the effect of adsorption of Cu is opposite to th a t of Fe or Mn11. Activity is increased by prolonged stoving, which effects dehydration and increases the O content, e.g., from MnOi.65 to M n 0 1.79, whilst an oxide which had adsorbed Cu was reduced from MnO^o! before to MnOi. 79 after catalysis.

C. A. S.A bility of m eta l oxides to decom pose nitrous

oxide, and their position in periodic system .G. M. S c h w a b , R. S t a e g e r , and H. H. v o n B a u m - b a c h (Z. physikal. Chem., 1933, B, 21, 65—83).—The catalysed decomp. of N20 on various oxides has been investigated. For the oxides of metals of a given group of the periodic system the apparent heat of activation, q, increases with decrease in the at. no. of the metal. On oxides of the principal sub-groups of the second and third groups the reaction is of the first order, whereas on ZnO, CdO, and CuO it is retarded by 0 2, and on ln 20 3 by N20 . For SrO q is not affected by partial poisoning with air, which shows th a t the active centres aro all alike. For a given catalyst q does not vary materially with the method of prep., showing the active centres to have approx. the same energy content irrespective of their mode of formation. R. C.

A dsorption of nitrogen by iron synthetic am m onia catalysts. P. H. E m m e t t and S. B r u - n a u e r (J. Amer. Chem. Soc., 1933, 55, 1738— 1739).—The ratio of the initial rates of adsorption of N 2 a t 400° by Fe alone, Fe promoted with A120 3, and Fe promoted with A120 3 and K 20 is approx. equal to the ratio of the rates of NH3 synthesis performed immediately after the adsorption. The rates of N2 adsorption are consistent with this process being the first step in NH 3 synthesis. The energy of activation of desorption of N2 from the surface of Fe catalysts is 49,000—57,000 g.-cal. (cf. A., 1931, 1247).

J . G. A. G.D e c o m p o s i t i o n o f n i t r o u s o x i d e o n g l o w i n g

p l a t i n u m a n d p l a t i n u m - i r i d i u m . J . L u k e and R. F r ic k e (Z. physikal. Chem., 1933, B, 20, 357—


360).—Schwab and Eberle’s observations on tho deeomp. on glowing Pfc (this vol., 33) have been confirmed. On a P t- I r wire the reactions follows Hin- shelwood’s equation (A., 1925, ii, 310) and the activity of the wire gradually decreases during use. I f the wire is rubbed continually during the reaction, the velocity increases again, presumably owing to the formation of new active centres, bu t when rubbing ceases it falls abruptly. R. C.

Rare earths. XXXVIII. E lectrolytic preparation of rare-earth am algam s. II. D ecom position of lanthanum am algam to obtain the m etal. R. E. M e i n t s , B. S. H o p k i n s , and L. F. A u d r i e t h (Z. anorg. Chem., 1933, 211, 237—240; cf. A ., 1931, 805).—La amalgam can bo prepared by electrolysing a 20% solution of LaCl3,H20 in EtOH. The pure metal is obtained by heating the amalgam contained in a crucible made of rare-earth oxides in a vac. furnace, finally a t 1000°. Ce and Nd are obtained similarly. F . L. U.

N ew form of electrolytically deposited chrom ium . B. R a s s o w and L. W o l f .—See B., 1933, 352.

P latin g of m eta llic surfaces w ith alum inium in an alum inium ch loride-sod ium chloride m elt.V. A. P l o t n i k o v and N. N. G r a z i a n s k y .—See B., 1933, 352.

Preparation of m acroscopic thallium crystals by electrolysis. A. S p r a n t s m a n (Acta Comm. Univ. Tartuensis, 1933, A, 24, 3—5).—Tho crystals were prepared by electrolysing aq. T12S 04, using a P t anode and a Cu cathode covered by a fihn of paraffin. Tho form of the crystals depends on the eoncn. and temp, of the solution, and on tho product of the free acid and applied p.d., but is independent ofc.d. between 0 -0 1 and 0 - 1 0 amp. per sq. dm.

E . S. H.Theory of addition agent action [in electro

deposition of m eta ls]. R. T a f t .— See B., 1933,431.Cyanide-free bath for deposition of copper on

steel. C. G. F i n k and C. Y. W o n g .—See B., 1933, 431.

Free cyanide in copper electroplating. L. C.P a n — See B., 1933, 432.

Theory of corrosion. I. R elation between passiv ity and corrodibility of m eta ls. W. J .M u l l e r (Ivorrosion u. Metallschutz, 1932, 8 , 253— 260; Chem. Zentr., 1932, ii, 3782).—If a metal, having a natural coating, when immersed in an electrolyte, becomes more noble, the phenomenon is term ed self- passivation ; i t is related to increase in the size of the pores of the layer. If the coating is affected by dissolution or colloidal swelling or solvation, the phenomenon is no t observed, and the coating is not protective. A. A. E.

Form ation of silane in hydrogen discharge. E.H i e d e m a n n (Z. physikal. Chem., 1933, 164, 20—32). —In the electric discharge in H 2 in quartz vessels there is much less fatigue of the pressure decrease than in glass vessels (cf. A., 1931, 440). There is no fatigue in the amount of condensable gas ultimately formed, which supports the view th a t the fatigue in glass is due to Na remaining adsorbed on the wall.

In presence of condensed Hg, HgH, bu t practically no silane, is formed. A review of the literature shows th a t all attem pts to dem onstrate the existence of neutral unexcited H 3 have failed, and th a t no conclusive evidence of the existence of neutral highly excited H 3 has been obtained. R. C.

H eterogeneous reactions in the silent electrical discharge. II—IV. S. M iy a m o t o (J. Sei. H iroshima Univ., 1932, A, 3, 79—97, 99— 115, 117— 136; cf. th is vol., 33).—F urther observations on the reaction of H 2 with 60 solid inorg. substances are recorded.

F. L. U-Graphitic oxidation at low pressure by electric

discharge or by Röntgen irradiation. V. S ih v o - n e n (Suomen Kem., 1933, 6 , 59—6 0 b ).— Tho reactions and equilibria which occur when electric discharges of various intensities are passed between P t and graphite electrodes iii either C02+ C 0 or in 0 2 are summarised with special reference to graphitic oxidation. J . W. B.

[Decom position of m ethane by condensed sparks.] P. M o n t a g n e (Bull. Soc. d ’Encour., 1933,132, 183—186; cf. A., 1928, 589).—A max. of 75% of the CH, may be transformed into C2H 2 and H 2 by a condensed spark a t 1— 11 mm. pressure, the C^Efi decomposing on further sparking into C and H 2. The am ount of C2H 2 increases with the capacity at const, pressure, and is almost independent of the pressure a t const, capacity. Small amounts of C2H4, C2H 6, and C3H 8 are formed. The amount of CH4 decomposed in a d.c. discharge is much smaller.

H. J . E.P hotosynthesis of hydrogen chloride. I. New

experim ental m ethod ; inhibiting effect of hydrogen chloride. II. “ O xygen-free ” m ixtures.M. R it c h ie and R . G. W. N o r r is h (Proc. Roy. Soc., 1933, A, 140, 99— 112, 112— 125).—I. A method for the measurement of rates of reaction and quantum efficiencies in the formation of HC1 involves the determination of light absorption by the Cl2 in the reaction mixtures. HC'l exerts a marked inhibiting effect in H 2-C12 mixtures containing 0 2.

II. The quantum efficiency of the photochemical reaction between H 2 and Cl2 can be represented over a wide range by the expression y=(2-8X 103[H2][C12])/ ([C y + l^H C ljX /a i« .)0"1. A max. quantum yield ofl-2 x 105 is obtained. The velocity of HC1 formation is proportional to a power of the intensity of the absorbed light approaching 0-5 (actually 0-6). Reaction chains are term inated mainly by self-neutralisation. The at. mechanism for such 0 2-free mixtures involves N ernst chains, of which the at. reactions compare closely with those of the corresponding H 2-B r reaction. L. L. B.

Photochem ical reaction of hydrogen and chlorine. A. J . A l l m a n d (Nature, 1933, 131, 656).—A reply to criticism (this vol., 132). L. S. T.

Behaviour of dry chlorine-hydrogen m ixture in ligh t. F. B e r n r e u t h b r and M. B o d e n s t e i n (Sitz. Preuss. Akad. Wiss. Phys.-Math. Klasse, 1933,6 , 25 pp.).—Experiments on the union of highly- purified and intensively-dried Cl2 and H 2 under the influence of visible and ultra-violet light s h o w that


the presence of H 20 vapour is not necessary. The contrary results of previous investigators are a ttr ibuted to the presence of impurities; E. S. H.

Photochem ical k inetics of reaction between chlorine, hydrogen, and oxygen. M. B o d e n - s t e in and P. W. S c h e n k (Z. physikal. Chem., 1933,B, 20, 420—450).—The fonnation of HC1 and H 20 from streaming mixtures of H 2 and Cl2 with a considerable am ount of 0 2 can be represented by the scheme (1 ) Cl,+Av=2Cl, (2 ) C1+H2= H C 1+H , (3) H + C12=HC1+C1, (4) H + 0 2+ M = H 0 2+M , (5) .01+ 0 2+ M = C 10 2+M , with slight modifications. The yield of H 20 depends on the ratio [H2] : [Cl2] : [HC1], which indicates th a t (4) is followed by reactions of H 0 2 w ith H 2, Cl2, and HC1. Acceptable schemes for these reactions have been worked out. Reaction (3) has a heat of activation 1900 g.-cal., the collision efficiency is 1 /2 1 , and there is also a stëric factor,< 1 . Reaction (4) occurs after every triple collision in which the steric conditions are favourable. Since the velocity coeff. of H + H C 1 = H 2+C1 is only lO"3 to 10“4 times th a t of reaction (3), the formation of HC1 cannot be hindered by HC1 a t room temp. The formation of HC1 can be represented by Thon’s equation (A., 1927, 323) modified to take into account the Cl atoms formed in reaction (1 ). The results are compatible with the mechanism H + 0 2+ H 2= H 20 + OH, 2 0 H + M = H 20 2+ M for the formation of H 20 2 sensitised by Hg, bu t not with the chain mechanism H + 0 2+ H 2= H 20 2+ H . R. C.

Photochem ical decom position of chlorine monoxide betw een 2350 and 2750 Â ., and interpretation of its absorption spectrum in this region. H. J . S c h u m a c h e r and R. V. T o w n e n d (Z. physikal. Chem., 1933, B, 20, 375—384).—The quantum yield a t 20° is 4-5, indicating th a t the primary process after light absorption is dissociation into 2C1 and O. The 01 atoms then react with the C120 as previously described (A., 1932, 237). Neither0 atoms nor 0 3 react with C120 . R. C.

Solarisation. VI. Solarisation by physical development. H. A r e n s (Z. wiss. Phot., 1933, 31, 317—323).—Solarisation occurs with secondary physical development only and always when it is produced with primary physical development. Emulsions showing solarisation with chemical development show less and m ay show no solarisation with physical development. B r', if added a t peptisation, reduces the production of solarisation. This effect is removed byr washing, and is no t restored by further addition of Br'. Increased temp, of peptisation increases solarisation, and inhibits the protective action of Br'. J . L.

_ Present position of the problem of fine grain [in photography]. K. F i s c h e r (Z. wisg. Phot., 1933, 31, 297—316).—-A review. The methods considered for the production of fine grain together with high sensitivity are : (1) composition and prep, of the emulsion, (2 ) efficiency of the plate, (3 ) hypersensitisation, (4) special developers; bleaching and redeveloping or sulphiding, (5) optical diffusion of the image on enlargement. J . L.

Colour centres of the latent im age in the e lectric field. O. S t a st w (Naehr. Ges. Wiss. Gottingen,1932, 261—267 ; Chem. Zcntr., 1932, ii, 3674).

A dditive coloration of alkali halide crystals.E. M o l l w o (Nachr. Ges. Wiss. Gottingen, 1932, 254— 260 ; Chem. Zentr., 1932, ii, 3673—3674).

Effect of solvent on reaction velocity. IV. Rate and critical increm ents of som e chlorination reactions. R . E. R o b e r t s and F. A. S o p e r (Proc. Roy. Soc., 1933, A, 140, 71;—78).—Velocity coeffs.. and crit. increments of the chlorination of certain phenolic ethers and anilides have been determined in a series of solvents, and in some cases zero crit. increments were observed. As in reactions where the polar nature of reactants and resultants are markedly different, e.g., the formation of quaternary NH 4 salts, the calc, reaction rates are anomalous.

L. L. B.Photochem ical reaction of m ono alley Im alonic

a cid s. D. C o s t e r and A. v a n d e r Z i e l (Z . physikal. Chem., 1933, B, 20, 385—397).—On irradiation of n-monoalkylmalonic acids w ith sunlight, the light of a Hg arc, or X-rays, there are formed new substances of unknown character, which are not fa tty acids. They have 2 mols. between the surfaces of identity.

R. C.Photosynthesis in tropical sunlight. VI. P re s

ence of form aldehyde in rain-w ater. N. R . D h a r and A. Ram (J. Physical Chem., 1933,37, 525—531).—• Freshly collected rain-water contains up to 1 mg. of CH20 per litre, the largest quantity being obtained ■when the shower has been preceded by bright sunlight. Probably the CH20 is formed in the upper atm . by the reaction C02+ H 20 = C H 20 + 0 2 under the action of ultra-violet light. D. R. D.

Photo-reduction of carbonic acid by chlorophyll. R . W il l s t a t t e r (Naturwiss., 1933, 21, 252—253).—This takes place only in presence of small quantities of 0 2. The H atoms of the chlorophyll react singly, and not in pairs, an application of H aber’s principle. I t is supposed th a t a monodehydrochlorophyll is first form ed: chlorophyll + 0 2= 0 2H+monodehydrochlorophyll. By wandering of a H atom to the M g-H2C03 complex, the dehydro - compound is produced. In the later stages, the light reaction, dehydrochlorophyll+H 20 = 0 H + m o n o d e - Im lrochlorophyil,— dehydrochlorophyll+H (going to the M g-H2C03 complex), takes place. After the giving up of 4 H atoms, the dehydro- and monohydrocompounds . regenerate chlorophyll in the l ig h t : monodehydrochlorophyll + H 20 — OH + chlorophyll. The radicals 0 2H and OH may again furnish monodehydrochlorophyll or give H ,0 , 0 2, and H 20 2.

A. J. M.R eaction m echanism of photosynthesis. K.

S h ib a t a and E. Y a k u s h i j i (Naturwiss., 1933, 21,' 267—268).—The ehlorophyll-H2C03 complex can add 4 H 20 by co-ordination a t the Mg. The light energy absorbed by the coloured mol. activates the H 20 to give H and OH, four quanta being used. The H 2C03 acts as acceptor to the four active H atoms thus obtained, and becomes reduced to CH20 and H aO; H 2C03+ 4 (H . . . 0 H )= 2 H 20 + C H 20 + 4 0 H . The four OH radicals remaining combine forming


H o0 2, which is then decomposed by leaf catalase into0 3 and H 20 . This reaction mechanism expla ins the taking up of four quanta, as shown experimentally by Warburg. The Blackman reaction, dependent on temp., is the catalytic decomp, of the H 20 2. The 0 2 given off in photosynthesis is derived entirely from H 20 . The action of leaf catalase can be shown by investigating the action of a sp. catalase poison, e.g., N H 2OH, which soon stops the evolution of 0 2.

A. JVM.D ecom position of ozone by a-particles and by

therm al m eans. B. L e w i s (J. Physical Chem., 1933, 37, 533—534).—The ra te of decomp, of 0 3 by a-particles from R n a t room temp, follows the equation -d [0 3]/dt=dp/dt—^ [ 0 3]15, where K is independent of p and [02]. The no. of mols. decomposed per ion pair oc [03]23. The rate of thermal decomp, of 0 3 a t 85° follows an equation of the same type, bu t K varies with p and initial concn, of 0 2.

D. R. D.D estruction of h ighly polym erised m olecules

by u ltrasonic w aves. A. S z a l a y (Z. physikal. Chem., 1933, 164, 234—240).—The mols. of starch, gum arabic, and gelatin are disintegrated by the action on the solution of a frequency of 722,000 hertz. Sucrose, paraformaldehyde, and hexamethylenetetr- amine are slightly decomposed. R. C.

Isolation of halogen com pounds of the rare g ases. A. vosr A n t r o p o f f , H. F r a u e n h o f , and K. H. K r u g e r (Naturwiss., 1933, 21, 315; cf. A .,1932, 1007).—The red compound previously isolated, and stated to be K r chloride, has now been shown to be a compound of NO and HC1. This does not, however, explain the decrease in pressure observed and does not prove th a t K r chloride does not exist.

A. J . M." V ariegated ” hydrogen. A. G u n t h e r -S c h u l z e

and F. K e l l e r (Naturwiss., 1933, 21, 235—236).— If a heavy discharge is passed through H 2 which has been intensively dried w ith P 20 5, a new modification is produced which gives an extraordinarily colourful glow discharge. I t is proposed to call the new form “ variegated ” (“ Bunter ” ) H 2. A. J . M.

Parahydrogen. E. J o s e p h y (Angew. Chem.,1933, 46, 256—258).—A review.

R eactions of atom ic hydrogen w ith alkyl halides. H. M. C h a d w e l l and T . T i t a k i (J. Amer. Chem. Soc., 1933, 55, 1363— 1376).— Under the conditions employed, the reactivity of at. H with Me halides increases from zero for MeF to 100% decomp, for Mel, thus indicating th a t the heat of activation decreases rapidly in the series MeF to Mel. The products are CH4, C2H 6, and a trace of C2H4, the proportions of which do no t vary greatly with relative[H], EtCl and E tB r yield the same products containing higher [C2H 0], In general, the % decomp, decreases with decreasing at. H : alkyl halide ratio. Decomp, of the chlorides affords HC1, whilst th a t of the bromides and iodides yields the H halide and free halogen, the proportion of which decreases with increase of [H]. The prim ary reaction for the Mehalides is M e X + H ----Me-j-HX, and the subsequentsteps are discussed. J . G. A. G

Sodium n itrosyl. E. Z i n t l and A. H a r d e r (Ber., 1933, 6 6 , [R], 760—761).—The action of NO on Na in liquid Nil., a t —50° gives N a nitrosyl (I), (NaNO)„, which is not identical with N a hyponitrite.(I) and H 20 yield N 20 , NaOH, Na hyponitrite, and N 0 2'. A reducing action of (I) towards Fehling’s solution, HgO, or Ag20 -N H 3 could not be certainly established. (I) does not react with NH 4C1 in liquid NH 3 or yield a hydroxamic acid with PhCHO. N20 is vigorously evolved by the action of HCl-anhyd. E t20 . H . W.

Influence of substituents in the bases and the anions on the co-ordination index of a m eta l. I. N. Co s t a c h e s c u and A. A b l o v . II. A. A b l o v (Ann. Sci. Univ. Jassy, 1933, 17, 149—172, 173— 187).—I. The ammines derived from Cu(OAc)2 (I) or halogen-substituted (I) and 6 -methylquinoline, (3- naphthoquinoline, 2 -methylquinoline, quinoline, and C5H 5N are described.

II. The ammines derived from (CH2Ph-C02)2Cu,(I), Cu amygdalate, benzilate, glycollate, phenoxy- acetate, cupriglycollate, cupribenzilate, and cupri- amygdate and NH3, C5H 5N, ii-picoline, and (CH2-NH2)2 are described. The compositions of these compounds are compared and discussed w ith reference to the influence of substituent groups. J . W. S.

Silver ferrites. VIII. Orthoferric hydroxide w ith a side-chain . A. K r a u s e and I. G a r b a c z 6 w n a (Z. anorg. Chem., 1933, 211, 296—302; cf. this vol., 474).—Oxidation of aq. FeS04 w ith dil. H 20 2 gives a red orthohydroxide sol which is quicldy converted into a yellow ppt. consisting of its sulphate. The latter, when treated with aq. N H3, yields a brick-red orthohydroxide having a T-shaped mol. with 8 atoms of Fe. The “ ageing ” of this substance in presence of alkali has been followed by the Ag ferrite method. The end-product is goethite. F. L. U.

C om plexes of silver and zinc w ith nitrogen bases. A. T a m is ie r (Bull. Soc. chim., 1933, [iv],53, 157— 166).—The composition and stability of the compounds have been determined by the solubility method and, for Zn complexes, by the partition method also. The Ag ammines contain 2 mols. of base to 1 atom of Ag and, in agreement with earlier measurements, the prim ary saturated aliphatic amines give Ag compounds of practically the same stability, with the exception of NH 2Me, which gives an ammine of lower stability. The stability is also diminished by the presence of a double linking, an alcoholic group, or nuclear N as in C5H 5N. Zn gives several complexes with N H 3 or mixtures of the complexes containing 2 and 4 mols. of NH 3 per atom of Zn, respectively. From determinations of the stability of NH 2Me and N H 2P r complexes this appears to decrease with increasing length of chain. More than one ammine is present in these cases also.

M. S. B.E xistence of the elem ent 87. P. R e m y -G e n -

NETf: (Bull. Soc. chim., 1933, [iv], 53, 140—144).— A review of the evidence for the existence of eka- cajsium (I) and a criticism of Allison’s magneto-optical m ethod of analysis (A., 1930, 1541). From the universal association of Li and the heavy alkali metals in mineral waters and minerals, and also the asso


ciation of alkali metals and He in certain minerals rick in He, but lacking in U and Th, Lepape concluded th a t the He of the ancient lagoon deposits is due to the disintegration of (I) which has practically disappeared from the earth ’s surface.

M. S. B.Colorations in g la sses and various com

pounds due to alkali m eta l vapour. J . H o f f m a n n (Z. anorg. Chem., 1933, 211, 272—276).—The origin of the colours produced by N a vapour a t 500— 700° in various glasses, quartz, Na2S04, Na4P 20 7, and Na borates is discussed. F. L. U.

Properties and constitution of tricalcium phosphate. A. S a n f o u r c h e (Compt. rend., 1933, 196, 935—936).—Ca3(P 04)2,H20 loses no H 20 below 180° and then only 33%, a t 475° 75%, and a t 900° 95%, complete dehydration requiring a bright red heat. I t is also more acid (pa 6 -8 ) th an CaH P04 ipn 7-5) (cf._A., 1932, 696). These facts are explicable if the H 20 is “ H 20 of constitution,” the substance being an acid salt of “ hydroxyphosphoric acid ” HoP,Og, the “ neutral salt ” of which is 4Ca0,P20 5 (cf. ibid., 1204). This acid thus forms the link between H 3P 0 4 and P(O H )5 (cf. A., 1904, i, 807).

C. A. S.Preparation of phosphorescent zinc sulphide.

R. Co u s t a l (Compt. rend., 1933, 196, 1306—1307; cf. A., 1930, 576).—By fusing ZnS under 160 kg. of N2 the optimum concn. of Cu for phosphorescence is shown to be lO*5 when prepared a t 2000°; w ith no Cu the product is probably slightly phosphorescent.

C. A. S.Spontaneous oxidation of zinc and the nature

of “ p y ro p h o r ic” zinc. W. S . S e b b o r n (Trans. Faraday Soc., 1933, 29, 659—663).—W hen finely- divided Zn (either ordinary commercial Zn dust or Zn sponge prepared electrolytically) is moistened with 10% NaOH or KOH in presence of air or 0 2, bu t not of an inert gas, and the excess H 20 is removed by filter paper, a reaction occurs after a few min. H eat is evolved and oxidation to ZnO takes place with incandescence. The presence of NaOH or KOH is essential, probably in order to remove the protective surface of ZnO. W ith Cd the reaction is much less vigorous. M. S. B.

Am m ines of double chlorides. L. T. Ca t o n (Ann. Sei. Univ. Jassy, 1933, 17, 199—204).—The compounds [CdCl6](SrAm2)(CdAm2),3H20 (where Am =N H 2Ph or C6H 5N) are formed by the addition of powdered SrCl2,2CdCl2,7H20 to a solution of the amine in equal vol. of anhyd. EtO H , w ith subsequent agitation and addition of excess of light petroleum (b.p. 55—75°). J . W. S.

M ercurous oxide. R. F r ic k e and P. A c k e r m a n n (Z. anorg. Chem., 1933, 211, 233—236).—The X-ray diagram of “ Hg20 ” prepared by different methods shows only interferences characteristic of HgO, with some diffuse blackening due to Hg. No satisfactory evidence of the existence of Hg20 has yetbeen produced. F . L. U.

Oxides and hydrated oxides of a lu m in iu m .J . D. E d w a r d s and M. T o s t e r h d (J. Physical Chem,, 1933, 37, 483—488).—The different forms of A120 3

QQ

and its hydrates are described. I t is shown by chemical, X-ray, and therm al analysis th a t there is a second form of A120 3,H20 , distinct from diaspore (cf. this vol., 214). D. R. D.

A lkali alum inium silicates. VII. Behaviour of m ineral zeolites tow ards liquid am m onia.E. G r u n e r (Z. anorg. Chem., 1933, 211, 385—397; cf. A., 1932, 482).—The dehydration of zeolites and their base-exchange products by the Biltz N H 3 extraction method (A., 1928, 852, 854) resembles th a t of permutites. P a rt of the H 20 in Ca zeolites is present as [Ca(H20 )2]" (removable by NH3), and part as H 2Si0 3 or H 4Si04 (partly removable by N H3). H 20 in the anion is not extracted by NH3. Alkali zeolites yield no H 20 on treatm ent with N H 3. Formulae are suggested for desmin, alkali desmins, chabasite, alkali chabasites, heulandite, and alkali heulandites. H. J . E.

H alides of the rare earths. VII. H alides of thulium and lutecium . G . J a n t s c h , N. S k a l l a , and H. G rttbitsc h (Z. anorg. Chem., 1933, 212, 65— 83; cf. A., 1932, 1194).—Anhyd. TuC13, m.p. 821+3°, and LuC13, m.p. 892+2°, were prepared by heating the hydrated chlorides in HC1 a t 350°. T u l3, m.p. 1015+10°, and LuI3, m.p. 1045+10°, were prepared by heating the chlorides in H I a t 600°. The thermal decomp, of these compounds was studied. Partial reduction to Tu or Lu occurred on heating tho halidesin H , a t 700—900°. H . J . E.

G erm anium . X III. Calcium germ anide and unsaturated germ anium hydride. P. R o y en and R. S c h w a r z (Z. anorg. Chem., 1933, 211, 412— 422; cf. this vol., 79).—The compound CaGe was prepared from Gc and Ca or CaH2 a t 950°. Acid hydrolysis of CaGe yielded the compound GeH2, an amorphous yellow non-volatile solid, sol. in conc. NaOH to form H^, GeH4, and N a2Ge02. GeH2 reacts explosively with 0 2, forming Ge and H 20 . H . J . E.

Preparation of germ anous iodide and action of silver nitrate on halogen derivatives of m ethane.A. T c h a k ir ia n (Compt. rend,, 1933, 196, 1026— 1028);—Although GeHCl3 boils a t 75°, in presence of H 20 nothing distils over below 102°, the solution, d 1-6, finally containing 0-5 g. GeCl2 and 0-3 g. HC1 per c.c. Acid solutions of K I and GeCl2 give GoI2; Mel added to aq. (but not dry) GeCl2 slowly forms Gel2, as also does CH2I 2, bu t to a smaller extent. CHI3 (in CHC13 solution) and P h i have no action. On mixing E tO H solutions of AgN03 and CH4_71X„ no action occurs w ith X=C1, n = 2 , 3, or 4 ; X = B r, n =2 or 3. In all cases when ? i= l A gX ispptd ., the order of rapidity being I> B r> C l, as also when m=2 and X = I . These results point to the following formulae : [C+IVX 4]°, [C+nX 3]_H +, [C°X2H 2]°, [C -uH J+X -, and [C-ivH 4]° (cf. A., 1931, 322; 1932, 830). C. A. S.

T herm al decom position of am m onium [di- hydrogen] phosphate. (M m e .) R £ c h i d (Compt. rend., 1933, 196, 1163—1165; cf. this vol., 475).— (NH4)H2P 0 4 was heated for varying periods a t a series of temp., 218—800°; the product in each case was dissolved in H 20 a t 0°, and excess E tO H added, when an oil, which frequently crystallised, is p p td .; i t is neither ortho- nor pyro-phosphate. These facts


and conductomctric determinations compared with those for the N a salt show th a t firstpasses partly into a dimetaphbspliato, thence into a hexametaphosphate a t 218°, and thereafter perhaps into a tetram etaphosphate; but ;at the same time NH 3 is steadily lost, more and more free metaphos- phoric acid in the insol. form being formed, and this alone remaining after 5 min. a t 800°. This explains the supposed formation of an insol. NH 4 metaphosphate (cf. A., 1900, 651). C. A. S.

A m photeric oxide hydrates, their aqueous solutions and crystalline com pounds. XVII. Vanadic acids, polyvanadates, and vanadium sa lts as exam ples of the form ation and decom position of m ultim olecu lar inorganic com pounds in solution. G. J a n d e r and K. F . J a h r (Z. anorg. Chem., 1933, 212, 1—20; cf. this vol., 475).—Prom measurements of ionic diffusion cooffs., alkali vanadate solutions aro shown to contain successively mono-, di-, tetra-, and penta-vanadate ions, ¡with increasing p„. Each typo of ion is stable over a definite p a range. Pentavanadic acid corresponds with the hexavanadic acid previously reported (Dullberg, A., 1903, ii, 733). Totravanadic acid is transformed into pentavanadic acid through the intermediate octa- vanadic acid. H . J . E.

Com plex acids. EX. Tantalic acid. R eactions of alkali niobate and tantalate solutions w ith organic acids. H. T. S. B r it t o n and R . A. R o b in s o n (J.C.S., 1933, 419—424; cf. A., 1932, 999). —Conductomotric and potentiometric titration of K tan talate solutions affords no evidence of the existence of definite IC tantalates. Comparison of the p a data with those found for Nb20 5 provides an explanation of the C02 separation of Weiss and Landecker.

H C 02H, CH2C1-C02H, AcOH, and CH2Ph-C02H caused immediate pptn. of Ta20 5; Nb20 5 was pptd. only by excess AcOH and CH2Ph-C02H. H 2C20 4 and hydroxy-acids caused no pptn. of either Nb20 5 or Ta2Os, although lactic, tartaric, and malic acids form no definite complexes. Relatively largo amounts of H 2C20 4 are needed to dissolve Ta2Os. J . S. A.

C onstitution of nitrosylsulphuric acid, and the reactions in the lead cham ber. L. C a m b i (Atti R. Accad. Lincei, 1933, [vi], 17, 204— 206).—The formation of additive compounds by NO, and its autoxidation and reduction, aro discussed in relation to the reactions in tho Pb chamber, and, in particular, to tho formation of H 2S 0 5N. H . F. G.

C om plex m etallic sa lts of sulpham ide : an optically active inorganic sa lt. F. G. M a n n (J.C.S., 1933, 412—419; cf. A., 1932, 1101);—S 0 2(NH2)2 is of the class of chelate co-ordinating groups unable fully to saturate 6 -co-ordination metals. This is not duo to combination of 2 mols. only in the iraws-position, since Na[(H20 )2Rh(N2H 2S 0 2)2], having been resolved into optical isomerides having [J / ] 57g0 +31° and —34°, has the cis structure. Tho compounds X[(H20 )2Rh(N2H 2S 0 ,)2] (where X - H , NH 4,' d-a- plienylethylamine, and d-nor-^-ephedrine), the stable dihydrate Na3RhCl6,2Ho0 , and the compounds X[(NH3)(OH)Pt(N2H 2SO“2)2], where X = N a , K, H, were prepared. J . S. A.

“ B lue acid .” E. B k r l , K. W i n n a c k e r , and H. H. S a e n g e r (Z. anorg. Chem., .1933, 211, 379— 384; cf. A., 1932, 1219).—A reply to criticism by Manchot (this vol., 240). The compound H 2S 0 4,N 0 is formed from 100% H 2S 0 4 and NO under pressure. N 20 3 and S0 2 are not necessary. They are formed in a side reaction. H. J . E.

Colorim etric stud ies on heteropolym olybdates.P. K rum holz (Z. anorg. Chem., 1933, 212, 91—96).— Extinction coeff. measurements on the yellow solutions obtained on adding successive amounts of H 3P 0 4, Na2Si04, or N a2Ge04 to molybdic acid a t const, temp, show maxima, attributed to the complexes H 3P 0 4,12Mo03, H 4Si04 ,12Mo03, and H 4Ge04,12Mo03 in solution. Excess of H 3P 0 4 converts H 3P 0 4,12Mo03 into colourless H 3P 0 4,9Mo03. The Si and Ge compounds are more stable, and form no corresponding products with excess of H jS i04 or H 4GeOt.

. H. J . E.Preparation of telluric acid. L. I. G i l b e r t s o n

(J. Amer. Chem. Soc., 1933, 55, 1460—1461).—Te or T e02 is refiuxed with a 2 : l (vol.) m ixture of 30% H 20 2 and conc. H 2S 04. J . G . A. G.

Influence of substitution on co-ordination num ber. R . R a s c a n u (Ann. Sci. Univ. Jassy, 1933,17, 70—77).—UO" compounds form ammines with NHPhAc containing 3 mols. of the latter and various nos. of mols. of H 20 . W ith NPhMeAc, however, the ammines contain only 2 mols. of tho amine, and attem pts to former higher ammines or hydrated ammines have proved unsuccessful. The prep, and properties of tho compounds U 0 2Ex2(N 03)2, U 0 2Ex2C12, and U 0 2E x2Br2 (Ex=NPhMoAc) are described. J . W. S.

Fluorides of b ivalent m eta ls. II. Behaviour of m eta l fluorides tow ards am m on iu m , p otassium , and sod ium fluorides. A. K u r t e n a c k e r , W. F i n g e r , and F . H e y (Z. anorg. Chem., 1933, 211, 281—295; cf. this vol., 476).—Solubility measurements a t 20° and 50° in tho systems MF,>-M'F-Ho0 (M =N i, Co, Zn, Cd, Cu; M '= N H 4, K, Na") are given in tables and triangular diagrams. W ith NH4F double salts MF2,2NH4F,2H20 are formed in every case. Mixed crystals are not formed. W ith K F the solid phase consists of an extensive range of mixed crystals the constitution of which is doubtful. The same is tru e o fN a F . F . L. U.

Preparation and properties of atom ic chlorine.G. M. S c h w a b and H. F r ie s s (Naturwiss., 1933, 21, 2 2 2 ).—At. Cl was prepared by passing a discharge through purified Cl2 in a W ood’s tube of quartz. To distinguish between at. and mol. Cl use was made of the effect on a thermocouple of the heat of recombination. The recombination follows a first-order equation, and takes place on the walls. Tho life period of the atoms was 6 x 10"3 sec. S and red P react with Cl slowly, Cu and Cr20 3 more quickly. S n destroys the activity of the gas completely at first, then melts, and volatilises, after which the activity of the gas returns. The % concn. of Cl remains approx. const, between pressures of 003 and 0-1 mm. A. J . M.


Tervalent rhenium and univalent ruthenium .W. M a n c h o t and J . D u s in g (Z. anorg. Chom., 1933, 212, 21—31; cf. A., 1932, 133).—In the a u to m ation by 0 2 a t 2 0 ° of the green solution containing Re111, obtained by electrolytic reduction of K 2ReCl0, 1 equiv. of 0 2 is absorbed rapidly, tho solution becoming brown. Three additional equivs. of 0 2 are absorbed more slowly, the solution becoming deep red, violet, and then almost colourless. The violet colour is attributed to ReVI. Oxidation by KM n04 gives tho same colour changes. In aq. HC1 Re111 absorbs only 1 equiv. of 0 2, K 2ReClG crystallising out. Re111 is reduced by N aH 2P 0 2, probably to Re11, H 2 being evolved. Aq. N aH 2P 0 2 and salts of Re111 or Tim reduce salts of R u111 or Ruir to Ru1, H 2 being evolved. H. J . E.

Crystalline system s of m icrocrystalline ferric oxides. A. G i r a r d and G . C h a u d r o n (Compt. rend., 1933, 196, 925—927; cf. this vol., 351).— Magnetisation-tcmp. curves indicate th a t tho apparently colloidal ppt. obtained by rapid oxidation a t room temp, of Fe(OH )2 in excess of 0 2 in a basic medium consists of very fine particles of cubic Fo20 3; the similar ppt. obtained in an acid medium is not ferromagnetic and gives a hazy rhombohedral X -ray diagram. Rapid dehydration of lepidocrocite results in a m ixture of cubic and rhombohedral Fe20 3; hydrolysis of L iFe02 or K F e0 2 at room temp., as also oxidation a t 1 0 0 ° of pptd. hydrated Fe30 4, give the cubic variety. C. A. S.

Active iron. 0 . B a u d i s o h (Science, 1933, 77, 317—319).—A discussion of Fe oxides. L. S. T.

Ferrous hydroxide, and a ferrom agnetic ferric hydroxide. G. S c h ik o r r (Z. anorg. Chem., 1933,2 1 2 , 33—39).—Aq. FeS04 and aq. NaOH evolve H 2 on mixing only when excess of FeS04 is present. The prep, of greyish-white Fe(OH )2 under these conditions is described. On oxidising this F e(0H )2 with air or H 20 2 the dried product has the formula FeO'OH, and is ferromagnetic. Oxidation of aq. FeS04 in presence of (NH4)2S 0 4 and aq. NH 3 yielded a green hydroxide containing < 2 atoms of Fo11 per atom of Fem . H. J . E.

Analogy betw een iron and ruthenium : sodium rutheninitropentacyanide . W. M a n c h o t and J. D u s i n g (Z. anorg. Chem., 1933, 2 1 2 , 109—112; cf. A., 1930, 899).—The compounds Na4Ru(CN)G and Na4Ru(CN)G,3H20 wero prepared by acting on aq. RuCl3 with excess of NaCN. The compound Na2Ru(NO)(CN)5, prepared by warming Na4Ru(CN)G with aq. H N 0 3 on a H 20-bath , resembles the K salt, already described. Characteristic reactions are given with alkali sulphides and salts of Ag, Cu, Ni, and Co. I t resembles K 2Fe(NO)(CN)s. H . J . E.

Optical a c t i v i t y . III. d- a n d Z - C o b a lt io x a l - a t e s . C. H. J o h n s o n and A. M e a d (Trans'. Faraday Soc., 1933, 2 9 , 626—640).—[Co(C20 4)3]" ' has been resolved into its optical isomerides through the difference in solubility of the strychnine salts, and strychnine l-cobaltioxalate has been isolated. The analyses, absorption coeffs., and variation of rotatory power ■with wave-length have been determined for strychnine and K d- and Z-cobaltioxalates. The mol. ro tatory

power of K (¿-cobaltioxalato is probably the highest recorded for a puro substance. The curves of ro tatory dispersion are not symmetrical with respect to the active absorption band, tho position of zero rotation (6280 A.) being displaced about 250 A. towards the long wave-length from the max. absorption a t 6020 A. Tho results aro discussed in relation to K uhn’s work (A., 1930, 980; 1932, 1 1 1 ). S trychnine salts of d- and Z-cobaltioxalates crystallise with14 and 10 I I20 , respectively. The solid Z-salt racem- iscs completely when kept for a few weeks, but the cZ-salt quickly loses about 25% of its activity and then remains practically unchanged. M. S. B.

Preparation of norm al nickel carbonate by Senarm ont’s m ethod and the form ation of solid solutions of nickel chloride in nickel carbonate.J . K r u s t in s o n s (Z. anorg. Chom., 1933, 2 1 2 , 45—- 48).—NiC03 made by heating CaC03 with aq. NiCl2 in a sealed tube at. 180° (Senarmont, Ann. chim. phys., 1850, [iii], 3 0 , 138) always contains NiCl2, which is shown by X -ray analysis to be in solid solution in NiC03. Pure CoC03 m ay be made by Senarm ont’s method. H. J . E.

Com plex com pounds of ethylenic substances w ith p latinum sa lts . P . P f e i f f e r and H . H o y e r (Z. anorg. Chem., 1933, 2 1 1 , 241—248).—Ethylenic substances react with K 2PtCl4 to give yellow complex compounds which are often too sol. to be crystallised alone, in which case they m ay be purified with the liolp of other complex salts. The following compounds or cryst. derivatives aro described :

[Cl3Pt(Z)][Co en2Cl2], whore Z = C H 2:CH-CH„-OH, CH'CH-CHvOAc, CHMelCH-CBVOH, \

CHMe:CH-CH“2-OAc, or CHMelCH-CHO;[Cl3Pt(CHMe:CH-CH2-OH)]2[Pt(NH3)4];

[Cl3Pt(CHMe:CH-CH2-OH)][Co en2(C20 4)] ; [Cl3Pt(CHMe;CH,CH2,OH)]K. No reaction occurred in the absence of an ethylenic linking. F. L. U.

M athem atical form ula for chem ical analysis in a tw o-phase system . J . F. M cCl e n d o n (Science, 1933,77, 189—190).—A formula for calculating tho to tal “ unknown ” from two extractions (CC14 from aq. solution) is given. L. S. T.

Quantitative analysis in sm all and ultra- sm ali am ounts of liquid by m eans of potentio- m etric titration. I. T itrations in m acro-drops.K. S c h w a r z (Mikrochem., 1933, 1 3 , 6— 17).—The drop to be titra ted is suspended in a wire ring which forms one. electrode. For acidimetric and oxidation titrations a P t ring is used, for AgN03 titrations a Ag ring. The p.d. between this and a comparison electrode (Ag in 0-001iV-AgN03) is measured by a Lindemann electrometer. Quantities of the orderlO-6 g. may be determined within 1%. J . S . A.

Differing spectrographic sensitiveness of an elem ent when isolated and when m ixed w ith other elem ents. V. G a z z i (Annali Chim. Appl., 1933, 2 3 , 71—75).—The amount of an element revealed by the spark spectrum, using C electrodes, is greatly diminished when other elements are present. The observations are especially disturbed when a trace of an element, such as Fe, occurring in the electrodes is sought. T. H. P.

582 BRITISH CHEMICAL ABSTRACTS.— A

Indirect volum etric determ inations. V. C.B o r d e ia n u (Arch. Pharm ., 1933, 271, 209—215).— Titrations involving back-titration are theoretically more accurate if only a slight excess of reagent is used. This is verified for five simple determinations. An apparatus for the prep, and storage of carbonate- frce NaOH solution is described. R, S. C.

Sim ple quinhydrone electrode. K . S a n d e r a (Chem.-Ztg., 1933, 57, 303).—A soil ex tract or other solution is placed in a small crystallisation dish, and in this is stood a porcelain or glass crucible having a porous bottom and containing a solution of standard 2>n- P t electrodes dip in the inner and outer vessels.

A. G.R ecom bination of hydrogen atom s. I. I.

Am dur [with A. L. R o b i n s o n ] (J. Amer. Chem. Soc., 1933, 55, 1395—1406).—Objections to the calorimetric determ ination of at. H in mixtures w ith H 2 are immaterial under certain conditions. The contribution of wall reaction to the to tal rate of combination of at. H is small, bu t H , mols. are approx. four times as efficient as H atoms in causing recombination a t ternary collisions. J . G. A. G.

P otentiom etric determ ination of very sm all am ounts of chloride. K . S c h w a r z and C. S c h l o s - s e r (Mikrochem., 1933, 13, 18—30).—On account of the solubility of AgCl, titra tion of Cl' is not possible in aq. solutions more dil. than 0-001iV. In 80% EtO H potentiometric titration is possible down to [C l']= 2 x 10'5iV and in 98% COMe2 down to [C l']= 2xlO-°iV. J . S . A.

Volum etric determ ination of chlorine ions in presence of sod ium fluosilicate. S. K. C h i r k o v (J. Appl. Chem., Russia, 1932, 5, 1103—1106).—The solution is made ju st alkaline w ith NaOH (phenol- phthalein) and titra ted with AgN03 (K2Cr04).

Ch . A b s .D etection and determ ination of free chlorine in

chlorinated drinking' w ater. L. W . W i n k l e r .— See B., 1933, 414.

Colorim etric determ ination of iodine by m eans of chloroform . K. L. M at. t a r o v and V. B. M a t - s k i e v t t s c h (Mikrochem., 1933, 13, 85—90).—The presence of NajSO^, MgS04, or CaS04 in concns. up to 2 0 0 g. per litre does not interfere, bu t in presence of > 15 g. NaCl, 12-5 g. CaCl2, or 10 g. MgCl2 per litre, low results are obtained. Empirical formulas are given for correction of results in presence of the above salts. J . S. A.

D eterm ination and occurrence of iodine in phosphate rock. W. L. H il l and K. D. J a c o b .— See B., 1933, 346.

M odification of the W illard-W inter m ethod for fluorine determ ination. W. D. A r m s t r o n g (J . Amcr. Chem. Soc., 1933, 55, 1741— 1742; cf. this vol., 242).—A sharper end-point is obtained with 3 drops of 0-05% aq. Na alizarinsulphonate in 40 c.c. of F ' solution. J . G. A . G.

D eterm ination of hydrogen fluoride in air.Y. D. Go l d e n b e r g (J. Appl. Chem., Russia, 1932,5, 1088—1096).—Absorption in Ti(S04)2-H 2S 0 4 is satisfactory. Air is washed with H 20 , P 0 4'" is

separated w ith AgNOs ; the max. flow of air is 120 litres per hr. Ch . A b s .

A nalysis of liquid sulphur dioxide. F. A. E u s t i s .—See B., 1933, 384.

D eterm ination of sulphurous acid and alkali sulphites by potassium perm anganate. E. C a rr i e r s and R. L iau t£ (Compt. rend., 1933, 196, 933—934; cf. A., 1909, ii, 264).—H 2S 03 is accurately determined if its solution is poured into a known amount of acid aq. KM n04, 0 -0 2 A'' in KM n04 and< 5-5N in H ,S 04, and the excess KM n04 is titra ted : 5H2S0 3+2H M n0 4==3H2S04 +2M nS04+ 3 H 20. Na2S 0 3 can bo determined by means of neutral or alkaline aq. K M n04 : 3Na,S034-2KM n04-]-H20 =3Na2S0 4+ 2 K 0 H + 2 M n 0 2. C. A. S.

Oil-field w ater analysis. I. D eterm ination of sulphate by benzidine. II. Volum etric determ ination of calcium in presence of m agn esiu m . D. G. J o n e s and C. E. W o o d .— See B., 1933, 366.

N ephelom etric determ ination of sulphate in drinking w ater. H. M o h l e r .—See B., 1933, 366.

D eterm ination of nitrogen by K jeldahl’s m ethod. A. F r i e d r i c h (Mikrochem,, 1933, 13, 91— 115).—A summary of literature.

Presum ed and actual errors in m acro- and m icro-K jeldahl d istillation . E . S c h u l e k andG . V a s t a g h (Z. anal. Chem., 1933, 92, 352—356).— The chief errors arise from use of rubber stoppers and connexions, and from mechanical spraying of alkali, which may be eliminated by regulating the excess of alkali used. Dissolution of alkali from glass condensers is negligible. J . S . A.

Conductom etric titration of am m onium salts, zinc sa lts , and cyanates by the v isua l m ethod.O. P f u n d t (Angew. Chem., 1933,46, 21S— 219).— The method gives accurate results in the titra tion of NH 4C1, (NH4)2S04, and NH 4N 0 3, cither alone or mixed with alkali salts, using 0-5iV-NaOH, b u t phosphates interfere. ZnCl2, bu t not ZnS04, m ay be similarly titra ted w ith NaOH, inflexions in the curve being obtained when all the free acid is neutralised and when all the Zn is converted into Zn(OH)2. • Visual conductom etric titra tion of aq. NaCNO or KCNO with iY-AgN03 gives accurate results when the concn. is

150 mg. in 50—60 c.c. A. R. P.Volum etric determ ination of n itrates with

ferrous sulphate as reducing agent. I. M. K o l t h o f f , E. B. S a n d e l l , and B. M o sk o v it z (J. Amer. Chem. S o c ., 1933, 55, 1454—1457).—20 mg. of K N 0 3 are rapidly determined to within 0-5% and 2 mg. of N 0 3' to 3% by reduction a t 100° in an atm . of C 02 w ith excess of FeS04 in conc. HC1 and (NH4)0Mo7O24 as catalyst. C103', B r0 3', and I 0 3' interfere, b u t M n " and P 0 4'" have no effect.

J . G. A. G.D iphenylam inesulphonic acid as a reagent for

the colorim etric determ ination of n itrates. I . M.K o l t h o f f and G. E . N o p o n e n (J. Amer. Chem. Soc., 1933, 55, 1448—1453; cf. A., 1931, 1141).— Optimum conditions have been found, and determinations, accurate to within 5%, are made when


the colour produced by adding 0 -1 c.c. of 0-006.5/- Na diphenylaminesulphonate to a cooled mixture of 1 0 c.c. each of conc. H 2S04 and a solution containing 0-001—0-05 mg. of N 0 3' and 8—12 g. of KC1 per litre is compared with standards prepared a t the same time. N 0 2' interferes and is removed by boiling with NH 4C1. J . G. A. G.

C hrom om etric m ethod of determ ination of N 0 3'. J . W i e r c i ń s k i (Przemysł Chem., 1933, 17, 57—59).—The N aN 0 3 content of commercial N aN 0 2 is determined by adding the solution dropwise to boiling acidified aq. carbamide in an atm. of C 02, thus eliminating N 0 2', and reducing residual NOs' to NHoOH by addition of CrCl2, excess of which is determined by titra tion w ith standard Fe2(S04)3 in presence of KCNS as indicator. This method gives more accurate results than does direct titration with KMnO.j. R. T.

Determ ination of phosphorous, hypophos- phorous, phosphoric, and hypophosphoric acids.W. J ung (Diss., Berlin, 1930 ; Bied. Zentr., 1932, 3,A, 153).—Phosphites are oxidised by I in N aHC03 solution, and hypophosphites in acid solution. Hypophosphates are oxidised by K 2Cr20 7.

Colorim etric determ ination of phosphoric acid in argillaceous products. P. U r e o h .—See B., 1933, 345.

Colorimetric determ ination of arsenic by the M ayencon-Bergeret m ethod. J . F . R e i t h (Pharm. Weekblad, 1933, 70, 369—373).—The presence of Sb, Bi, and Fe makes the test described in the Dutch pharmacopoeia less sensitive, bu t i t is still satisfactory as a qual. test. In presence of these metals and Hg, Cu, and Se i t is necessary to separate As before determ ination (cf. B., 1933, 90). S. C.

Qualitative analysis of the arsenic and iron groups by specific reactions. T. G r o s s e t (Ann. Soc. Sci. Bruxelles, 1933, B, 53, 16—40).—The following tests suffice for the detection of the metals of the As group in the presence of one another : N a2H P 0 2 in conc. HC1 for As, E tO C S2K for.Mo, cacothelin for Sn, rhodamin-i? for Sb. Similar distinctive tests for the metals of the (NH4)2S group are : K4Fe(CN ) 0 for Fe, dimethylglyoxime for Ni, NH 4CNS in E t20 and C5Hu -OH for Co, diphenylcarbazone for Cr, (NH4)2S20 8 and AgN03 for Mn, N E t2Ph and K 3Fe(CN) 8 for Zn, alizarin-yellow for Al, H 20 2 for Ti, and tetrahydroxy- anthraquinone for Be. Analytical details are given.

A. R. P.Volum etric analysis of fluosilicic acid. V. Y.

A n o s o v . and S. K. Ch ir k o v (J. A p p l. C h em ., Russia,1932, 5, 1097— 1102).—Penfield’s method is accurateif EtOH is added after the KC1 solution. Sahlbom’s method is satisfactory if the titra tion is carried out a t room temp. Schucht’s method is less satisfactory; Treadwell’s is unsatisfactory. Ch. A b s .

Rapid sem i-m icro-determ ination of carbon dioxide in air. L. W . W i n k l e r .—See B., 1933, 366.

Technique for determ ination of radioactive content of liqu ids. R. D. E v a n s (Rev. Sci. Instr.,1933, [ii], 4, 216—222).—Methods for the removal of

radon, and for the measurement of small quantities of radon or thoron, are described. N. M. B.

P icrolonic acid, a reagent for alkali m etals.Y. V o l m a r and (M l l e .) M . L e b e r (J. Pharm. Chim., 1933, [viii], 1 7 , 366—372, 427—432).— Addition of N /50 picrolonic acid (I) to solutions of KC1 or NaCI produces a ppt. of K or Na picrolonate, provided th a t the concns. of the chlorides exceed jV/ 1 2 or iV/9 , respectively. NH4, Ca, Sr, and Ba, bu t not Li, picrolonate likewise readily separate from solutions.(I) is a useful reagent for N a and K in qual. analysis. Methods of using (I) for the separation of Na and K are outlined. W. O. K.

Polarographic determ ination of the alkali m etals. V . M a j e r (Z. anal. Chem., 1933, 92, 321—351; cf. Heyrovsky, A., 1932, 1101).—Heyrov- sky’s polarographic method is applied, using a dropping Hg cathode and large Hg anode to fulfil the requirement of unpolarisability. Electrolysis is performed in presence of a large excess of another electrolyte. The use of NMe4 salts (deposition potential for NMe.j’ —2-6 volts) permits simultaneous determination of Li (deposition potential —2-033 volts) and N a + K (—1-860 volts and —1-883 volts, respectively). The la tter are not separable. Ions of other metals present are removed either by pptn. or by complex formation. Mg and Ti are pptd. as Mg(OH)2 and Ti(OH)4; Al is converted into aluminate. Ca and Fe are best removed by pptn. w ith H 3P 0 4+NM e40H .

J .S . A.P recipitation of sm a ll am ounts of potassium

as potassium sod ium cobaltinitrite. R. S. H u b b a r d (J. Biol. Chem., 1933, 100, 557—559).—The technique of a method for the determ ination of 0-05—0-S mg. of K giving a ppt., the composition of which corresponds exactly with the formula K 3NaCo(N02)6, is described. A. L.

C olorim etric determ ination of sm a ll am ounts of potassium . A. E. S o b e l and B. K r a m e r (J. Biol. Chem., 1933, 100, 561—571).—The intensity of colour of the yellow Co-cysteine-H 20 2 complex a t a ratio of cysteine +0-5H 20 2 to Co of < 12 to 1 varies linearly w ith the Co concn. The technique of a method for the determ ination of K based on this fact is described, 10—40 mg.-% of K in 0-2 c.c. of solution being determined by colorimetric determination of the Co in the cobaltinitrite ppt. with an error of ±1-9% . The at. ratio of K to Co in the cobaltin itrite ppt. obtained under the conditions specified is const. (1 ; 0-6). A. L.

M icrochem ical contributions. VIII. L.R o s e n t h a l e r (Mikrochem., 1933,13, 83—84; cf. A.,1932, 1103).—(1) The uranyl acetate test for Na fails with NaNO,. The type of ppt. observed is given also by K N 03, but is not sp. for N 0 3'. (2) “ Hexa- methyldiaminoisopropanol di-iodide ” (Iodisan) gives w ith Cd" solutions a ppt. of clustered rod-like crystals. Zn" (also F e" ’) gives the reaction only on evaporation.

J . S. A.D eterm ination of strontium as oxalate. K. N.

P o c h in o k (J. Appl. Chem., Russia, 1932, 5, 1078— 1087).—Procedures are detailed for the determ ination of Sr alone and of Sr and Ca together. C h . A b s .

584 BRITISH CHEMICAL ABSTRACTS.-—A.

Precipitation and separation of the cations of the third and fourth groups in qualitative an a lysis .C. P a l m ie r i jpfficina, 1932, 5, 136—141).—H 2S is removed, the solution oxidised, and Li, Ba, Sr, Mg, Ca, Fc, Al, Cr, Mn, Zn, Ni, and Cr are pptd. by addition of (NH4)2H P 0 4 and aq. NH3. The ppt. is dissolved in HC1, Ba, Sr, and Ca being pptd. with H 2S 0 4 and EtOH. Otherwise the procedure is normal. Ch. Abs.

Volum etric determ ination of barium . A. R om eo (Annali Chim. Appl., 1933,2 3 , 94).—The author acknowledges the priority of Garclli and Ravenna for the method described by him (this vol., 244).

T. H. P.Direct fusion m ethod for determ ining the

radium content of rocks. R. D. E v a n s (Rev. Sci. Instr., 1933, [ii], 4, 223—-230).—Powdered rock specimens are boiled w ithout flux in an evacuated graphite resistance furnace, the evolved gases being led to an ionisation chamber. D ata for the % of radon removed from biotite granite as a function of temp., duration of heating, and fineness of grain indicate dependence on temp, only, radon removal being complete a t 1800°. N. M. B.

A nalysis of m agnesium carbonates and hydrocarbonates. (Mme.) L. W a l t e r -L e v y .—See B., 1933, 345.

D eterm ination of lead in acid calcium phosphate. D. W. K e n t - J o n e s and C. W. H e r d .—SeeB., 1933, 384.

Rapid determ ination of copper in brass, alum inium alloys, etc. M. V. C h u r a k o v .—See B., 1933, 431.

D eterm ination of copper and lead in potable w ater. J. A. W i e g a n d .— See B., 1933, 446.

Determ ination of indium and gallium w ith 8-hydroxyquinoline. W . G e i l m a n n and F . W . W r ig g e (Z. anorg. Cliem., 1933, 212, 32; cf. this vol., 43).—Priority is acknowledged. H. J. E.

D etection and determ ination of m anganese in drinking w ater. L. W . W i n k l e r .— See B., 1933, 366.

M icrochem ical reactions of rhenium . E.K r o n m a n n and N. B e r k m a n n (Z. anorg. Chem., 1933, 2 1 1 , 277—280; cf. this vol., 138).—Characteristic cryst. ppts. are obtained by mixing a drop of dil. K R e0 4 with conc. aq. H I and a sol. salt of K, Rb, Cs, Ag, Tl1, or Hg-. The first three are the most suitable. Mo03 and W 0 3 should be absent.

F. L. U.Q uantitative electrolytic reduction of iron.

G . G a l e a j a n and W . T a r a j a n (Z. anal.' Chem., 1933, 92, 357—361; cf. this vol., 138).—Pb, Cu, and Zn may be used for cathodes. Hg and graphite proved unsuitable. Pr, Cu, Pb, or graphite m ay be used for the anode. J. S. A.

P otentiom etric determ ination of iron and vanadium in ferrovanadium , and of iron and chrom ium in ferrochrom ium . P. D i c k e n s a n dG. T h a n h e i s e r .— See B., 1933, 430.

Volum etric determ ination of nitroprusside. 0 . T omIc e k a n d Z . R e k t o b ik (Coll. Czech. Chem. Comm., 1933, 5, 129—135).—The ionic product of

Ag2Fe[(CN)5NO] is 7-8 X 10~13, i.e., the solubility approximates to th a t of AgCl. Fe[(CN)5N 0]" may be titra ted potentiometrically with AgN03 in presence of Br', I ', or C N S'; if Cl' is present, i t is pptd. simultaneously and quantitatively. T itration of Fe[(CN)5NO]" by Volhard’s method is satisfactory, bu t with Mohr’s method the end-point is less clear.

H. F. G.Application of 2 : 2'-dipyridyl to the determ in

ation of ferrous and total iron in natural w aters.H. M ü l l e r .—See B., 1933, 366.

Volum etric determ ination of cobalt. C. N ik o - l o w (Przemysł Chem., 1933, 17, 46—i8).—The solution of Coni is made acid with AcOII, and Co is pptd. as K 3Co(N02)c by KNO,,. Pptn. is completed in about 18 hr., when the washed ppt. is dissolved in acid aq. KM n04, excess of K I added, and I is titra ted with Na2S20 3. The accuracy of this method compares favourably with th a t of other methods, and its simplicity and rapidity render it particularly useful for steel analysis, since it is not necessary' to eliminate other metals. R. T.

Potentiom etric determ ination of chrom ic anhydride in chrom ium -plating baths. N . I. Ch ło p i n .— See B., 1933, 432.

D eterm ination of chrom ium , m anganese, and vanadium present together in special steels. W. H i l t n e r and C. M a r w a n .— See B., 1933, 349.

D eterm ination of tungsten by 8-hydroxyquinoline in a com plex oxalate m edium . A.J ź l e k and A. R y s a n e k (Coll. Czech. Chem. Comm., 1933, 5 , 136—138).—Neither W VI nor SnIV is pptd. by 8 -hydroxyquinoline from a solution containing a mineral acid; from a neutral solution containing NH 4OAc the W is pptd., bu t the SnIV salt is hydrolysed and yields a ppt., whilst in presence of tartra te, only W VI is pptd., bu t not quantitatively. Quant, pptn. of W vx and separation from SnIV are obtained from (NH4)2C20 4 solution. In the method recommended, the solution (> 0 -1 g. W VI) is treated with 5 g. each of H 2C20 4 and NH 4OAc, neutralised with NH3, and diluted to 150—200 c .c .; a 3—4-fold excess of the reagent is added to the solution a t 60-—80°, and after 1 — 2 hr. the ppt. is removed, washed first with a neutral solution containing (NH4)2C20 4, NH 4OAc, and the reagent, and then with H 20 , and ignited at S00°. Weighing after drying a t 100—130° is not satisfactory. H. F. G.

D eterm ination of the im purities in tin by m eans of the quartz spectrograph. C. S. H it- c h e n .—See B., 1933, 351.

T antalum and niobium cathodes versu s platinum cathodes for electro-analysis. D. F . C a l- h a n e and C. M. A l b e r (Trans. Electrochem. Soc., 1933, 6 3 , 61—67).—In the electro-analytical determ ination of Cu a cathode of perforated Nb sheet gave results as accurate as the usual Pfc gauze. A similar Ta cathode gave slightly low results, and inconsistent vals. were obtained if the cathode w a s not scratch- brushed before use. Both ISTb and Ta cathodes are satisfactory in the determ ination of Zn, A g, and Ni. Zn can be deposited directly on such cathodes.

H. J . T. E.


D eterm ination of n iobium by 8-hydroxyquinoline. P. S u e (Compt. rend., 1933, 196, 1022— 1024).—About 40 mg. of Nb20 5 are brought into aq. solution (120—150 c.c.) as K niobate (in which case 0-2—0-5 g. of H 2C20 4 is added), or in aq. H 2C20 4, 5 c.c. of 10% aq. NH4OAc are added, and the mixture is neutralised with aq. NH3, heated at 70°, excess of 3% solution of 8 -hydroxyquinoline in aq. EtO H (30 : 70) added, and the whole boiled for 30 m in .; after 15 min. the cryst. ppt. is collected, washed, and dried for 2 hr. a t 115°. I ts composition is then Nb20 5,5-5C9H 70N ,4H 20 ; the 8 -hydroxyquinoline in the ppt. is determined volumetrically (cf. A., 1927, 847). The accuracy is about ± 1 % . Qualitatively, 0-01 mg. is detectable in 1 c.c.

0. A. S.Determ ination of palladium by m eans of ethyl

ene. S. C. O g b u r n , jun., and W. C. B r a s t o w (J. Amer. Chem. Soc., 1933, 5 5 ,1307—1310).—C2H 4 ppts. Pd quantitatively from aq. PdCl3 and the separation from a mixture of the chlorides of the P t metals is within 0-75% of theoretical. J . G. A. G.

Apparatus for recording the rate of cooling of a kata-therm om eter. C. P. B l a c k (J. Sci. Instr., 1933, 10, 101—105).—A simple harmonic wave trace is made on an oscillating drum. C. W. G.

Crookes’ radiom eter and the intensity of radiation. G. R u s s e l l (Phil. Mag., 1933, [vii], 15, 997— 1001).—The no. of r.p.m. of the vanes is proportional to the intensity of the radiation and to the cosine of the angle of its incidence, and inversely proportional to the square of the distance of the source. Infra-red radiation was most effective in producing rotation of the vanes. H. J . E.

Autom atic apparatus assem bly for therm al analysis. C. T. E d d y (Rev. Sci. Instr., 1933, [ii],4, 200—205).—Improved apparatus for determining thermal crit. temp., formation temp, of allotropic modifications, resistivity, and thermo-energy is described. N. M. B.

Elim ination of error of parallax in therm om eter readings. A. P e r a r d (Compt. rend., 1933, 196, 1090—1091).—The therm om eter is graduated on two diametrically opposite portions of the stem.

New m odel polarim eter. N. D e e r r (Intern. Sugar J ., 1933, 35, 138—139).—The polarimeter moves in a vertical plane, so th a t it may be used in the “ microscope position.” An arrangement for protecting the polariser and analyser prisms against fungoid etching, whilst permitting easy access for cleaning, is described. In place of dichromate solution, a gelatin filter is recommended. The scales of the polarimeter are engraved in glass and mounted vertically for reading by transm itted light.

Chem ical applications of the polarising m icroscope. N. H . H a r t s h o r n e (Chem. and Ind., 1933, 367).—Examples are given of the use of the polarising microscope for applying qual. tests to cryst. materials.

D. R. D.O ptical activity. II. N ew type of polari

m eter. C. H. J o h n s o n (Trans. Faraday Soc., 1933,

29, 618—625).—A cheap and easily constructed type of polarimeter, for the measurement of the variation of optical rotatory power with wave-length in the visible spectrum, is described. I t is intended prim arily for the examination of coloured optically active compounds undergoing racemisation in H ,0 . I ts range can probably be extended to the near u ltra violet. I t is suitable for measuring small rotations and, although making use of white light, the application is in effect monochromatic. R otatory power may be determined a t any no. of wave-lengths. Although not so accurate as the ordinary polarimeter for the examination of transparent substances a t sp. wave-lengths, it is remarkably trustw orthy in regions of strong absorption. M. S. B.

Sim ple m ethod of colour determ ination applied to fluorescence colours. E. H a s c h e k and M. H a it in g e r (Mikrochem., 1933, 13, 55—82; cf. A.,1931, 928).—The light passing through red, green, and blue filters is compared photometrically with th a t reflected from a standard white body. The results are plotted on the triangular diagram of Konig and figures representing the colour-tone, saturation, and intensity of the fluorescence are derived. The method is illustrated by application to a no. of fluorescent compounds. J . S. A.

Laboratory m odification of the Pulfrich refractom eter. V. N. T h a t t e (J. Sci. Instr., 1933,10, 1 2 0 —1 2 1 ).—By mounting two triangular glass cells on opposite sides of a rectangular glass block the use of a collimator can be avoided, C. W. G.

Sonic nephelom eter. J . S. W i l s o n (J. Sci. Instr., 1933, 10, 97— 101).—-The principle of the flicker photom eter is applied to detect differences in the intensity of two beams of light which illuminate alternately a photo-electric cell after passing through the material under test. C. W. G.

U se of a sim p le D uboscq instrum ent for colorim etry, nephelom etry, and the colorim etric determ ination of hydrogen-ion concentrations.J. G r a n t and J . H . W. B o o t h (J. Sci. Instr., 1933, 10, 106—110).—Side illumination is used for riephelo- m etry. C. W. G.

Photographic m ethod of m easuring the relative intensities of spectral lines. K. B. T h o m s o n and0 . S. D u f f e n d a c k (J. Opt. Soc. Amer., 1933, 23, 101—104).—A step diaphragm is substituted for the slit of a spectrograph. N. M. B.

M ultiple-prism g lass spectrograph. D. H.R a n k (J. Opt. Soc. Amer., 1933, 23, 84—87).—A simple instrum ent is described giving resolving power and dispersion comparable with a 2 1 -foot grating, with freedom from ghosts, and allowing many prism and lens combinations by simple adjustments.

N. M. B.Calibration of an infra-red spectrom eter w ith

a rock-salt prism . P. C. Cr o s s (Rev. Sci. Instr., 1933, [ii], 4', 197;—199).—D ata for temp, correction of dispersion, and correction for prism angles between 59° and 61°, are tabulated. N. M. B.

Experim ent bearing on T albot’s bands.A. C. G. B e a c h (Proc. Physical Soc., 1933, 45, 474—


481).—A form of spectroscopic diffraction pa tte rn is discussed and is used to explain Talbot’s bands.

W. R. A.Reference spectrum for spectrography in the

visib le spectrum . V. G a zzi (Annali Chim. Appl., 1933, 23, 75—78).—As a reference spectrum, the Fe spark visible spectrum is open to the objections th a t the lines in some places are faint and in others are so close together th a t the blank spaces are small. Good results are obtained with a m ixture prepared by heating FeCl3 5 g., CuS04,5H20 1 g., M nCl^HgO 0-1 g., (NH4)6Mo7024,4H,0 0-05 g., 0-5 c.c. of 0-lN- NaOH, and 10 c.c. of HNOa (d M l) . T. H. P.

Photo-electric instrum ent for com paring the strengths of coloured so lutions. E. W. H. S e l w y n (J. Sci. In str., 1933, 10, 116—118).—A photo-electric cell and a wedge are used. C. W. G.

Apparatus for the m easurem ent of h igh electrolytic conductivity. I. S o r g a t o (Annali Chim. Appl., 1933, 23, 133—140).—This apparatus serves for measuring electrolytic resistances of the order 1 0 5 ohms with an accuracy of 0 -1 % and a sensitivity of 1 :10,000. T. H. P.

A utom atic apparatus for electrom etric titration . H. V o g e l s (Bull. Acad. roy. Belg., 1933, [v], 19, 452—460).—Small equal vols. arc run from an electrically operated burette, and potential measurements are made simultaneously. C. W. G.

N ew type of apparatus for experim ents in secondary electron diffraction. W. T. S p r o u l l (Rev. Sci. Instr., 1933, [ii], 4, 193—196).—Using a single W crystal, small-angle secondary beams can be analysed, and contact potential difficulties are eliminated. N. M. B.

A utom atic Sprengel pum p. R . C a s t r o (Bull. Soc. d ’Eneour., 1933, 132, 187— 194).—Hg is raised to the upper reservoir by a filter pump and air-leak device. The upper reservoir feeds the Sprengel fall tube and also has an overflow tube through which excess Hg raised runs back to the collecting vessel.

H. J . E.Sim ple tap less m icroburette. K . S c h w a r z

(Mikrochem., 1933, 13, 1—5).—The liquid level is maintained hy capillarity, liquid being expelled by pressure. Accuracy of 0-2% m ay be attained on a to ta l vol. of a few cu. mm. J . S . A.

A utom atic g la ss burette jet. D. R. P a r a n j p e and D. V. Ch a n d e r k a r (J. Indian C h em . Soc., 1933, 10, 33—34). A. S. C. L.

Fractionation colum n. J . R o s i n (Chem. Fabr., 1933, 6 , 174— 175).— Ordinary columns are unsatisfactory in th a t they are effective only over a limited temp, range. The condenser described has an outer jacket in which a small quantity of a suitable liquid is placed; around the top of the jacket is a second jacket through which cold H 20 passes. The liquid should be such th a t it is kep t a t its b.p. by the vapour entering the condenser, and th a t the whole of the heavier fraction condenses; MeOH is suitable for the fractionation of E t0 H -H 20 mixtures. Typical rectification curves for aq. EtO H, light petroleum, and di- and tri-chloroethylene mixtures, obtained with the new and with ordinary columns, are given. A

special type of apparatus for use with liquids of b.p. >100° is described. H . F . G.

M easurem ent of sm all gas velocities. A.B a a d e r (Chem. Eabr., 1933, 6 , 171).—The principle of the apparatus described is th a t the stream of gas bubbles up through, and displaces, H 20 contained in a graduated tube; the tim e required for the H 20 level to fall a known distance is noted. The result is accurate to w ithin 0-003 c.c. per sec. a t moderate velocities. The apparatus does not require special calibration. H. F. G .

Sim ple device for regulating gas flow , E. G.G r e g o r y (Ami. Bot., 1933, 47, 427—428).

U niversal gas regulator, especially su ited to the regulation of vacuum . V. jELiNEK (Mitt. Kohlenforchungsinst. Prag, 1932, No. 3, 137—144).— The device consists of two chambers, an outer pressure chamber and an inner lenticular chamber, the sides of which are equipped with one or two flexible membranes. The two chambers a;re connected by a tube, capable of being closed by a valve. The inner chamber is connected between the pump and the experimental vessel. In use the two chambers are placed in communication and evacuation is commenced. On reaching the desired vac. the valve isclosed. If now the pressure in the inner chambcr falls, the membranes are forced together and the experimental vessel is isolated. The apparatus is unaffected by changes in barometric pressure. I t can be adapted to regulate pressures > atm . or incorporated in a therm ostat for controlling the temp, of gas-heated apparatus. A. H . E.

W ide-range variable gas flow -m eter. B. W.B r a d f o r d (Chem. and Ind., 1933, 363—364).—-With the flow-meter described, the ra te of flow m ay be measured or kept const, w ithin 1 % over the range 100 c.c. to 10 litres per min. D. R. D.

U niversal ebullioscope and its applications.W. S w ie n t o s l a w s k i (Rocz. Chem., 1933, 13, 176— 180).—A universal ebullioscope is described. R. T.

B eaker for quantitative analysis. G. P. B a x t e r (J. Amer. Chem. Soc., 1933, 55, 1462).—The beaker has two lips, one for pouring and the other for retaining the stirring rod. J . G. A. G.

Continuous extractor. R. J . B l o c k (J. Biol. Chem., 1933, 100, 537—541).—The apparatus has an aq. layer of high d, a middle layer of HjO-immiscible solvent, and an aq. layer of low d, a stirrer having blades in each layer being introduced. The m aterial to be extracted is placed in the bottom and collects in the top layer. A. L.

Balance for the rapid determ ination of surface tension . H . V. H u g h e s (Trans. Inst. Rubber Ind., 1933, 8 , 473—477).—A simple m ethod applicable to liquids such as rubber latex employs a modified laboratory balance, one arm of which carries a P t strip and the other supports a vertical metal rod which is partly immersed in paraffin. Small variations in load necessary to separate the P t strip from the surface of the latex or other liquid are obtained by the movement, in the paraffin, of another uniform cylinder suspended in such a way th a t its movement

GEOCHEMISTRY. 587

can be measured accurately. The results quoted include those for latex over a range of concns.

D. F. T.V iscosity as a constant of m ateria ls and its

m easurem ent. L. U b b e l o h d e (Chem. Fabr., 1933,6 , 165—167).—Detailed criticisms of a paper by Fischer (this vol., 45). F . L. U .

D iam eter of tube in the falling-sphere v iscosi- meter. 0 . M e r z (Farbe u. Lack, 1933, 201—202).— Experimental da ta are tabulated which show th a t the influence of the glass walls on the rate of fall of the sphere through low-rj cellulose n itrate solutions can be neglected w ith tubes having much smaller dian. th an th a t of the standardised apparatus. A sma'ler quantity of m aterial can therefore be used. The dimensions of the English, American, and German instiuments are compared. S . M .

Ajarm clock operating at short intervals in a laboratory. M. H a s s e l b l a t t (Chem.-Ztg., 1933, 5 7 , 195).—The clock is used when readings have to be taken a t regular intervals. . C. I.

Uriversal d ilatom eter. R . H o lc o m b (Science,1933, 7 7 , 261—263).—An apparatus for measuring the change in vol. which occurs when liquids are mixec is described. L. S. T.

Vaiuum evaporating plant for laboratory use.H. R is t r ic k : and G. S m it h (Biochem. J ., 1933, 2 7 , 96—9!).—The apparatus, consisting of six 5-litre flasks with a common central condenser and capable of disilling 2-5—4 litres per hr., is described.

F. 0 . H.Vapur pressure of vacuum cem ents. R. M.

Z A B E i(R ev. Sci. Instr., 1933, [ii], 4 , 233—234).—Ion currens as a measure of pressure for 28 cements a t a const, evacuation speed are tabulated. N. M. B

M olcular refraction in dilute solutions. I. Differential buoyancy m ethod for precision measirements of density. W. G e e f c k e n , C. B e c k m n n , and A. K r u i s (Z. physikal. Chem., 1933,B, 20,398—419)—By a modification of Lamb and

Lee’s method (A., 1913, ii, 1026) the d of solutions relative to the solvent a t concns. up to 1-5A7 m ay be determined -with a precision ranging from about 0 '0 S2 for the highest concns. to about 0 -0 82 below O-IX. Measurements with aq. NaCl and Na„C03 solutions are described. * R. C.

Sim ple m ethod for accurate determ inations of vapour pressures of solutions. D. A. S in c l a ir (J. Physical Chem., 1933, 3 7 , 495—504).—Bousfield’s isopiestic method (A., 1923, ii, 460) has been modified so th a t equilibrium is reached within a few days, it being found th a t the time required in the original method was much longer th an supposed by Bousfield. D ata have been obtained for aq. sucrose, NaCl, and ■p-0 6H,Mc-S0:iK , using aq. KC1 as standard. All the curves show an irregularity a t 0-8—l*3ilf.

D. R. D.Preparation of thin, free m etallic m em branes.

C. M u l l e r (Physikal. Z., 1933, 3 4 , 340—341).—A method for preparing very th in membranes of Ni and Fe is given. A. J . M .

Apparatus for filtration at h igh tem peratures.A. S t a d l e r (Mitt. Kohlenforschungsinst. Prag, 1931,No. 2, 80—81).—The funnel is supported in an A1 block which when heated electrically or by a gas burner serves as a heat reservoir. Even inflammable liquids m ay be filtered using a block pi'e-heated by a flame. . E. S .

Apparatus for filtration at low tem peratures, particularly for the determ ination of paraffin.B. G. S im e k (Mitt. Kohlenforschungsinst. Prag, 1931,No. 2 , 74—79).—A1 blocks, shaped to hold filters etc., are cooled with liquid air and function as cold- accumulators. E . S .

Phosphoric anhydride as drying agent. H. W . T h o m p s o n (Chem. and Ind., 1933, 308).—A reply to criticism. E. S . H.

H istory of m icrochem istry . I. H. H a r m s (Apoth.-Ztg., 1932, 4 6 , 1454—1458; 4 7 , 1274— 1275, 1293—1294, 1307—1310, 1324— 1325; Chem. Zentr.,1933, i, 1).

G eochem istry.Ozoe in the atm ospheres of p lanets. D. J.

E roi’k i (Naturwiss., 1933, 2 1 , 2 2 1 —2 2 2 ).—The quantit of 0 3 in the atm . of the outer planets has been caj. In the atm . of Venus there is less 0 3 than in the erth’s atm ., w hilst in th a t of Neptune there is approxJ.OO times as much as in air. T hat there is a high oncn. of 0 3 in the higher atm . of the planets is showiby comparison of wave-lengths of sp. bands in the sjctra of the large planets with those of the weak O3ibsorption bands in the visible spectrum of air. T h e is no qual. difference between the atm. gases of le earth and other planets. A. J . M.

Ozone in the atm osphere of p lanets. R.W il d t (aturwiss., 1933, 2 1 , 286).—The contention of Eropki (preceding abstract) th a t there is no qual. difference between the gases of the earth ’s atm . and thosof the atms. of other planets is disputed, referenceto evidence being given. A. J. M.

H elium content of natural gas. E. v o n A n -g e r e r and H. F u n k (Z. physikal. Chem., 1933, B, 20, 368—374).—The He content is determined by removing the other constituents of the gas with activated C, the purity of the residue being established by exciting i t to spectral emission by electron bombardment. The gas from the Diirkheim spring is the only German natural gas which is comparable in He content with the He-bearing natural gases of N orth America.

R. C.Iodine content of the atm osphere in H olland.

J . F. R e i t h (Biochem. Z., 1933, 2 6 0 , 115— 120; cf. A., 1930, 1628).—The I content (I) of the atm . is measured by determining (I) in rain. Although the first 0 -2 —0 -3 mm. of rain following a dry period washes out most of the I from the atm ., I continually returns to the atm., so th a t the rain is never free fromI. No support is given to the view th a t the atm . near the sea contains more I th an does the inland atm .,


except when the wind blows from the sea. The atm . in north Groningen (II) contains twice as much I as does th a t in the Rhine-M aas delta (III), probably because a t (II) there is a greater evolution of I from the ground (which is rich in it) th an a t (III).

W. McC.Petroliferous w aters. M eans of fixation of

hydrocarbons. D. A. C h a h n a z a r o e j? (Ann. Gueb- hard-Sdverine, 1932, 8 , 289—292).—Possible mechanisms whereby petroleum and H ,0 may have been produced simultaneously are discussed. J . W. S.

M ud from Lake Dapkhur, R ussia . V. I.N i k o l a e v , A. M. S o l o v o v , a n d M. A. F r is h m u t (J. Appl. Chem., Russia, 1932, 5, 809—814).

Ch . A b s .Radioactivity of w ell w aters from D um fries.

J . Mum (J. Roy. Tech. Coll., 1933, 3, 7—20).—II20 from a well 450 ft. deep in a bed of red sandstone covered with 328 ft. of agglomerate igneous rock contained 60 X 10-12 curie of RaEm , whilst th a t from a well only 1 0 1 ft. deep in the igneous rock contained 150 X l0 ~12 curie. N either H 20 contained perm anent radioactivity. A. R. P.

T herm al h istory of the earth. A. H o l m e s (J. W ashington Acad. Sci., 1933, 1G9— 195).—A lecture.

C. W. G.Chem ical com position of the earth. C. J . v a n

N i e u w e n b u r u (Chem. Weekblad, 1933, 30, 278— 280).—A lecture, dealing particularly with the frequency of occurrence of the elements as a function of the at. no. H. F. G.

M ineral deposits from M onte R osso di Verra (Monte Rosa group). II. T. Ca e p a n e s e (Atti R. Accad. Lincei, 1933, [vi], 17, 192-—196; cf. this vol., 482).—Mineralogical data for the titaniferous olivine and ampliibolite deposits of this group are given. 0 . J . W.

Q uartz-kyanite-rocks from Shetland Islands and their bearing on m etam orphic differentiation. H. H . R e a d (Min. Mag., 1933, 23, 317—328).—Quartz-kyanite-rocks occur as veins in kyanite- chloritoid-schist on the island of Unst. The latter rock is poorer in S i0 2 and relatively richer in A120 3 than the surrounding argillaceous rocks of the Saxa Vord Group. I t is suggested th a t here, as also in other types of quartz veins, there has been a segregation of S i0 2 in the veins in consequence of the metamorphism. L. J . S.

Stichtite from Shetland Islands. H. H. R e a d and B. E. D i x o n (Min. Mag., 1933, 23, 309— 316).—Rose-pink stichtite, d 2-19, a' 1-543, y 1-559, occurs as an alteration product of chromite in a serpentine-rock a t Cunningsburgh. Deducting large amounts of intim ately intermixed chromite and serpentine, analysis gave Cr20 3 17-75, Fe20 3 3-50, MgO 39-49, CO, 6-83, H 20 32-43. A discussion of this and previous analyses leads to the general formula 2(Cr,Fe)(0H)3,5Mg(OH)„MgCO3,Mg[C03,(0H),],4H,O.

l : j . s :Lapis lazuli and sp inel in crystalline lim estone

in A fghanistan. J . B a r t h o u x (C ornpt. r en d ., 1933, 196, 1131—1134).—T h e la p is la z u li o f B a d a k - shan, containing fine c r y s ta ls o f la z u r ite t h e c o lo u r o f

which is sometimes intensified by the presence of pyrites, occurs in cryst. limestone, associated with phlogopite, humite, and forsterite. Spinel with almandine and rose corundum was found a t Siz on the Oxus and a t Jagdalik in cryst. limestone associated with humite, chondrodite, phlogopite, fuchsite, rutile, sphene, haematite, and pyrite. Diopside and pargas- ite occur in the limestone, the last-named with phlogopite in emerald-green crystals containing: S i0 2 53-08, A120 3 5-04, C r,03 0-27, FeO 0-30, MgO23-86, CaO 13-36, Na„0 1-91, K 20 0-69, TiO„ 0-78, MnO 0-07, H 20 (+ ) 0-24, H 20 ( - ) 0-22, to ta l “99-62; d 3-028. C. A. S.

Zeolites. IV. Ashcroftine (kalithom sonite ofS . G. Gordon). M. H . H e y and F. A. B a n n i s t e r (Min. Mag., 1933, 23, 305—308).—X -Ray and optical determinations made on the “ kalithomsonite ” of Gordon (A., 1924, ii, 8 6 8 ) show th a t it is not a K- bearing variety of thomsonite. I t is tetragonal ivith a very large unit cell, a 34-04, c 17-49 Â., containing 40[NaK(Ca,Mg,Mn)Al4Si50 18,8H20] ; d 2-61. The refractive indices, nr 1-545, n a 1-536, are higher than those of artificial K-thomsonite and the optical orientation is different. Being a distinct species, i t is named ashcroftine. L. J . S.

O rigin of gold at Kivu. J; d e l a V a l l é e P o u s s i n (Bull. Acad. roy. Belg., 1933, [v], 19, 461— 466).—The origin is considered to be granitic.

C. W. G.T rilobites and palaeozoic phosphatic deposits.

L . Ca y e u x (C o m p t.ren d ., 1933,196,1179—1182; cf. A ., 1932, 715).—A n a ly ses of n in e d ifferen t species of tr ilo b ite sh o w th a t se v e n co n ta in o n ly 0-077—0-353, average 0-138%, of P 20 5, and tw o 1-108 and 2-162%, a m o u n ts in su ffic ien t to a cco u n t for p a læ ozoic p h o sp h a tic d ep o sits , w h ich m u st b e d u e to som e h ith erto u n recogn ised organ ism . C. A . S.

O rientation of arsenolite and senarm ontite on m ica. R. H o c a r t (Compt. rend., 1933,196, 1234— 1235).—When arsenolite or senarmonite is sublimed on to mica i t is deposited in octahedra, respectively isotropic and birefringent, oriented so th a t similar dimensions of the crystal meshes coincide, e.g., As40 613-54, Sb40 R 13-64, mica 13-66 Â. (cf. th is vol., 214).

C. A. S.C om position of the m agnetite contained in the

basalt of Aci Trezza (Catania). F. Scajfile (Annali Chim. Appl., 1933, 23, 78—84).—This anal- citic basalt contains 5% of titaniferous magnetite (d 4-45), in which 6 mois, of Fe30 4 are present per 5 mois, of FeT i03. The S% of impurities include Mn, presumably as Mn30 4 (0-5%). T. H. P.

G eochem istry of noble m eta ls. V. M. G o l d s c h m id t and C. P e t e r s (Nachr. Ges. Wiss. Gottingen, Math.-pliys. Kl., 1932, 377—401 ; Chem. Zentr., 1933, i, 38—39).—The concn. of Os, lr , and P t in rocks is too small to perm it the use of a spectrographic method on the original material. The limits using an arc spectrum (admixture with S i0 2 or A120 3) are : Ag 0-0001; Au, Ru, Rh, Pd 0-001; P t 0 005 ; Ir, Os 0-01%. A concn. method employing P b was therefore used ; 0-5 g. of original material could then be employed and the following quantities (x lO -6 g.)

g e o c h em istr y . 5S9

could be detected : Ag < 0-1; E h, Pd, P t, Au 0-1; R u O'25; Os 2-5, I r 0-5. Fe meteorites were examined; all contained P t metals and Au. Ni-rich Fe meteorites are frequently particularly rich in noble metals. Basaltic Fe, chromite, Mo- and Sn-minerals were examined. P t metals and Au are : siderophile> chalkophile>lifchophile; Ag is : chalkophile>siderophile. The distribution of noble metals in arsenides, antimonides, and sulphides, and their occurrence in Co and Ni minerals containing As and Sb, have been studied. A. A. E.

G eochem istry of beryllium . V .M . G o l d s c h m id t and C. P e t e r s (Nachr. Ges. Wiss. Gottingen, Math.- phys. E l., 1932, 360—376; Chem. Zentr., 1933, i, 37—38).—Probably the quantities of Li and Be in accessiblo rocks are < the average vals. for the whole earth. Spectrographic determinations show Be to be markedly conc. in granites and neplieline syenites (average 0-001, 0-01% BeO, respectively). Be was not found in olivine and olivine rocks, bu t is present in alkali felspar; neplieline, pyrtoxeno, amphibole, and mica. The average BcO content of rocks is determined as 0-0005%, and the average val. for meteorites is about the sam e; hence the Be, content is held to bo about 0-0002% and >0-0004%." A. A. E.

Altered pyrophysolite. I. D. W a l l e r i u s (Geol. For. Stockholm Forh., 1932, 54, 279—280; Chem. Zentr., 1933, i, 200—201).—The purple m aterial, d2-76, contained no F, and consisted chiefly of S i0 2 and A120 3 w ith a trace of Mn. A. A. E.

German ore deposits ; rare elem ents present or suspected. H. S c h n e i d e r h o h k (Metallwirt.,1932, 11, 617—622; Chem. Zentr., 1933, i, 201).— Necessary investigations are discussed. A. A. E.

Non-transparent m inerals in the lavas of Mt. Elgon, B ritish E. Africa. O. H. O d m a n (Geol. For. Stockholm Forh., 1932, 54, 285—304; Chem. Zentr:, 1933, i, 200).-—Magnetite is accompanied by perowskite, spinel, valleriite, pyrrhotine, chalcocite, covelline, bornite, chaleopyrite, proustite, and unidentified minerals, maghemite, haematite, ilmenite, ferric hydroxide, and pyrite. A. A. E.

D eterm ination of chlorine and fluorine in Etna lava. A. G ia m m o n a (Annali Chirn. Appl., 1933, 23,120— 124).—A method is described. Most of the Cl in the lava is not ionic, bu t forms p art of complex salts. The F is present partly as insol. fluoride and partly as complex ion. T. H. P.

M etam orphism of quartzite of Sarrabus. A.CAVin a t o (Atti R. Accad. Lincei, 1933, [vi], 17, 236— 241).-—The mineral is described and its structure is discussed in some detail. H. F. G.

A rtificial transform ation of felspar into kaolin.R. S c h w a r z (Naturwiss., 1933, 2 1 , 252).—The theory th a t kaolin is formed by hydrolysis of felspar has been tested experimentally by treatm ent of felspar with dil. mineral acid in a pressure bomb a t 300° for 250 hr., when kaolin was produced. Leucite can be converted into kaolin by a similar process.

A. J . M.Siw aliks and recent volcanic rocks in A fghani

stan. J . B a r t h o t jx (Compt. rend., 1933, 196, 944—947).—Several occurrences are described, and

the following analysis of a dacitoid from Zardalu consisting of phenocrysts of oligoelase-andesine, albite, pericline, biotite, and hornblende in a vitreous ground mass is given : S i02 62-74, A120 3 16-40, Fe20 3 1-60, FeO 2-67, MgO 1-90, CaO 4-82, Na20 4-53, K 20 2-59, T i0 2 0-78, P„0 5 0-15, MnO 0-10, H„0 2-08, to tal100-36. ; C. A. S.

P lasticity of rock-salt in w ater and in the dry state. L. P ia t t i (Nuovo Cim., 1932, 9, 180—188; Chem. Zentr., 1932, ii, 3665—3666).

H abit and paragenesis of fluorspar. K. O b e- n a t je r (Neues Jahrb . Min., 1932, A, 66, Bl-Bd., 89— 119; Chem. Zentr., 1932, ii, 3693).

Salt deposit on Chelekeni Island. K. P. K a l it z k i (Neft. Choz., 1931, 20, 341—354).

Ch . A b s .N ew m eteoric iron from Kyancutta, South

A ustralia. L. J . S p e n c e r [with M. H . H e y ] (Min. Mag., 1933,23, 329—333).—A mass of 72 lb., ploughed up in 1932, has the structure of a medium octahedrite and contains Fe 90-57, Ni 7-30, Co 0-39, Cu trace, S 1-12, P nil, Cl trace, C 0-13, insol. 0-22=99-73, d 7-735. The spellings, W idm anstätten, Widmann- städten, etc. (14 variants are listed), commonly applied to the lamellar octahedral structure of meteoric irons, are all incorrect; the etched figures were first observed in 1808 by A. J . F. X. Beckh von W idm anstetter (1754— 1849). L. J . S.

[Coal deposits in the B arzas d istrict.] V. A . Or e s t o v (Khim. Tverd. Topi., 1931, 2, No. 11—12,121—127). Ch . A b s .

Revised classification of so il types. E . B. D a v ie s (New Zealand J . Sei. Tech., 1933, 14, 255— 256).—A modification is suggested of Grim m ett’s scheme of soil nomenclature (ibid., 1926, 8 , 123) based on mechanical analyses. A. G. P.

Soil processes in volcanic ash-beds. Ash- beds of northern K ing-country and their secondary alum ina m inerals. N. H. T a y l o r (New Zealand J . Sei. Tech., ,1933, 14, 193—202).—The occurrence in these soils of minerals rich in A1 is explained by a series of soil-forming processes resembling those taking place a t the present time. Rhyolitic ash-beds are altered by podsolisation and andesitic beds by laterisation. When an acid humus layer is present, podsolic changes are superimposed on lateritic ones. A. G. P.

Deluvial so il processes. J. Ż ó ł c iń s k i (J. Landw., 1933, 81, 45—6 6 ).—Analytical data and profile characteristics of deluvial soils are recorded and the manner of their formation is discussed.

A. G. P.Soil form ation in southern N igeria (the

“ Hepa ” profüe). H. C. D o y n e and W. A. W a t s o n (J. Agric. Sei., 1933, 23, 208—215) —Profile characteristics of these soils formed over acid igneous rocks subjected to alternating periods of percolation and surface evaporation are recorded. The mechanism of the formation of the soil and of the concretion layer is discussed. A. G. P.

Soil structure. II. P. E h r e n b e r g (Z. Pflanz. Düng., 1933, 29, A, 25—37).—Current views are discussed. A. G. P.


H um us in [hollow] pollarded w illow s. P.H a g e n e (Compt. rend., 1933,196,1333—1335).—The humus accumulating in hollow pollarded willows, (a) old trees growing near water, (6 ) younger trees growing between a main road and large river, consists

largely (37—77%) of particles < 2 mm. diam., losing on calcination (a) 71-38—94-2, (6 ) 44-1—47-3%; p a 5-5—7-4; sol. in H 20 6-5-—8-48%; coeff. of hygro- scopicity after drying in air (a) 34—39, (b) 20-3—24-8%. C. A. S.

Organic Chem istry.H igher aliphatic com pounds. III. Preparation

of paraffins. (Miss) P . C. C a r e y and J . C. S m it h (J.C.S., 1933, 346— 347; cf. A., 1932, 468).—Hexa- decyl (I) and octadccyl iodide with Zn dust and boiling AcOH give liexa- and octa-decane, trimorphous, m.p. 27-6° (transparent form), 28-02° (opaque form), and 29-7¿0-1° (clearing of melt), respectively. Hcxadecyl bromide is partly and the chloride entirely unaffected by this trea tm ent; alternatively (I) is reduced by Zn-Cu in hot E tO H or is hydrogenated (Pd-CaC03) in PrOH. Hexadecyl formate, dimorphous, m.p. 22-7° (transparent) and 25° (26° in a capillary) (opaque), has b.p. 200°/20 mm., or 310° (slight decomp.)/760 mm. with or w ithout addition of Fe or C. (I) is largely unaffected by hydrogenation (Pd-B aS04) in CGH 4Me2. R. S. C.

Chlorination of paraffins. II. E. W e r t y - p o r o c h [with W . K w a s n i e w s k i ] (Ber., 1933, 6 6 , [£], 732—739; cf. A., 1932, 258).—Chlorination of n- (I) and wo-CsH 12 (II), n-C6H 14 (III), ?i-C7H 16 (IV), cyc/ohexane (V), and petroleum fractions, b.p. 30— 50° (VI), 50—60° (VH), and 60—70° (VIII) has been studied. Chlorination is not accelerated hy SbCl8, which is readily pptd. as an unstable double compound, the portion remaining in solution appearing to act restrictively. I has little action w ith (I) or (II), but increases in reaction through (III) and (V) to (IV). In absence of catalyst, moist Cl2 is very advantageous for the production of Cl-compounds, its effect decreasing in the sequence (I) and (II), (III), (V), (IV). Tho ratio of mono- to poly-cliloro is somewhat smaller with dry than with moist Cl2. (I) yields mainly a- and S-chloro-p-methylbutane and a little a-chloropentane. SbCl5 yields much dichloride. L ight scarcely accelerates the action of moist or dry Cl2. In simultaneous presence of light and SbCl5, the ratio C lj- : d e c o m pounds is shifted from 1 : 1 to 9—11 : 1. (II) gives all four isoamyl chlorides. (I ll) affords mainly ¡3- with little a-chlorohexane. Only a-chloroheptane is obtained from (III) with moist or dry Cl2 or in presence of I or SbCl5. Chlorination of (VI), (VII), and (VIII) gives equally good yields of Clr dcrivatives with moist Cl, or in presence of SbCl5 and sunlight. Moist has more action th an dry Cl2 on (V), bu t yields a greater proportion of dichlorides. H. W .

A ddition to doubly-linked groups. A. B u r a - w o y (Z. physikal. Chem., 1933, 1 6 4 , ] — 19).—In polymerisation, B r addition, and other reactions addition apparently occurs directly to the unsaturated atoms of the biradical mols. (cf. A., 1931, 144, 1052). The more saturated are these atoms, the more biradical mols. are present a t equilibrium, and the smaller is the ra te of addition. A mechanism is suggested for trans addition. The ra te of addition of ketens and some other compounds increases with

their polarity, suggesting th a t the first step is the relatively slow formation of a mol. compound, which rapidly changes into tho normal additive product. In additive reactions yielding heteropolar compounds the decisive factor is the transfer of electrons. The energy content of biradical mols. is calc, to be2-5—9-0 kg.-cal. > th a t of the mols. as ordinarily formulated. Reaction with biradical mols. probably requires activation. R. C.

Acetylene polym erides and their derivatives. V III. a-Alkyl-|3-vinylacetylenes. IX . N ew synthetic rubbers. IV. (3-Chloro-a-aIkyl-AaV- butadienes and their polym erides. R . A. J a c o b s o n and W. H. Ca r o t h e r s . X. Chlorination of the hydrochlorides of vinylacetylene. W. H. Ca r o t h e r s and G. J . B e r c h e t (J . Amer. Chem. Soc.,1933, 5 5 , 1622— 1624, 1624— 1627, 162S—1631).—VIII. Successive treatm ent of CH2!CH-C:CH with NaN H, (in liquid NH3) and Me2S 0 4 gives a-methyl-fi- vinylacetylene, b.p. 59-2°/760 mm. a -Ethyl-$-vinylacetylene, b.p. 84-5—85-3°/75S mm., is similarly prepared using E t2S 0 4 or |)-C6H 4Me-S03E t (in Bu20), whilst <x-n-butyl-,b.p. 62—63°/61 mm., and «.-n-heptyl-, b.p. 74-5°/9 mm., - fi-vinylacetyhnes are obtained using BuBr and heptyl bromide, respectively. These hydrocarbons polymerise slowly to yellow syrups.

IX . y-Chloro-ts^-pentadiene, b.p. 99-5—101-5°/759 mm., -hexa.dic.ne, b.p. 68-2—69°/117 mm., -octadiene, b.p. 64—65°/lS mm., and -undecadiene, b.p. 74—76°/ 1 mm., are prepared from the above CH2!CH-C:C-ALk (1 mol.), conc. HC1 (approx. 2 -2 mols.), CuCl (0-25 mol.), and NH 4C1 (0-2 mol.). Condensation of these with a-naphthaquinone and subsequent oxidation with air in EtO H -N aO H gives 2-chloro-l-meihyl-, m.p. 181°, -1 -ethyl-, m.p. 151—152°, -1-n-butyl-, m.p. 129—130°, and -l-n-hcj)tyl-, m.p. 112-5— 113-5°, -antliraquinone, respectively. In the last case, the intermediate2-chloro-1 -heptyl-1 : 4 : 11 : V2-tetrahydroanthraquinonc, m.p. 96—98°, is isolated. The above Cl-derivatives polymerise more slowly th an chloroprene (B., 1932, 156) to rubber-like substances of inferior quality to polychloroprene.

X. S-Chloro-Aa0-butadieno (I) (A., 1932, 1231) and Cl2 (1 mol.) under various conditions give fiyS-trichloro- k a-butene (II), b.p. 40—41°/10 mm. [oxidation (aq. KM n04) product, CH2C1-CHC1-C02H], and ayS-trichloro-/\P-butene (HI), b.p. 64— 65°/10 mm. (oxidation product, CH2C1-C02H ) ; (II) predominates a t —70° to —60°, whilst (III) is the m ajor product a t 40—50°. Saturation of (I) with Cl2 affords aPyy8 -pentachloro- butane (IV), b.p. S5°/10 mm. In all the above experiments about 2 0 % of undistillable m aterial is produced. p-Chloro-A“y-butadiene (1 mol.) and Cl, (1 mol.) give .about 50% of undistillable material and a mixture of products [probably containing 25—30% of (HI)].

ORGANIC CHEMISTRY. 591

pS-Dichloro-A0-butene and Cl2 afford (II), (IV), and y.$yy-tetrachlorobutane (V), b.p. 90°/32 mm., 55—57°/ 10 mm. ; (V) is the major product a t 40—60°, whilst(II) or (IV) (according to the am ount of Cl2 used) predominates a t —70° to —60°. H. B.

R eactions of substituted divinylacetylenes.A. T. B lom quist and C. S. Ma r v e l (J. Amer. Chern. Soc., 1933, 55, 1655— 1662).—Stereoisomeric '0-- dihydroxy-ti-dimethyl-A^-lelradecinenes, b.p. 144—:146°/2 mm. (I) and m.p. 86—87° (II), are prepared and dehydrated by Dupont’s method (A., 1914, i, 134) to X,i-dimethyltctradeca-kH-diene-to-inene (III), b.p. 95—98°/0-5 mm. (ozonolysis products, AcC03II and n-valerie acid), which is reduced (H2, P t0 2, Pt-black, AcOH) to fy-dimethyltetradecane, b.p. 103—• 104°/l-5 mm. Svj-Di-w-propyldeca-A^-diene-A'-inene(IV) (Dupont, loc. cit. ) is similarly reduced to S^-di-w- propyldecane, b.p. 92—93°/l-5m m. (cf. loc. cit.). (I ll) and (IV) are more stable to air th an divinylacetylene ; they add Br readily (but H B r is evolved even a t 0°) and give amorphous adducts with maleic anhydride in xylene. (IV), conc. H 2S 04, and AcOH a t about 25° afford (probably) 4 : 5-diethyl-3 : ti-di-n-propyl-A3- oyclohexenone, b.p. 107— 110°/0'7 mm. (2 : 4 -dinitrophenylhydrazone, m.p. 97—98°), oxidised (0,) to PrC02H, (probably) y-lccto-^-ethyl-a-n-propylhexoic add, b.p. 110—112°/0’6—0-7 mm. (semicarbazone, m.p. 194—195°), and a neutral compound, b.p. 82— 88°/0 -l mm., and reduced (as above) to a hydrocarbon, C16H32, b.p. 97—100°/l-5 mm. (I ll) is similarlyeon- verted into an unsaturated ketone, C10H 28O, b.p. 128—131°/l-5 mm. (2 : 4:-dinitrophenylhydrazone, m.p. 104—105°), reduced to a hydrocarbon, C16H 32, b.p.101—103°/1’5 mm. 8-/]-Dihydroxy-S-/--di-M-propj'l-At- decinene (V) and aq. H gS04 a t 100° give 3-Ice to- 2 : 2 : 5 : 5-tetra-n-propyltetrahydrofuran, b.p. 96— 10070-9 mm., and not the cyclic acetylene described by Dupont (loc. cit.). (V) is reduced (H2, P t0 2, EtOH) to 8rr dihydroxy-8-t)-di-n-propyl-Af-decene, b.p. 136—138°/1‘5 mm., which is dehydrated to 2 : 2 : 5 : 5 - tetra-n-propyl-2 : 5-dihydrofuran, b.p. 92—94°/l-5 mm.3-Keto-2 : 5 -dimethyl-2 : 5-di-n-amyltetrahydrofuran, b.p. 112—U S0/! mm., is prepared from (I). Çi-Di- hydroxy-Çi-dimethyl-fri-tetrazlecenes, b.p. 128— 130°/ 0-4 mm. and 149—151°/2 mm., are obtained by similar reduction of (I) and (II), respectively; both forms are dehydrated to 2 : 5-dimethyl-2 : 5-di-n-amyl-2 : 5-dihydrofuran, b.p. 100—10173 mm. H. B.

H exafluoroethane. F. Sw a r ts (Bull, Soc. chim. Belg., 1933, 42, 114— 118; cf. A., 1931, 601).—C2F„ has m.p. —106-3° and —94° (dimorphous). Vais, of d of thé gaseous and liquid phases a t —78° to 18-5° are represented graphically. When heated by a P t spiral a t 700° in presence of H 20 in a glass vessel, SiF4, CO, C02, and (probably) CF4 are formed. H. A. P.

Selenium dioxide, a new oxidising1 agent. III. Its reaction w ith alcohols and esters. S. A stin , A. C. C. N e w m a n , and H. L. R il e y (J.C.S., 1933, 391—394; cf. A., 1932, 1108).—In the following reactions the nature of the product depends largely on the temp., since the product is often sensitive to Se02. EtO H a t 150—230° gives glyoxal (yield under optimum conditions 41%), E t2Se03, and a substance, (CH2),„

m.p. 52°, according to the conditions. Pr°OH gives Pr%Se03, b.p. 132—133°/25 mm., a substance, (CH2)„ (n=approx. 30), m.p. 60°, a trace of AcCHO, and polymerised products. BuaOH gives Bua2SeOs, unstable, and a hydrocarbon. CH2Ph-OH gives q uantit- atively PhCHO. E t2 malonate a t 120—130° gives E t2 mesoxalate (32-3% y ield ; best known m ethod of prep.). E t2 succinate with an excess of Se02 a t 170° gives E t2 and E t H fum arate. Se is produced either in a grey “ metallic ” or a vitreous form ; the la tte r is usually contaminated with org. m atter and often explodes in 0 2. Se02 is best recovered by H N 03.

R. S. C.Preparation of the optically active form s of

secondary butyl alcohol. F . V id it z (Biochem. Z .,1933, 2 5 9 , 294— 300).—The method of Pickard and Kenyon (J.C.S., 1923, 1 2 3 , 1 ) is considerably simplified. The conditions for the separation of brucine (-)-) sec.-Bu phthalate, af, +39-0°, are described and the existence of a second form is detected. Isolation of the (—)-isomeride is not so complete, the best sample having a“ —35-33° (95-2% pure). The dissociation const, of r-sec.-Bu H phthalate is determined.

P. W. C.Dehydration and rearrangem ent of pinacolyl

alcohols and related com pounds. F. C. W h it .m o r e and P. A. K r u e g e r (J. Amer. Chem. Soc., 1933, 5 5 , 1528—1535).—Z£,-Dimethyldecan-z-ol (I), b.p. 112— 113°/15 m m ., and y-methyl-y-butylheptan-$-ol (II), b.p. 112—112-5°/14 mm., are obtained by reduction (Na and aq. Na2C03 in presence of C6H 6) of ^-dim etliyl- decan-E-one, b.p, 63—63-5°/l'5 mm., 216—217°/735 mm., and y-methyl-y-butylheptan-(3-one, b.p, 70— 71°/2 mm. [semicarbazone, m.p. 107-2— 107-7° (corr.)], which are prepared by Meerwein’s method (A., 1920, i, 2 ), respectively. (I) and (II) are dehydrated by distillation with conc. H 2S0 4 to c^-dimethyl-A3- (III) and -Ac-decene (IV) and p-methyl-y-butyl-A'3-licpt- ene (V), the structures of which are proved by ozonolysis ; relatively more of (HI) and (IV) are obtained from (II) than from (I), indicating the greater mobility of the Bu group. None of the expected p-methyl-y- butyl-Av-heptene (VI) is produced from (II), b u t (V) and (VI) are obtained by dehydration of e-isopropyl- nonan-z-ol, b-p. 75—75-5°/2 mm., which is prepared from Pr^CO,Et and MgBuBr. Octyl alcohol and T)-methylpentadecan-i-ol (dicapryl alcohol), b.p. 130— 13272 mm., are dehydrated by H 2S0 4 to defines, b.p. 122—128°/733 mm., and 106—lll° /m m ., in approx. 90% yield. H. B.

Action of periodic acid on polyhydric alcohols and on hydroxy-acids. P. F l e u r y and J . L a n g e (J. Pharm . Chim., 1933, [viii], 17, 313—326).—Oxidation of mannitol, dulcitol, volemitol, and inositol (I) by H I0 4 (II) proceeds in accordance with Malaprade’s results. (I) gives slowly, bu t quantitatively, H C 02H only. Pentaerythritol.glycollio, malic, and citric acids, which do not contain OH groups on adjacent C atoms, are unaffected by (II). Tartaric acid and (II) (1 mol.) give glyoxylio acid (III) (2 mols.). Gluconic acid and (H) (4 mols.) give CH20 (1 mol.), H C 02H (3 mols.), and (HI) (1 mol.). Saccharic acid and (II) (3 mols.) give H C02H (2 mols.) and (III) (2 mols.).

R. S. C.

592 BllITISH CHEMICAL ABSTRACTS.— A.

Alkyl peroxides. X . P eroxides of form aldehyde. Pertrioxym ethylene and tetraoxy- m ethylene diperoxide. A. R i e c h e a n d R . M e i s t e r (Ber., 1933, 6 6 , [B~\, 718—727).—Cryst. dihydroxy- methyl peroxide (I) is obtained w ith certainty by extracting formalin and perhydrol with E t20 , prolonged desiccation of the extracts over Na2S 04, and finally over P 20 5, followed by preservation of the mixed solutions (CH,0 : H 20 2= 2 : 1) a t room temp.(I) is converted by CH20 (2 mois.) in E t20 in presence of P 20 5 a t 0° into dihyaroxymethyl peroxide dihydroxy- methyl ether (II) (0H-CH2-0-CH2-0-)2> a moderately explosive liquid in which active 0 is much more accurately determined with H I th an with TiCl3. (I) becomes slowly transformed into a cryst. product which has a strong odour of CH20 and sublimes partly a t 140—145°, leaving a residue CGH 120 7 (possibly -[CH 2-0 y C H 2-0-0-CH2-[0-CH2V-), m.p. 152°. Prolonged action of P 20 5 on (II) in E t20 yields per-trioxymetliylene, CH2<C o.qjj2.ô> b-P- 35—36°/12 mm.,which very readily explodes with production of trioxymetliylene and, possibly, pertetraoxymethylene,0<C qh 2.Q.q h 2.5• Intense action of P 20 5 in E t ,0 on(II) affords tetraoxymethylene diperoxide (III),

° < C H 2-0-0-CH2> 0 , which detonates a t 94° (block) without previous melting. (I ll) is extraordinarily sensitive to pressure or friction. I ts constitution is established by its conversion into H C 02H and CH20 when its solution in E t20 is left in contact w ith aq. FeS04. II. W.

N itrates of propylene g lycol and the butylene glyco ls. C. M a t i g n o n , H. M o u r e u , and M . D odé (M em . Poudres, 1932— 1933, 2 5 , 176—188).—The yield of af3-propylene glycol dinitrate, b.p. 106°/ 27 mm., is unaffected by temp, between —10° and 10°, and only very slightly affected by the ra te of addition of the glycol to the H 2S0 4-H N 0 3. Estérification is markedly retarded by H 20 ; the max. yield is obtained with 1-1 equiv. HNO;! and sufficient H 2S0 4 to give a mass ratio H 2S0 4 : H 20 a t end of reaction=2-43. The dinitrates of œp-, b.p. 65°/l mm., 109°/28 mm., (iy- (mixed stereoisomerides), b.p. 56—58°/l mm., and cr.y-n-butylena glycol, b.p. 00°/4 mm., and of a(3-iso- hutylene glycol, b.p. 70°/6-5 mm., are similarly prepared. H . A. P.

Preparation of ay-butylene g lycol d initrate.M. A ttbry (Mém. Poudres, 1932— 1933, 2 5 , 194— 196). —Details are given for the prep, of aldol in “ almost quant.” yield, its hydrogenation to OH'CHMe'CHo'CHo'OH, and conversion of th is into its d in itrate by H N 0 3 (d 1-5) a t —10° to 0°.

H. A. P.N itroisobutanetriol [p-nitro-p-hydroxym ethyl-

propane-ay-diol] trin itrate. M. A ü b ry (Mém. Poudres, 1932— 1933, 2 5 , 197—204).—Improved processes are described for the prep, of nitrometliane (I), its condensation with CH20 (3 equivs.) to give N 0 2-C(CH,'0H)3, and conversion of this into trin itra te (with H N 03, d 1-52). The yield of (I) is increased to 70% (calc, on CFLChCOoH) by use of the Ca in place of the Na salt. “ H. A. P.

E lectrolysis of trihalogenated aliphatic acids. Trifluoroacetic and chlorodifluoroacetic acids.F. S w a r t s (Bull. Soc. chim. Belg., 1933, 4 2 , 102—113).—Electrolysis of aq. CF3-C02H gives C02, 0 2, HF, C2F 6, CF4, and trifluoromethyl peroxide, b.p. —40° to —32°, which reacts slowly with K I : (CF3),0 2-[- 2 K I+ 2 H 20 = 2 1 + 2C02+ 2 K F + 4 H F . In presence" of H F the main products are H 2 and 0 2 (containing much 0 3) in equiv. proportions, a little C2F G, and, apparently, no CF4. Equimol. amounts of CF3'C 02H and CF3-C02Na give much less 0 2, and the anodic gases contain 30% by vol. of C2F 6. CC1F2-C02H gives Cl2, C02, 0 2, HF, and CCI2F2 (possibly contam inated w ith CC1F2*CC1F2). The results are difficult to reconcile w ith the oxidation theory of the Kolbe synthesis, and the anodic formation of the free radical CHal3 is postulated. H. A. P.

E xam ination of certain azelao-glycerides obtained during the oxidation of som e sim ple synthetic and natural glycerides. T. P. H il- d itc h and S. A. S a le to re (J.S.C.I., 1933, 52, 101— IOot).—The separation of triazelain (I) or of diazelao- monosaturated glycerides (II) from the products of oxidation of natural fats by KM n04 in COMe2 solution is not practicable as an analytical means of determination of tri-unsaturated or of di-unsaturated- monosaturated glycerides. Monoazelao-clisatu rated glycerides (III), on the other hand, m ay often be isolated in a fairly pure state from the oxidation products if the corresponding mono-oleo-disaturated glycerides form a substantial proportion (50% or more) of the whole f a t ; bu t here, again, the amount isolable falls considerably below the to tal quantity present. The synthesis of some oleodistearins and oleodipalmitins is described, together with the corresponding azelao-derivatives obtained on oxidation of these and of a natural oleodistearin. Evidence is adduced which suggests th a t the p-oleo-aa'-distearin is the isomeride present in Allanblaclcia seed fat, cacao butter, Borneo tallow, and lard, thus pointing to a selected configuration in the natural oleodistearins.(II) (from dioleomonostearin or dioleomonopalmitin) and (I) (from triolein or from castor oil) have also been prepared, bu t (I) was- not obtained in anything approaching purity. These products are sol. in aq. K H C 03 and may thus be separated to a large extent from (III), when it is desired to isolate the latter. When azelaodistearin is treated in E t20 with KOH- EtO H (2/3 th a t necessary for complete saponification) “ alcoholysis ” occurs and E t stearate is produced in some quantity.

Decarboxylation of unsaturated [3-hydroxy- acids ; synthesis of alioocim ene. F . G. F isc h e r and K. L o w e n b e r g (Ber., 1933, 6 6 , [B \ , 669—674; cf. A., 1932, 600).—Aldehydes or ketones which contain one or more double linkings in conjugation with CO or belong to the aromatic series smoothly yield (3-OH-esters when treated w ith CH2Br*C02E t and Zn and then with H 20 (not mineral acid) a t 0°. The ¡3-OH-acids readily suffer therm al decom p.: 0H-CR'R"-CH 2-C02H —> (a) CR'R":CH 2+ C 0 2+ H 20 or —-> (6 ) CR'R":CH-C02H + H 20 , reaction (a) being facilitated by the accumulation of double linkings in the mol. Decarboxylation is not accelerated by


amines. The probable intermediate production of p-lactones is discussed. Crotonaldeliyde is converted into E t (3-hydroxy-A*-hexenoate, b.p. 75—77°/l mm. The corresponding acid is decomposed a t 145° into sorbic acid and A®-pentadiene, b.p. 42—44° (37%). Cinnamaldehyde yields non-distillable E t P-hydroxy- 8-phenyl-Av-pentenoate, transformed into fi-hydroxy-8- phenyl-Av-pentenoic acid, m.p. 105—106° (decomp.), whence cinnamylideneaeetie acid, m.p. 166— 167°, and a-phenyl-A“y-butadiene, b.p. 83—8 4 °/ll mm. Et $-hydroxy-$-methyl-&>'€-octadienoate, b.p. 82—83°/0-2 mm., affords non-cryst. {i-hydroxy-fi-methyl-AYi-ocla- dierwic acid, whence $-methyl-k.aVe-octatrienoic acid, m.p. 160—161°, and fi-methyl-k^'-heptatriene, b.p. 42—44°/14 mm. From methylheptadienone (I) are obtained Et $-hydroxy-%-dimethyl-b.vc-octadienoate, b.p. 94—95°/0-2 m m , and pi-dimcthvl-A^i-heptatriene. (I) and C!HMeBr-C02E t afford Et p-hydroxy■ aQZ-trimethyl-Aiy -octadienoate, b.p. 99—104°/0-2 mm., hydrolysed with difficulty to the acid, which gives P£- dimethyl-A^-octatriene (aZ/oocimene) in 75% yield. Treatment of (I) with M gEtBr affords mainly P- methyl-8-ethyl-AP-hcpten-^-ojie (II), b.p. 74—75°/13 mm. (semicarbazofie, m.p. 127— 128°), possibly accompanied by tert.-alcohol, which resinifies during distillation. (II) is hydrogenated to p-methyl-8 -ethyl- heptan-^-one (semicarbazone, m.p. 1 0 2 °). H. W.

Ricinoleic acid and /.-hydroxystearic acid.F. St r a u ss , H. H e in z e , and L. S alzm an n (Ber., 1933, 6 6 , [5], 631—639).—The incorrectness of the lit. observation th a t optically inactive X-hydroxystearic acid is obtained by reduction of ricinoleic acid (I) is established. The m ixture of acids obtained by hydrolysis of castor oil is frozen from alcohol and crude (I) is converted into the Pb salt, which is extracted with E t20. The sol. salt is transformed into the Me ester (II) (b.p. 165—166°/0-l mm., 153—155°/0-05 mm., [a]g +5-17°, [ajg6 +3-52° in CHC13, [afg +10-30° in C5H 5N), the b.p. of which is a poor criterion of purity. I t is best purified through the Bz derivative, b.p. 195—196°/0-08 mm., [a]fi +15-99°, the Ac compound, b.p. 170— 171°/0-l mm., [a ]T +24-20°, having a b.p. too close to th a t of (II). (I), [ajg+7-86°, is dimorphous. When not too strongly cooled, it solidifies slowly and melts a t 6 —8 ° (III). When preserved a t 7° it re-solidifies and then has m.p. 15—17° (IV). Molten (IV) when suddenly cooled to —30° or —40° retains its m .p .; if preserved a t 4—5° for several hr. and then cooled to 0 ° or somewhat lower, it passes into (III). The purification of (I) from EtOAc a t —45° to —50° is described. Hydrogenation of (II) in AcOH (W illstatter) is accompanied by absorption of an excess of about 10% of H 2 and production of Me stearate, which is readily removed. \-~>.-IIydroxystearic acid has m.p. 80-5—81°, [a]1,? —0-41° in CjHjN [Me ester, m.p. 35—37°, [a]jJ —0-32° in CBH BN, -0 -32° in CHC13, -0 -3 4 ° in C2H 2C14; its benzoate, b.p. 198—199°/0-05 mm., [a]1" -1 -2 5 °; acetate, b.p. 158—160°/0-l mm., 151—152°/0-01 mm., Mii +0-10°, and 3 : 5-dinitrobenzoate, m.p. 39—40°, M S -1 -04° in CHCI3). H. W.

Acetoacetic ester condensation. V. Condensation of h igher esters. R. R . B rxese an d S . M. McE l v a in (J. Amer. Chem. Soc., 1933, 55, 1697—

1700).—Tlio following are prepared in 74—84% yield from the appropriate Alk-CO,,Et by the method previously described (A., 1929, 1424) : E t a-valeryl- valerate, b.p. 109—110°/5 mm., a-hexoylhexoate, b.p.132—133°/5 mm., a-heptoylheptoate, b.p. 147— 148°/ 5 mm., a-octoyloctoate, b.p. 173—175°/5 mm., a- nonoylnonoate, b.p. 195—200°/5 mm., a-decoyl- decoate, b.p. 220—225°/5 mm., a -dodecoyldodecoate, m.p. 28—29°, and a-tetradecoyltetradecoate, m.p. 37— 38°. These are hydrolysed (KOH in 90% EtOH) to COBu2, and diamyl, m.p. 14— 15°, dihexyl, m.p. 30— 31°, diheptyl, m.p. 41—42°, dioctyl, m.p. 52—53°, dinonyl, m.p. 58—59°, diundecyl, m.p. 68—69°, and ditridecyl, m.p. 78—79°, ketones, respectively, in yields of 72—98%. H. B.

Syntheses w ith “ acetonised ” glyceric ester.I . H. 0 . L. F isc h e r and E. B a e r (Helv. Cliim. Acta; 1933, 16, 534—547).—Me a(3-isopropylidenedi- oxypropionate (I), b.p. 84—86°/15 mm. (the Et ester has b.p. 84—88°/9 mm.), prepared in 43-5% yield from Me glycerate, COMe2, and ZnCl2 (subsequently removed with quinoline), is hydrolysed [aq. Ca(OH)2] to the C asa it (+ H 20) of ap-isopropylidenedioxyprop- ionic acid [amide, m.p. I l l — 1 1 2 °, from (I) and MeOH-NH3; hydrazide, m.p. 78—79°; piperidide(II), b.p. 89—91°/0-4 mm.]. The Me ester, b.p. 81— 83°/15 mm., of ap-ethylidenedioxypropionic acid (hydrazide, m.p. 93—95°) is prepared from Me glycerate, MeCHO, and 84% H3P 0 4. (I), Na, and COMe., give $S-diketo-zX,-isopropylidenedioxyhexane, b.p. 107— 109°/11 mm. [purified through its Cu salt, m.p. 184— 185°; y-acetoxy-derivative, b.p. 100— 106°/0-8 mm., obtained by the action of Pb(0A c )4 in CfiH c]. yz-Di- kcto-'C,r\-isopropylidenedioxy-$$-dimethylheptam, b.p. 116—118°/8 mm. (Cwsalt, m.p. 163°), ^-dikelo-T^-isopropylidenedioxy-$-methyl-bP-octene, b.p. 143— 147°/ 10 mm. (Cu salt, m.p. 145—146°), Pli -Jceto-y8-iso- propylidenedioxybutyl ketone, b.p. 135°/0-4 mm. (Cu salt, m.p. 190—191°), and 2-a[3-isopropylidenedioxy- propionylzyc\ohexanone, m.p. 44— 46° (Cu salt, m.p. 198°), are prepared from (I), Na, and COMeBuy, mesityl oxide, COPhMe, and «/cfohexanone, respectively. MgMel and (II) give Me a^-isopropylidenedi- oxyethyl ketone, b.p. 57—66°/10 mm., which with E t2C20 4 and E tO H -N aO Et affords Et a.y-diketo-&z- hopropylidenedioxyhexoate, b.p. 96—97°/0-l mm. (Cu salt, m.p. about 175°) [the M e ester, b.p. 87—89°/0-l mm. (Cu salt), is prepared using Me2C20 4 and MeOH- NaOMe; its enol Me ether could not be obtained cryst.] ; definite products were not obtained by hydrolysis (dil. AcOH ; 0 -liV-HCl) of these esters. H. B.

R efractom etric determ ination of organic acids.(Mme.) G. A l l a r d (Compt. rend., 1933, 196, 1118— 1119 ; cf. th is vol., 621).—The Pb salts of glutaric (I), adipic (II), pimelic (III), and suberic acid (IV) are too sol. for determination of these acids by measuring n during pptn. by Pb(OAc)2. AgOAc is suitable in determining (II) (O-OliLf) and (IV) (0-005!/), bu t not for mixtures. Pptn. by Hg(OAc)2 gives results within a few % for (I)—(IV) and their Na salts, and in a mixture of (I), (II), and azelaic acid the errors are 2%, 15%, and 4-5%, respectively. A . C.

U nsaturated aS-dicarbonyl com pounds. V III. D erivatives of d im ethylfum aric acid. R . E.


L tjtz and R. J . T a y l o r (J. Amer. Chom. Soc., 1933, 55, 1585— 1592).—Dimethylfumaric acid {anilide, m.p. 267° (all m.p. are corr.); M e H ester (I), m.p. 81° [chloride (II), b.p. 90—91° (corr.)/20 m m .; anilide, m.p. 74—75°, hydrolysed (aq. E tO H-K OH) to di- methylfumaranilic acid, m.p. 195°]; E t H ester (III), b.p. 118°/1 mm. (chloride, b.p. 90—91°/14 m m .; anilide, m.p. 121-5— 122°)} and PG1S give dimethyl- fum aryl chloride, b.p. 79-5°/22 mm., which is rearranged by A1C13 a t 100° into the ^-dimethylmaleyl chloride of Otto and H olst (A., 1890, 1327). (I) isbest prepared by partial hydrolysis of Me dimethyl- fum arate (IV) with KOH in 95% MeOH; hydrolysis w ith KOH in E taO -EtO H gives (III). (II) and A1C13 at-100° afford MeCl and dimethylmaleic anhydride (V).(IV) and MeOH-NaOMe in cold E t20 give (mainly) a Me H mcthoxydimethylsuccinate,, b.p. 130—131°/2mm. ; the free acid, m.p. 133-5°, when heated to 200°, yields(V). E t dimethylfumarate, (IV), and (I) undergo rearrangement during alkaline hydrolysis in EtO H containing min. am ounts of H 20 ; in dil. (40% H 20) EtOH, dimethylfumaric acid results. Rearrangem ent m ust occur during hydrolysis, since the acid is stable under the conditions used. H. B.

P lant dyes, XLVII. Isom erism of the b ixins. Theory of form ation of carotenoid p igm en ts in plants. P. Iv a r r e r and T . T a k a h a s h i . XLVIII. Violanin. P. K a r r e r and G. d e Me u r o n . XLEX. Synthesis of perhydrocrocetin. P . K a r r e r , F. B e n z , and M. St o ll . L. Conversion of perhydrocrocetin into perhydronorbixin. P. K a r r e r and E. B e n z (Helv. Chim. Acta, 1933,16, 287— 292, 292—29G, 297—302,337—338).—XLVII. Partial hydrolysis of methylbixin w ith 1 equiv. of NaOH in E tO H a t 65° gives stable and labile bixins, and a m ixture, m.p. 130°, of methylbixin and bixin, converted by CH2N 2 into methylbixin. H asselt’s iso- bixin (cf. A., 1911, i, 550) was no t observed. In agreement with Herzig and Ealtis (A., 1923, i, 477), metliylation of norbixin w ith MeOH-HCl is found to give the Me2 ester of stable norbixin. I n reply to K uhn and Grundmann (this vol., 145) it is claimed th a t the carotenoids are built up in the p lant not necessarily from phytol alone, b u t from similar raw materials.

X LV III. Violanin is separated by crystallisation of its picrate from II20 into violanin-A (I) and violanin-B (II). (I) is very sparingly sol. in H 20and gives on hydrolysis glucose (1 mol.), rhamnose (1 mol.), 2>-hydroxycinnamic acid (1 mol.), and delphinidin (1 mol.). Oxidation with H 20 2 and tre a tm ent of the product w ith N H P hN H 2 gives an osazone, C3aH3gO:ioN4, containing both sugars and jj-hydroxycinnamic acid. The acid m ust therefore be attached to the disaccharide p art of the mol. (II) is a m ixture of delphinidin-3-glucoside with a little pseonidin-3-glucoside, and gives phenylglucosazone only on treatm ent w ith H 20 2 and NHP1i-NH2.

XLIX. [^-Dimethyl heptane-arr diol (this vol., 52) is converted by Na and E tI into its (mono)A'i ether, b.p. 126°/12 mm. (and some Et., ether, b.p. 115°/ 12 mm.), which with PBr3 gives the bromide. This with CHNa(C02E t )2 in abs. E tO H gives, after hydrolysis, Q-ethoxy-yrr dimethylnonoic acid, b.p. 130°/0-2

mm., the N a salt of which is converted by electrolysis into {iO^-tetrameihylhexadecane-aii-diol E t, ether, b.p. 167°/0-5 mm. By successive treatm ent with H B r in AcOH a t 100°, KOAc in EtOH , and hydrolysis with KOH, th is yields fiOZ-tetramethylhexadecane-xK-diol, b.p. 165^-167°/0-15 mm., which is oxidised by Cr03 in A c0H -j-K H S04 to perhydrocrotecin, (•CH2-CH2-CHMe-[CH2]3-CHMe-C02H )2 (diamide, m.p. 130°, identical with the product from natural sources).

L. pO^-Tetramethylhexadecane-ar-diol, prepared by reduction of perhydrocrocetin Me2 ester, is converted into its dibromide, which is treated with CHNa(C02Et)2, and the resulting tetracarboxylic ester hydrolysed and decarboxylated. Perhydronorbixin, m.p. 110-5— 1 1 1 °, identical w ith the natural product, is thus obtained. II. A. P.

Oxidation of citric acid. A. C. K tjyper (J. Amer. Chem. Soc., 1933, 55, 1722— 1727).—Oxidation of citric acid (I) witli KM n04 and dil. H 2S 0 4 is more complete (i.e., more C02 is produced) a t 20° th an at 1 0 0 °; the nature of the reaction changes a t about 60°. Below 60°, (I) gives C0(CH2-C02H )2 (II), which is oxidised to CH20 , H C 02H, and ,C02, and mol. 0 2 takes p art in the reaction; above" 60°, (II) decomposes to COMe2 before it can be oxidised. Small amounts of (I) in pure solution can be determined by oxidation w ith KM n04 in the Van Slyke const.-vol. apparatus by the use of proper conversion factors.

H. B.R eactions betw een citric and acetylsalicylic

acids. A. J. D ie t z l e r and R. E. N e l so n (J. Amer. Chem. Soc., 1933, 55, 1605—1608).—Acetyleitric anhydride and PC15 in light petroleum a t 25° givethe chloride, 0 < ^ ; § ^ Ac)'CH2‘C0C1, m.p. 92—93°,which with o-OH-CgHj/COaNa in cold CHC13 affords a compound (I), C15H 120 9, m.p. 162—163°, which could no t be acetylated and does not contain a phenolic OH-group (FeCl3) ; alternative structures are suggested. The ra te of hydrolysis of (I) by 0-0987A7- HC1 a t 38° is studied; the hydrolysis products are AcOH, o-0H-C6H 4-C02H, and citric and some aconitic acid. Unsuccessful attem pts to combine citric and acetylsalicylic acids are outlined. H . B.

Synthesis of d-ascorbic acid (ti-form of vitam in-C). T. R e ic h s t e in , A. Gr u s s n e r , and R . Op p e n a u e r (Helv. Chim. Acta, 1933,16,561—565).— cZ-Xylosone and aq. HCN a t 45° give a product which is hydrolysed (7-5% HC1 in C02) to 4-hydroxy-3-keto-5-hydroxymethyltetrahydrofuran-2-carboxylic acid(I), [<x]D —19-5° in MeOH [isopropylidene derivative, m.p. (vac.) 206—209° (corr.), which reduces I (in acid solution), A gN03, and 2 : 6 -dichloroph.enolindo- phenol (in neutral solution)]. The enolic form of (I) is considered to be ascorbic acid (cf. Micheel and Kraft, this vol., 489; Cox and H irst, ibid., 490). H. B.

Constitution of ascorbic acid. E. L. H ir st ,E. G . V. P e r c iv a l , and E. S m ith (Nature, 1933,131, 617; cf. A., 1932, 100).—Ascorbic acid Me2 ether (I),

C(^M e):C(0M ^0H 0H 'CH2'0H ’ from ascorblC acid and CH^N2, is neu tra l and reacts w ith 1 equiv. of warm 0-lN-alkali w ithout elimination of MeOH. The lactone ring of (I) appears to be opened and

ORGANIC CHEMISTRY, 595

hence both OMe groups are enolic. Cone, alkali produces decomp. The cryst. substance, in.p. 123° (this vol., 325), obtained from (I) with MeOH-NH3 is formed by the addition of NH 3 to the lactone group. The two OMe groups are retained in the product, CnH 190 7iSi, which behaves as an amide. The ring system in (I) has been elucidated by degradative oxidation of ascorbic acid Me4 ether (II). 0 3 gives aneutral substance,C02Me-C0-0-CH(C02Me)-CH(0Me)-CH2-0Me, which with NH 3 gives (CO*NH2)2and a-hydroxy-[3y-dimeth- oxybutyramide quantitatively. The hydroxydimeth- oxybutyric acid consists of 80% of |3y-dimethylthreonic acid and (3y-dimethyl+erythronic acid. The isolation of the two epimeric acids suggests enolisation a t C4 a t some stage and is im portant from the biological point of view. These results are incompatible w ith the furan- carboxylic acid structure for ascorbic acid previously rejected on crystallographic grounds (this vol., 490), and require either the structure given above for (II) or an unlikely alternative which is discussed.

L. S. T.Derivatives of glycuronic acid. I. Prepar

ation of glycuronic acid from glycuron. Comparison of their reducing pow ers. W. F. G o e b e l and F. H. B a b e k s (J. Biol. Chem., 1933, 100, 573— 581).—The prep, of glycuronic acid (I) from glycuron(II) (modified prep.) by Ba(OH )2 is described. (I) is quantitatively oxidised by N a I0 3 to saccharic acid, hut (II) is partly further oxidised. (I) and (II) have lower reducing vals. th an glucose by Shaffer and Hartmann’s method, particularly the micro-m ethod; standardisation of each batch of reagent is advisable.(I) reduces B ertrand’s reagent quantitatively, but(II) requires an excess of reagent. Pure (I) is about as stable as is glucose to Fehling’s solution.

R. S. C.Synthesis of hexuronic acids. II. Synthesis of

rf-mannuronic acid from d-m annosaccharic acid.C. N ie m a n n and K . P. L i n k (J. Biol. Chem., 1933, 100, 407—413).—¿-Mannosaccharodilactono (modified prep.) with N a-H g in dil. H 2S04 gives ¿-mannuro- lactone, m.p. 141-5— 142°, [a]jJ +92-8° (max.) in H 20 {Ba, [a]“ —4° in H 20 , brucine, m.p. 147-5— 148° (decomp.), [ajg - 2 2 -0 ° in H 20 , and cinchonine salts, m.p. 153—154° (decomp.), [a]j° +113-0° in H 20}, identical with the lactone obtained from natural alginic acids. The method of drying affects the m.p. and [a] of the alkaloidal salts. R. S. C.

M ethylglucosides of naturally occurring hexuronic acids. I. Preparation of methyl-iZ- galacturonide. S. M o rell and K . P. L i n k (J. Biol. Chem., 1933,100, 385—396).—The polygalactur- onide (I), [*]* +269-9° in O-ltf-NaOH, obtained by extraction of sol. substances from Citrus pectin by 70% EtOH, gives with hot, d ry HCl-MeOH the Me ester (II), + H 20 , sinters a t 136°, m.p. 138—140°, decomp. 140—141°, [a]g +124-1° in H 20 , of methyl-d- galacturonide (yield, about 15%), the Me4 ester of a Me glucoside of a tetragalacturonide (about 2 0 %), depolymerised and unchanged (I), and possibly some reversion products. (II), also obtained in 56% yield from ¿-galacturonic acid, with dil. aq. Ba(OH )2 gives methyl-d-galacturonide, + 2 H 20 , sinters a t 109°, m.p.

R R

112— 114°, decomp. 120°, [a]? +127-6° in H 20 [Ba salt, m.p. about 215° (darkens a t 200°), [a]p +99-1° in H„0]. (II) is considered to be an a-glucoside.

R . S. C.Isolation of a- and ß-rf-mannuronic acid. E.

S c h o eefel and K. P. L in k (J. Biol. Chem., 1933,100, 397—405).—a- and ß-d-Mannuronic acid, +0-5H 20 , m.p. indef. (sinters a t 110°; darkens a t 120— 130°) and 165— 167°, [« $ +33-51°— >+31-51° (min. +26-81°), and -47-90°— >-23-94° (in 24 hr.) in H 20 , respectively, are isolated from the Ba salt (A.,1932, 365). Both forms are hygroscopic and readily revert to the lactone, especially the a-form.

R. S. C.M ucondialdehyde . P . G. F is c h e r and K. L ö w e n

b e r g (Ber., 1933, 6 6 , [5], 665— 669).—Ozonisation of cycfohexene in AcOH a t —50° to —70° followed by catalytic hydrogenation of the ozonide affords adipdi- aldehyde (I), b.p. 92—94°/12 mm., in 60—70% yield. Successive addition of Br in CHC13 and EtO H to (1) and treatm ent of the product with powdered KOH at 130°/12 mm. yields mucondialdehyde tetraethylacetal, b.p. 139—14l°/12 mm., hydrolysed by tartaric acid in H 20 to mucondialdehyde (II), leaflets or needles, m.p. 121°. (II) remains unchanged when preserved as solid or in solution evon in the presence of light, and is little altered when heated for a short period above its m.p. I t is not autoxidised by atm . 0 2. I t is very slowly decomposed by mineral, bu t not by org., acids a t room temp., bu t is immediately darkened by alkali. I t could not be caused to react with CH2Br-C02E t and Zn or w ith CH2(C02H)2. Reduction with Al-Hg in H 20 or Zn dust in AcOH gives dark, polymerised products. Oxidation to the dicarboxylic acid could not be effected. The dihydrazone, m.p. 192°, diphenyl- hydrazone, m.p. 228—229a (Berl; decomp.), di-p- nitrophenylhydrazone, m.p. 264° (Berl), dioxime, decomp. about 200°, and disemicarbazone, m.p. 264° (Berl), are described, several of which are very sensitive to mineral acids. H. W.

Action of bleaching-pow der on ketones and ethyl acetoacetate, C. D. H u r d and C. L . T hom as (J. Amer. Chem. Soc., 1933, 55, 1646— 1649).— COMeEt gives CHC13 (45%) and E tC 02H (40-7%); furfurylideneacetone (I) affords CHC13 (55-5%) and ß-furylacrylic acid (89-5%); CELAcCOjEt yields CHC12*C02H (60%) and no CHClg? Oxidation (diJ. H N 0 3) of (I) gives some H 2C20 4 and NH 4 tetroxalate.

H . B.Preparation of dihydroxyacetone. A. I. V erta

n e n and M. N ordltjnd (Biochem. J ., 1933, 27, 442— 444).—A culture of A . suboxydans is incubated with4-55% glycerol in a 3% extract of yeast a t 20° and p a5-2 for 14 days. Dihydroxyacetone is isolated through its compound with N aH S03. H. D.

Products obtained by catalytic reduction of dioxim es and acetoxim e in acid m edium . M.K ra jö in o v iö and D. V r a n jic a n (Bull. Soc. ehim.,1933, [iv], 53, 145— 150).—Reduction [H2, Pt-black. aq. EtOH, HC1 (2 mols.)] of dimethylglyoxime (I) gives ßy-diaminobutane hydrochloride (44%) and NH 4C1 (56%); acetylacetonedioxime similarly affords ßS- diaminopentane hydrochloride (62%) and NH 4C1 (38%). Reduction of acetonylacetonedioxime in

596 BRITISH CHEMICAL ABSTRACTS.-— A.

E t0 H -I I 2C20 4 gives (NH.,)2C20 4 (8 %) and tho oxalate (r|-H ,0), m.p. 112°, of the sec.-hydroxylamiiie,

» ^CHMe-N(OH)-CHMe- . Inu- , , .(CH2)2< CHMo.N (OH)-CHlVIe^>( 2)2 ’ e 0 arises by condensation of the intermediate Se-di(hydroxylamino)hexane with acetonylacetone. and subsequent reduction. The difference in the behaviour of (I) and(II) is ascribed to the -weaker acidity [as determined by the method of Pfeiffer et al. (A., 1925, i, 270)] and more ready hydrolysis (by aq. EtOH-H Cl a t 17°) of (II) than (I). Resinous products are formed by reduction of glyoxime and succinaldoxime (a little, pyrrole is formed in this case); 16— 17% of NH 4C1 is also produced. Reduction of acetoxime gives mainly NH 4C1 and a little .sec.-hydroxylamine; GSBt2*N*OH and CPr2:N-OH aro more readily hydrolysed and afford much less NH4C1. H. B.

P entose reactions. I I I . Xylan. C. D . H urd and N. R. Cu r r ie (J. Amer. Chem. Soc., 1933, 55, 1521— 1523).—Oat hulls (I) are soaked in 2% aq. NH 3 for 2 days, extracted with hot 10% NaOH, the filtrate is treated w ith EtOH, and the pptd. m aterial tritu ra ted with AcOH; xylan (II), [a]™ —71-2° in aq. NaOH, is thus obtained in 22—24% yield. (II) does not exist as such in (I), since initial extraction of (I) w ith PhOH [in which (II) is sol.] has little effect on the yield. (II) is hydrolysed (dil. H 2S04) to xylose and with Ac20 and a little conc. H N 0 3 a t 70° gives di- acetylxylan, M 298 (f.p. in P h N 0 2), which is hydrolysed (10% K O H ) to (II). Saturation of an emulsion of (II) in H 20 with C2H 4 causes (after 3 weeks) 10% conversion into reducing sugar, none of which is formed in absence of C2H 4. H . B.

H ighly reducing sugar derivative (reductone).H. v o n E u l e r and C. M a.r t iu s (Svensk Kent. Tidskr., 1933, 45, 73—74).—Short treatm ent of an aq. solution of glucose w ith aq. NaOH-KCN and Pb(OAc)2 in N , a t 90° and decomp, of the pptd . Pb salt w ith H 2S gives a highly reducing substance (gluco-rcductone), C3H 40 3, m.p. 200—220° {Na salt). In reducing action and ultra-violet absorption spectrum (max. 268 mjx a t ]in 2—4 ; max. 287 mu a t p n 5-7— 10) i t closely resembles ascorbic acid (this vol., 490). Similar reducing compounds are obtained from xylose and G0(CH2-0H)2. J .iW .B .

Action of periodic acid on poly hydroxy lie com pounds. I I I . Action of periodic acid on sugars. P. F l e u r y and J . L a n g e (J. Pharm. Chim., 1933, [viiij,17, 409—417).—A detailed account of the oxidation of COiCHo'OHJo (I), glucose (II), and fructose (III) with H l0 4 (this vol., 376), the results of which show th a tthe reactions are : ( I )+ H I0 4-OH-CIVCOoH; ( I I )+ 5 H I0 4- 5HCO.,H: and ( I I I )+ 4 [0 ]— > either

H I03+CH20->5H I03-+CHo0+

( a ) CH 0 +

methylcellulose (Freudenberg and Braun, A., 1928, 399) does not lead essentially to 2 : 3 : 6 -trimethylglucose anhydride, bu t to a glueal-like compound (OMc=35-6%!) containing a double linking and a free OH. A similar mixture is derived from the product of the action of HC1 on 2 : 3 : 6 -trimethylglucose (I) in E t20 a t 0°. Reaction is considered to consist in removal of Cl and OMe by Na and reduction by tho liberated H. The non-volatile portion of the reaction mixtures gives (I) when hydrolysed with HC1-H20 and may be the desired anhydride. H. W.

2 : 3 : 6-T rim ethylglucose anhydride. K. F r e u d e n b e r g and E. B r a u n (Ber., 1933, 6 6 , [I?], 780—781).—The prep, of 2 : 3 : 6 -trimethylglucose anhydride is invariably successful when the initial material is cellulose m ethylated in cold solution to a product which retains the fibrous structure. Lack of success of Hess and Littm ann (preceding abstract) is ascribed to the use of powdered trimethylcellulose prepared in hot solution. H. W.

P artial acetonisation of sugars and sugar alcohols. I. 1 : 2-isoPropylidene-<Z-glucofur- anose 3 : 5-xnonoborate. L. v o n Y a r g h a (Ber.,1933, 6 6 , [B], 704—707).—Treatm ent of glucose with H3B 03 (1 mol.) and COMe2 containing H 2S04 rapidly yields 1 : '2-\xopropijliden<i-A-qlucoJuranose 3 : 5-mono-

borate H (I, A), m.p. (indef.) 90—110°,

H

rHÇ-0

/° -Q H (OH)2B / h c -

CMe 1

(A.)HÇ-0

CHo-OH

converted by distillation with MeOH into 1 : 2 -wopropyli- deneglucoso, from which (I) is derived by the action of H 3B 0 3 in COMe2,

furanoid grouping. (I) is

3HC02H + 0 H -C H 2-C02H or (b) 2CH20 + 2 H C 0 ,H + C H 0'C 02H-(-H20 , the last two reactions occurring simultaneously, (a) being the more important. General conclusions relating to tho effect of structure on the course of such oxidations are discussed. J . W. B.

Anhydride form ation of 2 :3 : 6-trim ethylglucose. K . H e s s and O . L i t t m a n n (Ber., 1 9 3 3 , 66, [.B], 774—779 ; cf. following abstract).^—The action of Na powder in E t20 on l-cliloro-2 : 3 : 6 -trim ethylglucose obtained by the action of HC1 in E t20 on tri-

thus establishing the transformed by BzCl or ■p-C6H 4Me-S02CJL in : C5H 5N into 1 : 2 -isopropylideneglucose 6 -benzoate and 6 - ^i-toluenesulphonate, respectively; more highly acyl- ated products cannot be obtained. W ith CPli3Cl in C5H 5N (I) gives 6 -triphenylmethyl-l : 2 -isopropylideneglucose (Bz2 derivative, m.p. 78—-79°, [a]“ —4-2° in C5H 5N). The presence of 2 OH groups attached to B is indicated by the necessity of using> 3 mols. of reagent in the prep, of the above compounds. Oxidation of (I) with KMnO., in anhyd. COMe2 gives K isopropylidenexyluronate. Reaction probably occurs in the sequence, ring transformation, estonfication, acetonisation. W ith 2 mols. of H 3B 0 3 acetonisation does not take place. Under similar conditions galactose yields dmopropylidenegalactose. H . W.

N ew class of sugar derivatives. F. M i c e e e l and F. S u c k e u l l (Annalen, 1933, 502, 85—98).—6 -Iodo-l : 2-3 : 4-dnsopropylidenegalactose is converted by hydrolysis (2.ZV-HCI in dioxan) and subsequent condensation w ith E tSH into 6 -iodogalactose diethylmercaptal, m.p. 123° (decomp.), [a]1,} 4*6-9° in C5H 5N, the tetra-acetate (I), m .p. 109— 110°, [a]1,; —2-3° in CHC13, of which with HgCl2, CdC03, and aq. COMe2 gives (under defined conditions) al-6 -iodogalactose 2 : 3 : 4 : 5-tetra-acetate, m.p. 1 2 2 ° (previous sintering), [a]f} — 3-7° in CHC13. (I) is also, converted by the above reagents into al-galactose 2 : 3 : 4 : ¡)- tetra-acetatehydrate (II), m.p. 150° (previous sintering),


and a syrup (III). (I ll) consists largely of galactopyranose 2 : 3 : 4 : 6 -tetra-acetate, since acetylation (Ac20 -C 5H 5N) gives a- and (3-galactopyranose penta- acetates, whilst p-nitrobenzoylation in CHC13-C 5H 5N affords a-galactose i - ’p-nitrobenzoata 2 : 3 : 4 : 6 -tetraacetate, m.p. 108°, and a product which when distilled a t 0-05 mm. yields p-NOo'CgHj-COjH and the te tra acetate, C14H 180 9, m.p. 110°, of Maurer and Mahn

H OAc (A., 1927,751). $-6alactose l--p-nitro- N' // benzoate 2 : 3 : 4 : 6-tetra-acetate, m.p.

123°, is prepared from p- N 0 2,C6H 4,C02Ag and acetobromo- galactose in quinoline. A solution of(II) in C5H 5N shows [a]D +7-8° ■— >-—28°; acetylation of the resultan t product gives a-, m.p. 128°, [a];?— 11° in CHC13, and (3-, m.p. 101°,

Mi? —78-3° in CHCI3, -galacloseptanose. penta-acetates (as IV), which are interconvertible by treatm ent with a little ZnCl2 in Ac20 . H. B.

D istinction betw een aldo- and keto-hexoses by m eans of the resorcinol reaction. C. S a m pietro and K . T a u f e l (Z. anal. Chem., 1933,9 2 ,241—245).— Selivanov’s reaction (A., 1887, 459) has been modified to render it suitable for the detection of keto-hexoses in coloured media, the 5-hydroxymethy]furfuraldehyde (I) being distilled in steam and the condensation with o-CfiH4(OH)2 effected in the colourless distillate. On heating for some time, (I) slowly undergoes some change, rendering it no longer volatile in steam.

D. R. D.T ransform ations of sugars in am m oniacal

m edium. J. P a r r o d (Ann. Chim., 1933, [x], 19, 205—262, and Bull. Soc. chim., 1933, [iv], 53, 196— 2 0 0).—P artly an account of work previously reviewed (A., 1930, 480; 1931, 852; 1932, 45, 369; this vol., 260). The following is new. Prolonged interaction (60 clays) of fructose and aq. NH 3 in absence or presence of Zn, Ca, Fe", F e '" , and Mn hydroxides in absence of air gives varying small amounts of 4-methyl- glyoxaline (I), b.p. 263°/760 mm., m.p. 55° (oxalate, m.p. 205—206°; picrate, m.p. 159— 160°); 4-methyl-2-hydroxymetliylglyoxaline, m.p. 129° (picrate, m.p. 82°), is also formed w ith Mn(OH)2. When air is passed through the above reaction mixtures, small amounts of 4-hydroxymethylglyoxaline (II) are produced [except with Ca(OH)2, when (I) results]. Passage of air through a m ixture of fructose, methylene-blue, and aq. NH 3 for 1 month gives (II), d- arabinotetrahydroxybutylglyoxaline, and glyoxaline- ‘i-carboxylamide (+ H 20), m.p. (anhyd.) 214° [hydrochloride, m.p. 220°; picrate, m.p. 208°). Work (lit.) on the synthesis of substances related to proteins is discussed. H. B.

B iological m ethod for determ ination of different sugars in starch-degradation products.A. S chultz and G. W. K ir b y (Cereal Chem., 1933,10, 149—155).—A selective method for the determination of glucose (I) or fructose (II), sucrose (III), and maltose (IV) in presence of each other has been devised. (I) or (II) was determined by measuring the vol. of C02 produced by complete fermentation with a mycoderma organism (a pure culture of an air-borne organism). A sugar- and maltase-free invertase prep.

was then added to the reacting solution and the vol. of C02 then evolved measures the (III) present. The to ta l fermentable sugar was determined with bakers’ yeast and hence, by difference, the (IV). Details of the procedure and apparatus are given. I t is advisable to control experiments with pure sugars. The method can also be used for detecting small amounts of invertase and maltase in plant materials.

E. A. F.Liquefaction of starch paste. H . P r in g s h e im ,

H. B o rch ar dt , and R. Lew y (Naturwiss., 1933, 21, 299—300).—No H 3P 0 4 was formed when starch paste was liquefied, even when considerable conversion into sugar had taken place. This is contrary to expectations if the formation of starch paste is due to the esterification of the outer substance of the starch granules with H 3P 0 4. A. J . M.

Starch n itrates. II. Starch n itrates from starches of different origin . J . H a c k e l and T. U r b a ń s k i (Rocz. Chem., 1933, 13, 221—225).—No marked differences were found in the N content or properties of the products of nitration of maize, wheat, rice, tapioca, potato, and sol. starch. R. T.

Action of solutions of orthophosphoric acid on cellulose. G. Ch a m t e t ie r (Compt. rend., 1933,196, 930—933; cf. A ., 1931, 941).—The action of aq. H3P 0 4 (1040 g. per litre) on cellulose (I) for 15 hr. gives 3C6H 10O5,H3PO4. By washing with H 20 all H 3P 0 4 is removed and (I) left unchanged. The X-ray diagram resembles th a t for cellulose save for being fainter. C. A . S .

[Attem pted] preparation of polyatom ic coordination r in gs. P . P f e if f e r and E. L ü b b e (J. pr. Chem., 1933, [ii], 136, 321—328).—Hexadeca- methylene-aK-dicarboxylic acid [the E t ester is prepared by electrolysis of K E t sebacate (cf. Ruzicka et al., A., 1929, 6 8 )] is converted through the chloride into the amide, m.p. 179° (softens a t 173°), and thence into the nitrile, m.p. 58° (softens a t 54°) ; th is is reduced (Na, EtOH) to octadecamethylene-<xa-diamine(I), m.p. 93° (previous softening) [dihydrochloride, m.p. > 225°; Bz2 derivative, m.p. 150° (softens a t 145°)]. Complex formation is not observed with various metal salts and (I), tetra-, penta-, and deca- methylenediamincs, and O-aminononoic acid.

H. B.N ew salts of quaternary am m onium bases.

Q. Min g o ia (Anriali Chim. Appl., 1933, 23, 104—114).—The following salts of therapeutic interest have been prepared : N3Iet , m.p. 80—82°, and NElA cacodylates ; N M ei and N EtA methylarsinates ; NM ei and NKtx camphorates, m.p. 58—60° ; NM e4, m.p. 70— 72°, and ATEti glycerophosphates. In each case, the p K val. of the 1 % aq. solution is unchanged by heating for 30 min. in an autoclave a t 120°. T. H. P.

Preparation of the nitric ester of (3-hydroxy- ethylam ine nitrate. M. A u b r y (Mém. Poudres, 1932— 1933, 25, 189—193).—Prepared from the free base, NH 2-CH2-CH2-0-N 02,H N 03, or its n itra te and HNOg (d 1*52), is too expensive and hygroscopic to be of val. as an explosive. N H. A. P.

Resolution of p-ethoxyam ines. W . R. B r o d e and I. J . W e r n e r t (J. Amer. Chem. Soc., 1933, 55,

HÇ-OAc AcO-ÇH AcO-ÇH

HÇ-OAc OH,— (IV.)


1685—1689).—Details of the resolution of ß-ethoxy- hexylamine into d-, b.p. 70-S—71-2°/15 mm., [«]“ + 8 -6 ° in 95% EtOH, and I-, b.p. 70-5—70-7°/14 mm., [a]?J —24-6° in 95% EtOH, forms and of ß-ethoxy-ß- phenylcthylamine into d-, [a]“ -(-104-5° in EtOH, andI-, [a]'fj —104-2° in EtOH, forms by ¿-tartaric acid (I) are given. Partial resolution of ß-ethoxy-butylamine and -amylamine could be effected only w ith (I) or d-camphorsulphonic acid. Salts of const, rotation (after about 2 0 recrystallisations) are often obtained, but these do not yield the fully resolved base. There is little difference in the solubility of the H ta rtra tes or camphorsulphonates of the d- and fam ines. When the salts of the enantiomorphic forms have markedly different Cryst. form, i t is possible to crystallise either from a saturated solution of, e.g., dAdlB by seeding with, e.g., dA dB or dAlB. H. B.

Chitins, lichen ins, and cellu lose. G. v o n F r a n cois (Diss., Zürich, 1930 ; Bied. Zentr.,1932, 3, A, 51—52).—Both plant and animal ehitin yield approx. 80% of iV-acetylglucosamine (I). Enzymic decomp, of acetylchitosan yields (I), whilst chitosan yields polyglucosamine. Lichenin from Cetraria islandica is optically inactive. I ts general properties and in particular the behaviour of its acetate indicate a close relationship to cellulose. The action of P B r5 on cellulose acetates suggests a 1 : 6 - in addition to a 1 : 4-linking of cellobiose. A. G. P.

Leucine and dileucine hydrochloride. Iso lation of leucine. H. M. B a r n e t t (J. B io l. C hem .,1933, 100, 543—550).—Iso la tio n of leu c in e (I) from case in and w h ea t g lu ten h y d ro ly sa te s is b ased on it s p p tn . b y NaCl. T h e sa ltin g o u t o f (I) a n d o f d ileu c in e h yd roch lorid e (II) a t v a r io u s p n is d escrib ed .(II) is p o ss ib ly

CH2Pr^CH (N H 2,HCl)-C02iSiH3,CH(C02H)*CH2P r5R. S. C.

O xidation of cystine in non-aqueous m edia.I. Solubility and stab ility of cystine in non- aqueous acid-base system s. G. T o e n n ie s and T . F. L a v in e (J. Biol. Chem., 1933,1 0 0 ,463—477).— Cystine is sol. in MeOH-HCl, b u t is esterified, whilst it is oxidised in solutions of HC104 (I) in A cO H ; it is sol. and stable in a solution of (I) in MeCN. I t is oxidised by free (I), b u t stable in the presence of C104' ions. H. D.

Catalytic decom position of nitroso-ß-alkyl- am inoketones. I. Preparation of diazom ethane. Evidence of the occurrence of diazotisation in the aliphatic ser ies. E. C. S. J o n e s and J . K e n n e r (J.C.S., 1933, 363—368).—The additive products of mesityl oxide and the appropriate amine with HNO2 a t 0 ° give good yields of nitroso-ß-methyl- (I), b.p. lIl° /0 -S mm., -ethyl-, b.p. 114°/0-5 mm., -n-propyl- (II), b.p. 120°/1 mm., -n-butyl-, b.p. 127°/ 0-6 mm., and -n-amyl-, b.p. 127°/0-3 mm., -aminoisobutyl Me ketone; these compounds decompose * to olefiries when heated. The following aromatic analogues, which were prepared similarly in 25% yield, nitroso-$-phenyl-, m.p. 59—61°, -m-, m.p. 78°, and -Y>-tolyl-aminoisobutyl Me ketones, m.p. 105—108°, give the diazo-compound with aq. alcoholic NaOH. ß- Benzylaminoiiobutyl Me ketone (hydrochloride) gives the AO-derivative, m.p. 85—86°. The decomp, of

(I) with various Na alkoxides gives varying yields of CH2N2, the max., 83-5%, being obtained with NaOPr/). W ith 50% aq. KOH the aliphatic nitroso-ketones give varying yields of define; (II) gives propylene, Pr°OH, and Pr^OH, whence the interm ediate formation of propyldiazonium hydrate is inferred. The nitroso-ketones can be used for alkylation of phenolic compounds, bu t the requisite conditions vary with different phenols. W ith conc. mineral acids defines are also formed, bu t the yield is poor owing to simultaneous production of amine, which is the sole product with H C l-E t20 . R. S. 0.

A lkylsem ioxam azides. G. T ie r ie (Rec. trav. chim., 1933, 52, 357—365).—The prep, of derivatives of the type X-CO-CO-NH-NH, (X = 0 R o r NHR) and their use as reagents for carbonyl is investigated. W ith the appropriate aldehyde E t oxalhydrazinate (Curtius, A., 1915, i, 787) affords E t oxal-j)-methoxy-, m.p. 161°, and -3 :4 -metliylenedioxy-, m.p. 169°, -benzylidene- hydrazinate; and from the similarly prepared Me oxalhydrazinate, m.p. 116°, are obtained M e oxal- benzylidene-, m.p. 150°, -p-methoxy-, m.p. 147°, and -3 :4 -methylenedioxy-, m.p. 215°, -benzylidene-hydrazinate. E t iV-methyloxamate, b.p. 120—124°/15 mm., m.p. 24° (improved prep, described), is converted by aq. NH 3 into semioxamazide and, by an improved method, the semioxamazones of anisaldehyde, m.p. 278° (decomp.), piperonal, m.p. 290° (decomp.), and vanillin, m.p. 265°, are prepai-ed. 5-Methylsemioxam- azide, NHMe’CO-CO’NH'NHjj, m.p. 197° (prep, from N 2H 4 and NHMe-C0-C02E t or from C02R-C0-NH-NH2 and NH 2Me), similarly affords the o-methylsemioxam- azones of PhCHO, m.p. 245°, anisaldehyde, m.p. 247°, piperonal, m.p. 280°, vanillin, m.p. 270° (decomp.), furfuraldehyde, m.p. 252—-258°, hydroxymethylfurfuraldehyde, m.p. 204—205°, C0Me2, m.p. 127°, and COPhMe, m.p. 179°. W ith the exception of the COMe2 derivative all are tasteless. J . W. B.

Reduction of a-am ino-nitriles. W. M cM eeking and T. S. S tev en s (J.C.S., 1933, 347—349).—Reduction of a-amino-nitriles, CRR '(CN )'N R"R '", by powdered N ain moist E t20 gives amines, CHRR'*NR"R"' (30—50% yield) (R " = R " '= :M e : R = H , R '=M e; R = R '= M e ; R —Ph, R ' = H ); however, with Na slices in E t20 -aq . K H C 03 the amine is formed in the yield stated if R or R ' is Ph (R = P h , R '= H : R " = R " '= H , 57 ; R " R " '= C 5H 10, 85; R "= M e, R " '= H , 19; R " = R " '= H , 46; R " = Ph, R '"= M e, 50; and R = R " = P h , R '= M e, R " '= H , 55%), whereas the diamine, CRR'(NR''R '")-CH 2-NH„ is formed if R and R ' are aliphatic (R " = R " '= M e , R = E t , R ' = H, 39; R = R '= R "= R " '= = M e , 22; R = M e, R '= H , R "= P h , R " '= E t , 55% ;R = R '= M e , R " = R " '= I I , entirely decomposed). The following are described: a-dimeiliyl- amino-n-butjTonitrile, b.p. 156— 158° [pierate, m.p. 148° (decomp.)]; a-amino-$-dimethylaminobutane dihydrochloride, m.p. 176° (decomp.); a-amino-fi-di- methylaminoisobutane dihydrochloride, deliquescent, m.p. 256—258°; a-ethylanilino-propionitrile, b.p. 133— 134°/10 m m .; a-amino-fi-ethylanilinopropane dihydrochloride, m.p. 199—200°, and picrate, m.p. 164°; benzylmethylamine picrate, m.p. 117— 118°; a neutral substance, m.p. 183°, as by-product in the prep, of a-methylaminophenylacetonitrile. R. S. C.


Preparation, toxicity, and absorption of b is m uth com pounds. IV. B ism uth com pounds of thiolacetic acid. W. M. L a u t e r , A. E. J u r i s t , and W. G. Ch r i s t i a n s e n (J. Amer. Pharm. Assoc., 1933,2 2 , 2 1 2 —214).—N a bismuthothiolacetate, (C02N a,CH2,S)2B i0H (32% absorbed in 27 days after intram uscular injection), and bismuthotriothiolacet- amide, Bi(S,CH2,GO,N H 2)3 (82% absorbed in 3 hr.), have the same order of toxicity (max. tolerated dose< 30 and < 50 mg./kg., respectively). The prep, of SH-CH2’C 02E t and Et bismuthothiolacctate is described.

E. H. S.Preparation of silicon triethyl halides. E. A.

F l o o d (J. Amer. Chem. Soc., 1933, 55,1735— 1736).— Si triethyl fluoride, b.p. 110°, S iE t3Cl, and S iE t3Br are obtained in almost quant, yield from (SiEt3)20 and the appropriate Na or NH 4 halide in conc. H 2S 04.

H. B.Oxidation of G rignard reagents. M . T. G o e b e l

and C. S. M a r v e l (J. Amer. Chem. Soc., 1933, 55, 1693—1696).—The rates of absorption of 0 2 by E t20 solutions (0-0052—-0-0162.M) of MgEtBr, MgBuCl, CHoPlrMgBr, MgPhBr, and Mg octyl (I) and cetyl (II) bromides a t 0—29° are determ ined; oxidation proceeds rapidly a t 0°, i.e., when the v.p. of E t20 is not high enough to prevent access of air. (I) and (II) are oxidised by 0 2 giving good yields of octyl and cetyl alcohol, respectively. H. B.

Yields of aliphatic tertiary Grignard reagents and lim its of their usefu lness as synthetic reagents. F. C. W h it m o r e and D. E. B a d e r t s c h e r (J. Amer. Chem. Soc., 1933, 55, 1559— 1567).— GMco'MgCl (I), CMe2Et-MgCl (II), CMeEt2-MgCl (III), CMeEtPi-MgCl (IV), CMeEtBu“-MgCl (V), CMe2Bu“-MgCl (VI), CEt,-MgCl (VII), and Mg dimethyl-»-amylcarbinyl chloride (VIII) are prepared in 58—SiO% yield. Of these, (I) only reacts with E t2C03. (I), (II), and (VI) react with ClCO,Et togive the appropriate CR3,C 02Et. (I) and AcCl give 40-7% of COMeBuv ; small amounts of Me ter/.-amyl ketone, y-methyl-y-ethylpentan-P-one, and yy-di- methylheptan-[3-one are similarly obtained from (II),(III), and (VI), respectively. ^j-Dimethylheptyl, b.p. 88—89°/15 mm., fi-methyl-fi-ethylamyl, b.p. 75-5—76°/15 mm., ¡3-methyl-$-ethylhexyl, b.p. 85-5—8 6 °/ll mm,, and fifi-diethylbutyl, b.p. 75—78°/12 mm., alcohols are prepared in 10—41% yield from CH20 and (VIII),(IV), (V), and (VII), respectively. (VI) and (VIII)react normally with C02. H . B.

G allium trim ethyl, ga lliu m trim ethyl etherate, and gallium trim ethylam m ine. C. A. K r a u s andF , E. T o o n d e r (Proc. N at, Acad. Sci., 1933,1 9 , 292— 298).—Ga trimethyl (I), b.p. 55-7±0-2°/762 mm., f.p.— 19°,' from ZnMe2 and GaCl3 (first a t room temp, and then a t 80—120°), is extremely reactive towards0 2. MgMel and GaCl3 in E t„0 and N 2 give Ga Me3 etherate (II), b.p. 98-3°, f.p. —76°, which is oxidised slowly by atm . 0 2, is hydrolysed by aq. KOH giving CHj- (1 mol. a t 35°; 2 mols. a t 100°), and with liquid NH3 affords Ga Irimethylapimine, m.p. 31°. (I) could not be obtained from (II) in a pure state. H. B,

Chlorination products of ga lliu m trim ethyl.C. A. K r a u s and F . E. T o o n d e r (Proc. N at. Acad. Sci., 1933, 19, 298—303).—Ga trimethylammine (I)

and excess of HC1 a t room temp, to 160° give CII4 (3 mols.) and A7/ / , tetrachlorogalliate, not m elted a t 200°.(I) and HC1 (2 mols.) in E t20 afford Ga dimethyl chloride monoammine, m.p. 54° (a diammine, m.p. 112°, is also described), also obtained from NH 4C1 and GaMe3,E t20 in E t20 ; the first-named reaction is GaMe3,NH3 HC1—> GaMe3-j-NH4C1—> GaMe2Cl ,NH3 + CH4. GaMe3 and NH 4C1 do not react in liquid N II3. Ga methyl dichloride, m.p. > 7 5 ° (vac.) (monoammine, m.p. > 8 0 ° ; pentammine), is prepared from(I) and HC1 (3 mols.) in E t20 or from GaMe3,E t20 and HC1 (2 mols.) in E t20 . H. B."

Carbon rin gs. XXIV. T w enty-three-m em - bered carbon ring. L. R u z ic k a and M. S t o l l . XXV. Introduction of a triple link ing in the fifteen- and seventeen-m em bered carbon rin gs.L . R u z ic k a , M. H u r b in , and H . A. B o e k e n o o g e n (Helv. Chim. Acta, 1933, 1 6 , 493—498, 498—505).— XXIV. Electrolysis of the Na salt of Me H undecane- oX-dicarboxylate, m.p. 49—50° [obtained by partial hydrolysis (dil. HC1) of the Me2 ester], in MeOIi gives 60% of the Me ester, m.p. 68—70°, of docosane- ax-dicarboxylic acid, m.p. 128—130°. Dry distillation of the Ce salt of this affords about 2% of cycloZri- cosanone (I), b.p. 175—177°/0-02 mm., m.p. 38-5—399 (purified through its semicarbazone, m.p. 174— 176°), (probably) Me docosyl ketone, and products of high b.p. (from which none of the expected ^46 -diketone could be isolated). (I) is reduced (Olemmensen) to cyclotricosane (II), b.p. about 177°/0-l mm., m.p. 49^—50°, The vals. of M jd for (I) and (II) agree with those calc, from similar rings; the m.p. and mol. refraction are not so regular.

XXV. Successive treatm ent of cycZopentadecene(III) with Br (in cold CS2) and E tO H -K O H (at 100°) gives impure l-bromo-A^cyclopentadecene, b.p. 128— 132°/0-25 mm., converted by more conc. E tO H -K O H (at 150—175°) into cyclopentadecinene, b.p. 158— 159°/14 mm. (ozonolysis product, tridccane-av-dicarboxylic acid), which is reduced (H2, P t0 2, EtOAc) to cj/c/opentadecane. 1 -Bromo-\x-cyc\oheptadecene, b.p. 147— 150°/0,5 mm., similarly gives cycloheptadecinene, b.p. 127—128°/0-25 mm. (ozonolysis product, penta- decane-ao-dicarboxylic acid). ci/cZoTriacontadieno(IV) (A., 1932, 58) gives mixtures, m.p. 63—69° and95—105°, of Br2-derivatives when treated as above; these could not be freed from Br by EtO H -K O H a t 180°/30 lir. Saturation of (III) with Br in CS2, trea tment of the resultant product with NHMe2 in CcH,j a t 140—150°, and addition of Mel to the resulting base gives cyclopentadecenyltrimethylam?nonium iodide, m.p. about 230° (decomp.). Tetramethyldiamiuocyclo- triacontadiene dimethiodide, m.p. 256°, is similarly prepared in 6 — 10% yield from (IV). H. B.

M echanism of the ionene synthesis. M. T. B o g e r t (Science, 1933, 77, 197—198; cf. this vol., 153).—Further evidence is given concerning the mechanism of th is synthesis in so far as the transition from a monocyclic tert.-alcohol to a dicyclic hydrocarbon is involved. L. S. T.

Anodic oxidation of cyclohexane and its derivr atives. M. Y o k o y a m a (Bull. Chem. Soc. Japan,1933, 8 , 71—d07).—The anodic oxidation of C6H G in jV-H2S04 proceeds with a highor current yield (up to

GOO BRITISH CHEMICAL ABSTRACTS.— A.

95% a t 70°) a t a P b 0 2 anode than a t a P t anode (> 55%), and with a lower temp, coeff.; the products include pyrocatechol, ^-benzoquinone, maleic acid, HC02H, CO, and C02. cycZoHexanc (I) is very difficult to oxidise ( < 10%) in A7-H2S 04; in a mixture of 2iV-H2S04 and COMe2 it yields adipic (II), succinic(III), malonic (IV), and, probably, glutaric acids. ('//c/oHcxanol yields on anodic oxidation cycZohexan- one (V), q/cZohexene (VI), and (I), (II), and (III), the current yield being up to 90% ; (V) behaves in an analogous manner. (VI) yields similar products to thoso obtained from (I), but the yield diminishes continuously throughout the process (max. 93%). cyclo- Hexanediol yields (II), (III), (IV), H C 02H, and traces of (V). Details are given of the yield of each product. The mechanisms of the reactions are discussed, particularly in relation to the differences of behaviour of saturated cyclic and aromatic compounds. I t appears probable th a t a persulphuric acid, formed at the anode, is the actual oxidising agent. H. F . G.

Slow com bustion of benzene. J . A m ie l (Compt. rend., 1933,1 9 6 ,1122— 1124).—Oxidation of mixtures of CGH G (1 part) and 0 2 (15 parts) a t an initial pressure of 1 atm . heated in sealed tubes for 2 hr. commences a t 420°, rapidly increasing between 435° and 485°. The C02 content of the gaseous products increases with rise of temp., whilst the CO content is max. (32—33%) a t 477°. Oxidation is completo above 510°, the gaseous composition curve coinciding with th a t for the oxidation of CO. A . C.

Jacobsen reaction. III. M onobrom o-derivatives of the three tetram ethylbenzenes. L. I.S m ith and C. L. M o y le (J. Amer. Chem. Soc., 1933, 55, 1676—1682; cf. A., 1932, 607).—Bromodurene(I) and conc. H 2S04 a t 25—30° give (after 10 days) di- bromodurene (92—99%), prehnitenesulphonic acid(II) (max. yield 25%), and amorphous material (25— 30%); much S 02 is evolved and traces only of </>- cumenesulphonic acids are produced. Similarly, bromoisodurene affords dibromoiiodurcne (80%) and(II) (35—40%), whilst bromoprchniteno furnishes (much more readily) dibromoprehnitcne (99%) and(II) (81%). The first stage in the reaction is sulphon- a tio n ; the sulphonic acid then rearranges (at 10—15° or 130—150°, hydrolysis and not rearrangement occurs). The Br2-derivatives do not rearrange in contact with H 2S04. L ittle or no depression of the m.p. of mixtures of tho Br- and Biyderivatives is observed; the latter are characterised by reduction (red P and H I a t 225°) to the hydrocarbons and conversion of these into (N 02)2-derivatives. Bromo- durenesulphonic acid (-fl-5H 20), m.p. 142—143° (decomp.) (chloride, m.p. 185°; amide, m.p. 194°), is prepared by short treatm ent of (I) with oleum a t 0°.

H. B.Catalysis of polym erisation by ozonides. II.

R. C. H o utz and H . A d k in s (J. Amer. Chem. Soc.,1933, 55, 1609—1617; cf. A., 1931, 597).—The course of tho polymerisation of styrene (I) by ozonides and other catalysts is followed by determinations of the viscosity of a 10% solution of the reaction m ixture in C6H 6, the wt. of polystyrene (II) produced, and the sp. viscosity of a solution of 26 g. of (II) per litre of C6H g. The sp. viscosity of (II) reaches a max. and

then decreases; it varies considerably with the experimental conditions and, contrary to Staudinger and Lautenschlager (A., 1931,1031), is a max. with the (II) prepared a t 100° in N2 in absence of a catalyst. Contra ry to these authors, Bz20 2 is a more active catalyst than 0 2 for the polymerisation of ( I ) ; i t is suggested th a t their specimen of (I) contained a catalyst. Diisobutylene ozonide (III) is a very active catalyst and also catalyses the polymerisation of Ph styryl, styryl Me, and Me AaV-pentadienyl ketones, A^-hexadienal, E t sorbate, and A1 ' 3-cycZohexadiene. cycZoHexene and0 3 in AcOH give a liquid ozonide which is much less active for the polymerisation of (I) than ( I I I ) ; the solid ozonides (Harries, A., 1915, i, 966) are practically inactive. The mechanisms of catalysis and polymerisation of (I) are discussed. H. B.

Nitration of jj-fluorotoluene. Y. D e s ir a n t (Bull. Acad. roy. Belg., 1933, [v], 19, 325—345).— Nitration of 2>-C6H4MeF (I) in CC14 with H N 0 3 in presence of P 20 5 gives 25% yield of a mixture of 4:-fluoro-3-nitro-, b.p. 241°/765 mm., m.p. 26-48°, and 4-fluoro-2-nitro-toluene (II), b.p. 213°/768 mm., m.p. 8-85°, identified by conversion into the nitro- toluidines. (II) has been synthesised by diazotisation of 2-nitro-^)-toluidine in presence of HF. The nitration of (I) occurs 74-5% m to the Me group, showing th a t F > C l> M e in orienting power.

J . W. S.R eplacem ent of brom ine by chlorine in or

ganic halides. II. P . P f e i f f e r and W. P r a e t o - r i u s (J. pr. Chem., 1933, [ii], 137, 27—39; cf. A.,1930, 333).—Stilbene dibromide (I) and HgCl2, slowly in boiling COMe2-CHCl, bu t more rapidly in boiling AcOH, yield stilbene dichloride (II), m.p. 190-5— 191°. As with SnCl4 (Zoc. cit.), N 0 2 has a protective action, so th a t 4-nitro- (III) and 2 : 4-dinitro-stilbene dibromide (IV) afford 7'-chloro-7-bromo-4-nitro-, m.p.180—181°, and 2 : 4-dinitro-dibenzyl, a, m.p. 159-5— 160-5°; p, m.p. 149—150-5°, respectively. 4 : 4'-Di- nitrostilbene dibromide (V) does not react. In cold dioxan, HgCl2 and 4-methoxystilbene dibromide (VI) give 1 -chloro-T-bromoA-methoxydibenzyl, m.p. 168— 169°; in tho boiling solvent the second B r is attacked without production of homogeneous i-methoxystilbene dichloride, m.p. 148—149° (obtained from 4-methoxystilbene and Cl, in CC14). a(3-Dibromo-(3-phenylpropionic acid (V llj, m.p. 195—196°, and HgCl2 do not react in boiling COMe2, bu t in boiling AcOH yield $-chloro-oi-bromo-$-phenylpropionic acid, m.p. 183— 184° (decomp.); in similar circumstances, no reaction occurs A vith ap-dibromo-4-nitrophenylpropionic acid. ap-Dibromo-4-methoxyphenylpropionic acid(VIII) and HgCl2 a t room temp, afford a-bromo-$- ethoxyA-methoxyphenylpropionic acid, m.p. 118-5— 119-5°; ill-defined results are obtained in dioxan. a$-Dichloro-$-4:-methoxyphenylpropionic acid has m.p.133— 134° (decomp.). In boiling EtO H or dioxan, respectively, meso- (IX) and rZZ-dibromosuccinic acids are not affected by HgCl2. (II), m.p. 190—190-5°, in EtO H a t 150° or COMe2 a t 200°, 4-nitrostilbene dichloride (X) in boiling EtOH, Bu^OH, or cyc/ohexanol, and 2 : 4-dinitrostilbene dichloride (XI) in boiling EtO H are indifferent towards LiBr. (II) is unchanged by L il in boiling EtOH, but a t 200° affords stilbene


(XII), also obtained from (I) in EtO H a t 150° or AcOH a t 100°. In boiling and cold COMe2, respectively,(III) and (IV) yield the corresponding substituted stilbenes. (II) does not react with N a l in E tO H at 150°, but in AcOH a t 200° gives (XII). At room temp, in COMe2 (I) and N a l yield (XII). Under similar conditions (III) and (VI) give the corresponding stilbenes, (VII) yields CHPh:CH-C02H, and (IX) affords fumaric acid. (X) and (XI) are indifferent towards CaBr„ in EtOH. H. W.

Synthesis oí hom ologous naphthalenes. E. d e - B . B a r n e t t and F . G. Sa n d e r s (J.C.S., 1933, 434—437).—Succinic anhydride, A1C13, and the appropriate hydrocarbon, best in C2H 2C14 (except with Ci0Hg), give the following (3-bcnzoylpropionic acids :4-Mc-, m.p. 129°, 4-Pr*-, m.p. 142°, 3 : 4-, m.p. 129°,2.: 4-, m.p. 114°, and 2 : 5-Mea-, m.p. 86°, b.p. 215°/1 mm. Reduction by Clemmensen’s method (Zn wool) (contrast lit.) readily afforded the following »(-butyric acids : y-^-tolyl-, m.p. 59°, -p-cumyl-, m.p. 50°, -o-, m.p. 53°, -7n:, m.p. 79°, .and -^-xylyl-, m.p. 70°, b.p. 175°/2 mm. Cyclisation by 80% H 2S04 at 100° led to the following 1-keto-l : 2 : 3 : 4-tetrahydro- naphthalenes : 7-Me-, m.p. 35°, 7-Pr&-, m.p. 36°, 6 : 7-, m.p. 49°, and 5 : 8-Jlfe2-, m.p. 33°, and 5 :7 -Me2-. By the Grignard reaction these yielded the following1 : 2 : 3 : á-tetrahydro-1 -naphthols : 1 : 7-Mer , m.p. 90°, lrMe-7-Prl3-, m.p. 83°, 7-Me-1-IV - and 1 : 6 : 7-Me3-, oils, and 1 : 5 : 8-Me^-, m.p. 136°, whilst Clemmensen reduction gave 6 : 7-, b.p. 128°/7 mm., and 5 :8 - dimethyl-1 : 2 : 3 : á-tetraliydronaphthalene, b.p. 120°/1 mm. and 254°/760 mm. Dohydrogenation of the hydrocarbons or carbinols by So at 300° (reaction in the vapour phase) led to the following substituted naphthalenes : 1 :4 -, b.p. 264° (picrate, m.p. 144°),1 :7-, b.p. 258° (picrate, m.p. 120°), and 2 : 3-Me2- ; 1 : 3-M er , b.p. 107°/1 mm. (p icra te , m.p. 118°) ; eudal- ene (picrate, m.p. 95° ; styphnate, m.p. 122°) ; 1 :4 :5 - and 1 :6 : 7-Me3-, m.p. 28° (picrate, m.p. 125° ; styphnate, m.p. 149°). R . S. C.

Dichloronaphthalenes and related interm ediates. R. W . B e a t t ie and F. C. W h it m o r e (J. Amer. Chem. Soc., 1933, 55, 1546—1548).—Details are given of the prep, of nine naphthalenesulplionyl chlorides from ' C10H 6Cl-SO3N a (prepared from NH2-Ci0H 6-SO3H by the usual method) and PC15. C10H 8Cl-SO2Cl and PC15 a t 160—165° give C10H 6C12 in 36—49% yield ; 1 :2 - , b.p. 295—298°, m.p.33—34°, 1 : 4-, m.p. 67-4—68°, 1 : 5-, m.p. 106—107°, and 2 : 6-, m.p. 136°, -C10H 6C12 are thus obtained.

H. B.[Regularity in the structure of the absorption

spectra of arom atic hydrocarbons. IX .] H.Co n r a d - B il l r o t h (B e r ., 1933, 6 6 , [¿?], 639—640).— A criticism of the work of Clar (this vol., 269) from a physical viewpoint. H. W.

Synthesis of phenanthrene and its derivatives. M .T .B o g e r t (Science, 1933,77,289).—1-Phenylethyl- cí/cZohexan-1-ol, prepared fromM gphenylethyl bromide and cî/cfohexanone, condenses (conc. H 2S04) to octa- hydrophenanthrene which yields phenanthrene by dehydrogenation with Se. L . S. T .

Isolation of a cancer-producing' hydrocarbon from coal tar. I—III. J . W. Co o k , C. L. H ew e t t ,

I . H ie g e r , and (in part) F. G o u l d e n (J.C.S., 1933, 395^405).—P artly a detailed account of work previously reported (this vol., 85). Medium soft pitch, by fractional distillation, crystallisation of the picrates, etc;, gives 2 : 3-benzcarbazole [2 : 7-dinitroanthraquin- one compound, m.p. 291—294° (decomp.)], chrysene,4 : S-benzjiyrcne (I), m.p. 181—187° (pierate, m.p. 235°) (probably not carcinogenic), 1 : 2-benzjnjrene (II), m.p.175-5—176-5° (picrate, m.p. 188— 192°) (highly carcinogenic ; gives the characteristic fluorescence spectrum of the carcinogenic fractions of tar), perylcne, and 1 : 2-benzanthracene (isolated by dissociation of the maleic anhydride adduct when sublimed a t 300°/5 mm.). Succinic anhydride, pyrcnc (III), and A1C13 in P hN 02 a t room temp, give (3-1 -pyrenoylpropionic acid, m.p. 183° (semicarbazone, m.p. 203—205°, unchanged by NaOEt a t 200°; Et ester, m.p. 90—91°), giving pyrene with ZnCl2 a t 160—170° or hot AcOH- H 2S04, and reduced by Zn dust-NaOH-aq. NH3 (but not by Zn and HCl-AcOH, or by Clemmensen’s method) to y-l-pyrenyl-y-butyrolactone, m.p. 178°, and y-l-l-pyrenylbutyric acid, m.p. 185— 186°, also obtained by reduction of the lactone. This acid with ZnCl2 a t 180°, or, much better, SnCl4 a t 115—120°, gives 4-'-keto-l' : 2' : 3 ': ‘i'-tetraliydro-l : 2-benzpyrene, m.p. 171-5—173-5° [oxime, m.p. 222—224° (decomp,)], whence by Se a t 300—340° (II) (AO;,-derivative, m.p.233—236°; quinone, m.p. 242—244°) was obtained. °-C6H 4(C0)20 , (III), and A1C13 in C6H 6 give 1 -pyren- oyl-o-benzoic acid, m.p. 224-5—225-5°, reduced (Zn dust-Cu-aq. NaOH) to 1-o-carboxybenzylpyrene, m.p.217—218°, which is cyclised by ZnCl2 a t 200° to a ketone [also obtained from o-toluoyl chloride, (III), and A1C13 in CS2 or P hN 02], not obtained pure, but reduced (Zn dust-ho t aq. NaOH) to 2 ': 3'-naphtha-1 : 2-pyrene, orange, m.p. 273° (probably not carcinogenic), which with maleic anhydride in hot xylene gives 2' : Z'-naphtha-\ : 2-pyrene-Y : 4'-endo-a[3-succinic anhydride, decomp. 270—280°. 4 -K eto-l: 2 :3:4- tetrahydrophenanthrene and MgPhBr or Mg(C6H n )Cl give 4-hydroxy-l : 2 : 3 : -i-tetrahydrophenanthre?ie, m.p. 140—141° (not completely dehydrated by picric acid in boiling EtOH), and an oil, whence by Se phenanthrene and a substance, C28H 160 , m.p. 312°, possibly a diphenanthrafuran, were obtained. Triplienylene, A1C13, and (C0C1)2 in CS2 a t room temp, give tri- phenylenecarboxylic acid, m.p. 325—326° (decomp.) (Na salt; Me ester, m.p. 122—124°). Reduction of pyrene with Na and amyl alcohol gives s-hexahydro- pyrene (IV), m.p. 132—133° (lit, 129—130°), also prepared by hydrogenation with Ni in tetrahydro- naphthalene (cf. A., 1907, i, 310), and zs-hexahydro- pyrene (V), m.p. 105— 105-5° (picrate, m.p. 147-5— 148°). The constitution of (IV) is proved by oxidation with KM n04 in KOH-aq. COMe2 to naphthalene-1 : 4 : 5 : 8-tetracarboxylic dianhydride, whereas(V) was more resistant and did not give a C10H5(CO2H)3. (IV), succinic anhydride, and A1C13 in P hN 02 give (3-1 : 2 :3 : 6 : 7 : S-hexahydroA-pyrenoylpropionic acid, m.p. 173-5°, reduced by N a-H g in NaOH to y -1 : 2 : 3 : 6 : 7 : %-hexahydroA-pyrenyl-y- butyrolactone, m.p. 150—154°, whilst the semicarbazone, m.p. 221—222°, with N aO Et-EtO H a t 180—190° gives y-1 : 2 : 3 : 6 : 7 : S-hexahydro-4-pyrenylbutyric acid, m.p. 133—134°; with S0% H 2S04 a t 100° this affords

602 BRITISH CHEMICAL ABSTBACTS.----A.

l'-i-eto-l : 2 : 3 : 6 : 7 : 8 :1 ' : 2 ': 3' : 4 '-decahydro-i : 5- benzpyrene, m.p. 147—148°, dehydrated by Se a t 320—340° to -(I) (picrate, m.p. 229—230°), believed to be identical also with the substance, m.p. 183°, stated to be C^-H^ or C1;H 10 by Meyer et al. (A., 1920, i, 589). R . S. C.

Chem ical reactions induced by ligh t. IV. L. V e c c h io t t i and C. P ic o in in i (Gazzetta, 1933, 63, 112—115; ef. A., 1932, 130).—Tho action of sunlight for 6 months on a m ixture of o-CGH.,Mo-N02 and NH 2Ph gave a product containing p-OH'CgHj'NHo, 2 '-inethylazoxybenzene, P h ,NOIN,C6H 4Me, m.p. 70°, and an isomerido of the latter, probably a benzene- azocresol, m.p. 88—89°. 0 . J . W.

Preparation of anils of sim ple aliphatic ketones. (M l l e s .) M. M o n t a g n k and. G. R o u s s e a u (Compt. rend., 1933, 196, 1165—1167).—Butyranilide and excess of M gEtBr form the complex CPrEt(OMgBr)*NPh,MgBr, which is hydrolysed to COEtPr, bu t is converted by heating in presence of C6H 6 or PhMo followed by hydrolysis into Et Pr ketanil (I), b.p. 114— 115°/li mm. (picrate, m.p. 102°), and an anil of a higher unsaturated ketone, b.p. 99— 103°/14 mm. (oxime, b.p. 138-—142°/14 mm.). (I) is reduced by N a-E tO H to y-anilinohexane, b.p. 123— 125°/13 mm. {phenylurcthane, m.p. 55°; acetate, b.p. 154— 155°/13 mm.). Butyro-^-toluidide gives E t Pr ketotolil, b.p. 130—133°/13 mm., reduced to y-p-toluid- inohexane, b.p. 138—139°/15 mm. Propionanilide gives, in addition to the unsaturated ketone, b.p. 90—93°/20 mm., E t2 ketanil, b.p. 110—111°/18 mm. {picrate, m.p. 143°), which is reduced to y-anilino- pentane, b.p. 114°/13 mm. (acetate, b.p. 153°/18 mm.). Butyrophenoneanil has b.p. 150°/3 mm. A. C.

M odified Curtius degradation. VII. D egradation of arom atic acids. C. N a e g e l i and A. T y a b j i (Helv. Chim. Acta, 1933, 16, 349—366; cf. A., 1929, 540).—Reactive Ar-COCl are heated with NaN3 in C6IL until evolution of N2 ceases and the resulting Ai-NCO (isolated or in solution) is warmed with conc. HC1 [sometimes with 60% (vol.) H 2S04],1—50% alkali hydroxide, or A c0H -A c20 , thus giving Ar*NH2,HCl, NH 2Ar, or NHArAc, respectively, to gether with varying amounts (0—98%) of CO(NHAr)2. The products thus obtained from tho azide or carbimidc from BzOH, m- and p-N 02-CgH4*C02H, 3 : 5-(N02)2C6H 3-C02H, and azobonzeno-m-carboxylic acid [chloride, m.p. 72°; azide (I), m.p, 76—77° (decomp.)], are studied in detail. i>-N02,C6H4*C0N3 is hydrolysed only w ith difficulty. ” Relatively largo amounts of (i»-N02<C6H 4-NH)2C0 aro usually formed during tho above treatm ents. (I) decomposes in C6H 6 a t 90—100° to m -benzeneazo- phenylcarbimide, m.p. 45—46°, which w ith H 20 or m-aminoazobenzene (II) gives s-di-{m-benzeneazo- phenyl)carbamide (III), m.p. 275—276°, with EtOH yields E t m-benzeneazophenylcarbamate, m.p. 102— 103°, and w ith Ac20 a t 90° affords 32% of (III) and29 and 21%, respectively, of the Ac and Ac2% m.p. 60—61°, derivatives of (II). m-NO^CgH^NCO and CC13-C02H in CgH6 give 17% of (m-N02-C6H4-NH)2C0 and 68% of m-nitrotrichloroacetanilide, m.p. 104° (also prepared from m -N02-C6H4-NH2 and CC13-C0C1). 3 : 5-Dinitrophenylcarbimide, m.p. 91°, passes into a

polymeride, m.p. about 330° (decomp.), when heated to 94—95°, m-CgH^Br-NCO (in C»He) is hydrolysed by 10% KOH to m-CGH 4Br-NH2 (90% yield).

H. B.Action of arom atic sulphur com pounds on

fungi. T. H a c h iy a and J . N i s h i m u e a .— See this vol., 638.

Fluorene derivatives. I. 3-Am inofluorene.M. H a y a s h i and A. N a k a y a m a (J. Soc. Chom. Ind. Japan, 1933, 36, 127—1 3 0 b ).—Tho ultra-violet absorptions of a no. of fluorene derivatives are determined. Tho following aro described : ‘¿-nilro-2-acetamido-, m.p. 200—201° (1-N02-? ; prepared from “ 3-nitro-2-aminofluorene ” from 2-acctamidofluorono; cf. A., 1902, i, 758); 7-nitro-2-acetamido-, m.p. 256— 257° (+ 1 H 20 ); 3-(or ? l)aini?io-2-acetamido-, m.p. 194-5—-195-5°, and 3-amino-fluorene, m.p. 151— 152° (Ac derivative, m.p. 189—190°). H. A. P.

Isatogens. X I. Reduction products of di- and tri-nitrodistyrylbenzene. P. R u g g l i , A. Zim- m e r m a n n , and W. H eit z (Helv. Chim. Acta, 1933,16,454—468):—4 : 6-Dinitro-l : 3-distyrylbenzeno is reduced by E tO H -N H 4HS to 5-nitro-2 :4 -distyrylaniline, m.p. 111° (Ac derivative, m.p. 235°), and by SnCl2 and AcOH-HCl, or, better, H 2, Ni, and aq. EtOH-EtOAc, to 4 : 6-distyryl-m-phenylenediamine, m.p. 201° (lit. 204°) (Ac2, m.p. 284—285°, and di-p- toluenesulplioiiyl, m.p. 233°, derivatives). 2 :4 :6 - Trinitro-1 : 3-distyrylbenzeno (I) is reduced (EtOH- NH4HS) to 3 : 5-dinitro-2 : 4-distyrylaniline, m.p.171—172° (Ac, m.p. 208°, and Ac2, m.p. 175°, derivatives), or a mixture of this and 5-nitroA : 6-distyryl- m-phenylenediamine (II), m.p. 175-5° [^lc2 derivative (III), m.p. 276°], according to tho conditions used.(II) is also obtained by catalytic reduction (as above) of (I). Reduction (Zn dust, AcOH) of (III) affords 3 : 5-diacetamido-2 : 6-distyrylaniline, m.p. 230°, acetylated (Ac20) to the ^lc3 derivative, m.p. about 334° (becomes brown > 290° and black a t 320°), of 2 : 4 : 6- triamino-1 : 3-distyrylbenzene, m.p. 161°. All the above amines aro purified through their Ac derivatives. Furthor aeetylation of (III) gives Ac3 (+AcOH), m.p. 224°, and Ac4, m.p. 150°, derivatives; these are readily hydrolysed (dil. EtOH-NaOH) to (III). H. B. ;

R eactions of s-di-(9-phenyl-9-fluorenyl)hydrazine. L. A. P in c k (J. Amer. Chem. Soc., 1933, 55, 1711— 1716).—9-Bromo-9-phenylfluorone andN2H 4,H20 in xylene a t 100° give %-di-(^-phenyl-^- fluorenyl)hydrazine (I), m.p. 195—196° (decomp.), and 9-phenylfluorenyl peroxido (II), m.p. 194°, and a little 9-phenylfluorene ( I I I ) ; a t room temp., (I ll) is the main product. (I) reacts with Na in liquid NH3 to give a Na-derivative [hydrolysed to (III)], is unaffected by “ active ” Ag,,0, and is oxidised (KMn04- COMe2; Bz20 2-CHC13) to" (II). (I) and Pd-black (IV) in C6H 6 give N2, (III), and a little diphenyldi(di- phenylene)ethane (V), indicating tho intermediate formation of azo-9-phenyl-9-fluorene, Air bubbled through (I) and (IV) in C6H 6 gives (II) and 9-hydroxy-9-phenylfluorene. (II) and (V) are reduced [H2, (IV), C6H 6] to (III). W ieland’s results (A., 1909, i, 836) on the probable transitory existence of (2f'CPh3)2 are confirmed. ,s-Di(triphenylmethyl)hydrazino and HC1


do not give the hydrochloride (cf. Wioland, loc. cit,), but afford N2H 4>2HC1 and CPh3Cl. H. B.

Interaction of acetonephenylhydrazone and phenylcarbim ide. P. J . W i l s o n , W . A. C a l d w e l l , J . C h a p m a n , and H . W. G o o d w in (J. R oy.Tech. Coll., 1933, 3 , 24—25).—NHPh-N:CMe2 and PhNCO (I) in boiling C6H 6 or a t 100° (no solvent) give acetone-p8-di- phenylsemicarbazone, m.p. 141° (also prepared from C0Me2 and pS-diphenylsemicarbazide), ap-di(phenyl- carbamyl)phcnylhydrazine, m.p. 208° [also obtained from NHPh-NHo and (I) (2 mols.) or from (I) and aS- or [38-diphcnylsemicarbazido], and ta rry products (cf. W hybum and Bailoy, A., 1928, 516). H. B.

Action of chlorosulphonic acid on phenol and p-cresol at low tem peratures. G. N. B u r k h a r d t (J.C.S., 1933, 337—338).—Interaction of C1S03H (I) (added in 20 min.) w ith PhOH in CS2 a t —15° during2 hr. affords approx. cquimol. proportions of P1iHS0 4 and i>-0H,C6H 4,S03H. Slow addition of (I) or long period for reaction favour sulphonato formation. Similarly -crcsol affords a product containing > 90% p-tolyl H sulphate. J . L. D.

T herm al decom position of phenyl v inyl ether,W. M. L atter and M. A. S p ie l m a n (J. Amer. Chem. S o c ., 1933, 55, 1572—1574).—Ph vinyl ether (I) heated a t 295—300°/3 hr. in a sealed tube gives PhOH, CHMe(OPh)2 [prepared by slow addition of PhOH to boiling (I) in C02], and a residue of high mol. wt. H. B.

B asis for the physiological activity of -onium compounds. XII. A ryl ethers of choline. R. R.R e n s h a w and C. Y. H o p k in s (J. Amer. Chem. Soc., 1933, 55, 1524—1528).—The following are propared from the appropriate C6H4R-0-CH2'CH2Br and NMe3 : $-p-hydroxy-, m.p. 254°, -p-methoxy-, m.p. 144°, -o-methoxy-, m.p. 139°, -p-benzoyloxy-, m.p. 208—209°, -p-acetoxy-, m.p. 152°, -p-amino-, m.p. 195° (hydrochloride, m.p. 265°), -p-acetamido-, m.p. 248°, -2-methoxy-i-allyl-, m.p. 147°, and -2-methoxyA-propenyl-, m.p. 158°, -phcnoxyethyltrimethylammonium bromides; none of theso is as active as OPh,CH2-CH2*NMe3B r (A.,1929, 1487) in stimulating respiration and blood pressure. p-Hydroxy- (I), m.p. 107°, p-acetoxy-,mp. 76-5— 77°, p-benzoyloxy-, m.p. 119°, p -methoxy-, m.p. 49— 50°, 2-methoxy A-prope,nyl-, b.p. 190°/12 mm., and 2-viethoxyA-allyl-, b.p. 182°/13 mm., m.p. 23° (all m.p. except this are corr.), -phenyl fi-bromoethyl ethers are prepared from CttH 4R-OH, s-C2H4Br2, and MeOH- KOH. Quinol di-$-bromoethyl ether, m.p. 115°, is formed with (I), a|3-D i-m -hy 'droxyphenoxy-, m.p. 165°, and afi-dianisyloxy- (described as a(3|dianisyl-), m.p. 147-5°, -ethanes are also prepared. H. B.

Stereochem istry of dicyclic ring system s.VII. S tereoisom erism of decahydronaphth-

alene and its derivatives. III. S tereoisom eric ^-substituted decahydronaphthalenes. W.H u c k e l , R. D a n n e e l , A. G r o s s , and H. N a a b . IV. »-Substituted decahydronaphthalenes. W.H uoicel and M. B lo h m (Annalen, 1933, 502, 99—114,

—136).—VI. Reduction (H2, colloidal P t, H 20) (the effect of pressure, amount of catalyst, and temp, are studied) of ar-tetrahydro-a-naphthol (1) gives decahydronaphthalene, liquid decalols, and (mainly) cis-

a-decalol (cia-decahydro-a-naphtliol) (II), b.p. 245° (corr.)/745 mm.j m.p. 93° (A., 1925, i,: 258) [acetate, b.p. 129°/15 m m .; I I phthalate, m.p. 176°; H succinate, m.p. 66°; succinate, m.p. 150°; oxalates, m.p. 98— 100° and 139°; p -nitrobenzoate, m.p. 83°; p-tolucne- sulplionate, m.p. 96—98° (decomp.)], also obtained in small amount (together with a compound, C20H 22O, m.p. 113—114°, and other products) by similar reduction of <x-C10H 7-OH. cw-a-Decalol, m.p. 55° (H phthalate, m.p. 142°), is prepared from (V) (below) and H N 02. Reduction (Ni ?) of a-C10H 7-OH a t 180— 210°/60—80 atm. gives tetra- and deca-hydronaphth- alenes, (I), 1-ketodecahydronaphthalene, trans-cc- decalol (III), m.p. 49° (A., 1930, 206) [acetate, b.p. 115°/10 mm., m.p. 30° ; I I phthalate, m.p. 121°; II succinate, m.p. 107°; oxalates, m.p. 77—78° (dimorphous ; also with m.p. 85°) and 143°; p-nitrobenzoate, m.p. 116°], and <ra?is-oc-decalol, m.p. 63° [acetate, b.p. 121°/12 m m .; I I phthalate, m.p. 168°; H succinate, m.p. 85°; oxalate, m.p. 111°; p-nitrobenzoate, m.p. 86°; phenylurethane, m.p. 114 (lit. 172°)]. Some(III) is also produced during Adams reduction of (I). Tho above pairs (r- and meso-forms) of oxalates are obtained by the action of (COC1), in C5H 5N and are separable through their differing solubilities in light petroleum ; the use of H 2C ,04 (A., 1926, 238) gives unsatisfactory results. ciS-P-Dccalol, m.p. 105° (acetate, b.p. 1220/9 mm., m.p. 32°), yields oxalates, m.p.64—65° and 120°, whilst ¿r<ms-[3-decalol, m.p. 75° (acetate, b.p. I I 8 7 9 mm.), affords oxalates, m.p. 148° and 90—102°. The acetate of ¿ra«5-P-decalol, m.p. 53°, has b.p. 110°/9 mm.

Reduction (H2, colloidal P t, AcOH) of ar-tetrahydro- acet-a-naphthalide gives tho Ac derivative, m.p. 181°, of cis- a-decalylamine (cis-decahydro-a-naphthylamine) (IV), b.p. 98°/10 mm., m.p. 8° (Bz derivative, m.p. 206°), whilst reduction (Na, EtOH) of cis-a- decaloneoxime affords a m ixture of (IV) and cis-a- decalylamine (V), b.p. 100°/12 mm., m.p. —2° (Ac, m.p. 141°, and Bz, m.p. 193°, derivatives), separable through their hydrochlorides. W hilst alkaline reduction of ira?i5-a-decaloneoxime gives trans- a-decalylamine (VI), b.p. 106°/16 mm., m.p. —1° (Leroux, Ann. chim., 1910, [viii], 21, 458), reduction with H 2 and Pt-black in AcOH affords (VI), ¿ra?i3-a-decalylamine (VII), b.p. 99°/ll mm., m.p. —18° [Ac, m.p. 130° (lit. 127°), and Bz, m.p. 112°, derivatives], and tvBJis-a-decahydronaphthylhydroxylamine, m.p. 113°. Reduction (H2, Pt-black, AcOH) of a-tetraloheoximo gives (IV) (65%), (V) (25%), (VII) (10%), and (VI) (trace only).

VII. trans-9-Nitrodecahydronaphthalene (VHI), m.p. 24°, is separable from the mixture of N 0 2-derivatives obtained by Nametkin and Madaev-Sitschev (A., 1926, 508), and is obtained directly by nitration of irans-decahydro naphthalene. Reduction (Al-Hg,moist E t20) of (VIII) gives trans-Q-hydroxylamin0-(IX), m.p. 121—123° (Bz derivative, m.p. 67—68°), and tvans-Q-nitroso-decahydronaphthalene, blue (unimol.), b.p. 87°/18 mm., m.p. —16°, and colourless (bimol.), m.p. 100°, forms [also prepared by oxidation (H20 2) of (IX)]. More prolonged reduction affords tr&ns-Q-aminodecahydronaphthalene (X), b.p. 222-6° (corr.)/757 mm., 90°/13 mm., m.p. —25° [Ac, m.p. 183°, and Bz, m.p. 148—149° (cf. loc. cit.), derivatives;


formate, m.p. 172° (decomp.)]. The non-cryst. fractions obtained during the separation (above) of (VIII) are similarly reduced to (IX), (X), and cis-9-awnno- decahydronaphthalene (XI), b.p. 111°/1S mm.,- m.p. —13° [Ac, m.p. 127°, and Bz, m.p. 147°, derivatives;

formate, m.p. 165—166° (decomp.)]. The 9-N02- and -NHo-eompounds of Nametkin and Madaev-Sitseliov (loc. cit.) are mixtures of the cis- and irans-isomerides. Reduction (Al-Hg, moist E t20) of 10-chloro-9-nitroso- decahydronaphthalene (XII) (A., 1930, 76) gives10-chloro-d-hydroxylami7iodecahydronaphthalene (X III), m.p. 116— 120° (decomp.) (hydrochloride, decomp.172— 174°; Ac derivative, m.p. 81—83°), whilst Zn dust and E t20-conc. HC1 afford (X III) and (XV) (below). Reduction (Al-Hg, moist E t20 , cone. HC1) of (XII) yields §-liydroxylamino-l()-hydroxydecahydronaphthalene (XIV), m.p. 115— 119° {Bz derivative, m.p. 99°). (X III) is converted by boiling 2JV-NaOH into 9-hydroxylamino-odahydronaphthalene, m.p. 138— 143° (decomp.) (Bz derivative, m.p. 48—50°), and an unsaturated by-product, b.p. 45°/2 mm. Reduction (Zn dust, E t20-conc. HC1, or Al-Hg and moist E t20 for10 days) of (XII) also affords 9-amino- Ai:10-odahydronaphthalene (XV), b.p. 95°/ll mm., m.p. -11 -5° [Ac (XVI), m.p. 141°, and Bz, m.p. 119—120°, derivatives; formate, m.p. 138—141°], reduced (H2, P t0 2, dil. HC1) to (XI) and a little (X). Rapid reduction (H2, P t0 2, E t20 ) of (XVI) gives the Ac derivative of (XI), whilst slow reduction (H2, Pd-C, MeOH) also affords about 25% of the Ac derivative of (X). Reduction (Zn dust, E t20-conc. HC1) of (XII) also gives 9- amino-\Q-hydroxydecahydronaphthalene, m.p. 103° [Ac, m.p. 171— 172°, and Bz (+ H 20), m.p. 150—152°, derivatives; 0 -formyl derivative formate, m.p. 185— 187°], also obtained as a by-product in the prep, of (XV), by reduction (H2, P t0 2, dil. HC1) of (XIV), and from A9:10-octahydronaphthalene oxide and conc. aq. NH3 a t 100°, which with H N 02 affords trans-9 : 10- dihydroxydecahydronaphthalene and (as the result of a pinacolin rearrangement) a little cycZohexanone-2- spirocycloTpentano (A., 1930, 76). (X) and HNO, give some tvans-9-hydroxydecahydroiiaphthalene, m.p. 54° (which with aq. C r03 in light petroleum affords a chromate), and cis-9-hydroxydecahydronaphthalene, m.p. 65° [also formed from (XI) and H N 02]; these alcohols are accompanied by mixtures of A1:9- and A9:10-octahydronaphthalenes. (XV) and H N 0 2 give an unsaturatcd alcohol, oxidised (Cr03, aq. AcOH) to (probably) l-keto-A9:10-odahydro7iaphtlialene [semicarbazone, m.p. 244° (decomp.); oxime, m.p. 148° (Bz derivative, m.p. 134°)], which is reduced (H,, Pd-C, E t20 ) to irans-l-ketodecahydronaphthalene.

H. B.A ntiseptics and anthelm intics. I. 1-AIkyl-

[i-naphthols. K. C. G u l a t t , S. R . S e t h , and K . V e n k a t a r a m a n (J. pr. Chem., 1933, [ii], 137, 47— 52).—p-Naphthyl esters are isomerised by A1C13 to1-acyl-p-naphthols, the ketonic nature of which is established by transform ation by Bz20 and NaOBz into 2-alkylnaphthaflavones, and these are reduced (Clemmensen) to l-alkyl-J3-napkthols. The following transformations are described : p-naphthyl propionate into 1 -propionyl-, m.p. 70—71° (2-methyl-$-naphthaflavonc, m.p. 110°), and 1 -propyl-$-naphthol, b.p. 143—145°/3 m m .; $-naphthyl n-butyrate, b.p.

164—165°/3 mm., into 1 -bu tyrybfi-naph thol, b.p. 167— 168°/1— 2 mm., 2-dhyl-[i-naphlhaflavone, m.p. 112°, and l-n-butyl-$-7iaphthol, b.p. 190°/3 mm., m.p. 80— 81°; $-n ap lith yl n -valerate, b.p. 166°/4 mm., into1-valeryl-$-nap)ithol, b.p. 165-—166°/1 mm., 2-propyl-fi- naphthaflavone, m.p. 103°, and l-n-a,myl-[i-naphthol, m.p. 84°; $-nap>lithyl 11-hexoate, b.p. 174— 176°/1—2 mm., into 1-hexyl-fi-naphthol, b.p. 188—190°/4 mm.,2-butyl-$-naphthaflavone, m.p. 103°, and l-n-hexyl-'fi-naphthol, m.p. 123°. H. W.

W alden inversion reactions of the jj-toluenesulphonic and -sulphinic esters of I-phenyl- m ethylcarbinol. J . K enyon , H. P hillips, andF. M. H. Taylor (J.C.S., 1933, 173—178; cf. A.,1930, 1177).—ź-CHPhMe*OH (I) [Ac derivative (II), b.p. 109°/1S mm., [a]5S93 —58-4°] with p-toluene- sulphinyl chloride in C5H 5N gives the Z-p-toluene- sulphinate (III) without inversion, since (III) gives (I) with EtOH and K 2C03. (I ll) with EtOH alone gives rf-a-phenyldicthyl ether (IV), also obtained (with a little di-^-tolylsulphoxide) when (I) is heated in anhyd. EtO H with ^-toiuenesulphinic acid. A similar reaction with ^p-toluenesulphonic acid on the d-alcohol gives I- a-phcnyldiethyl ether (V), inversion occurring in both cases. The ^-toluenesulphonate (VI) of (I) could not be isolated. Measurements of the relative rates of formation of (VI) and jj-tolyl-a-phenylethyl- sulphonefrom (III) in E tO H with air in presence and absence of K 2C03 are recorded. Action of EtO H and K 2C03 on (Vi) [prepared in s i tu in this and the following reactions by the action of H 20 2 on (III)] also gives (IV) with inversion, and a similar reaction with ?t-BuOH gives d-n-bu ty l a-phenylelhiyl ether, b.p. 102°/23 mm. [Z-isomeride, [oc]58M —53-8° in EtOH, from Bui and the K derivative of (i)]. (VI) with LiCl in Ac20 gives d-a-chloroethylbenzene (VII), and the ¿-form of(II). The latter is produced from (VI), since (VII) w ith Ac20 alone gives only a little acetate. (I ll) and (VI) in EtO H with LiCl and K 2C03 give (V), the reaction with (III) in presence of air giving a product of lower rotation than when air is absent. Reasons are given for assuming th a t (VII) is produced with inversion as an intermediate in th is reaction. (VI) with AcOH gives the ¿-form of (II), whilst similar treatm ent of (III) gives unusually the dZ-form. When the entering group forms an anion, (VI) undergoes replacement reactions with inversions similar to p-tolucne- sulphonates in which the asymmetric C atom is not directly attached to Ph. ( I ll) differs from purely aliphatic and hydroaromatic | 3- t o l u e n e s u l p h i n a t e s in undergoing inversion reactions, particularly in acid solution. A. A. L.

Catalytic hydrogenation of esters to alcohols.III. H. A d k i n s , B. W o j c i k , and L. W . Co v er t (J. Amer. Chem. Soc.,1933, 55, 1669—1676; cf. A.,1932, 599; this vol., 143).—Pure CH2Ph-C02E t (I) is obtained by heating the commercial product with catalytic Ni and H 2 a t 175°/100 atm . for 3 hr. and subsequent - distillation; CH2Ph-CN (the chief impurity) is eliminated partly as NT$-di-$-phenylethyl- phenylacetam ide, m.p. 143-5°. The best yields of CH,Ph-CH2-OH (II) from (I) and a Cu-Cr oxide catalyst (Ji) are obtained when reduction is interrupted [5—10% of (I) remaining]. 0 H ’CHPh-C0.2Et


is reduced [( /I); practically all experiments using (4) are a t 250°] to (II) and a little P h E t; Ni at 175° gives 95% of (I). (I) is reduced (Ni a t 200°) to E t cyclo- hexylacetate (77%) and thence (A ) to p-cyc/ohexyl- ethyl alcohol (94%). o-C6H 4Bz-C02E t gives (/I) o-CGH4Me-CH2Pli (93%); with Ni a t 150°, o-benzyl- henzoic acid (III) results (by way of the lactone of benzhydrol-o-carboxylic acid). The E t ester of (III) is reduced (Ni a t 150°) to Et o-hexahydrobenzylhexa- hydrobenzoate, b.p. 155—-158°/12 mm., converted further [A) into o-hexahydrobenzylcyclohexylcarbinol, b.p. 148—152°/10 mm., and a little 2-hexahydro- benzyl-l-methylcyclohexane, b.p. 125—131°/10 mm. o-C6H4(CO)20 is reduced (Ni a t 150°) to phthalide (34%), o-CcH4Me-C02H (36%), and hexahydro-o- toluic acid (23%); o-C6H 4(C02E t)2 (IV) gives (4)o-C6H4(CH2-OH)2 (0—9%), o-C6H 4Me-CH2-OH (0— 14%), and o-xylene (67—84%), whilst E t hexahydro- phthalate [from (VI) using Ni a t 200°] similarly affords the corresponding hexahydro-derivatives (0— 40%, 70—94%, and 6%, respectively). E t benzilate is reduced (A) rapidly a t 125° to oca-diphenylethylene glycol (77%), probably through the tautomeric form,CPh2< ^ Q j j j .Q g t ; CHPh2-C02E t similarly gives (at200°) CHPh2-CH2-OH (58%) and CHPh2Me (38%). Attempts to modify (4) so th a t reduction of (I) gave increased amounts of (II) were unsuccessful. H. B.

Rearrangem ents of polyinenes. IV. s-T etra- phenyldi - (y - m ethyl-y-ethyl-Aa-pentinyl )ethane.J. H a r m o n and C. S. M a r v e l (J. Amer. Chem. Soc., 1933, 5 5 , 1716—1722; cf. this vol., 56, 57).—M e d iphenyl-(y-m ethyl-y-ethyl-ha-pen tin yl)m eth yl ether, b.p. 143—147°/0-32 mm., prepared from the corresponding carbinol (A., 1932, 496) by the method of Moureu et a l. (A., 1925, i, 136), and 40% Nar-Hg in E t20 and N 2 give Na diphenyl- (y-methyl-y-ethyl-Aa-pentinyl)methyl (I), which with C 02 affords d iph en y l-(y -m d ]iy l-y -e th y l-A a- pentinyl)acetic a c id (II), m.p. (block) 141— 142°, (tube) 153—154° (softens a t 140°). (II) is oxidised (Cr03, AcOH) to BzOH, COPh2 (57%),o-CfiH4Bz-C02H, and anthraquinone; COPh2 (57%) and BzOH result from KM n04 and 1% KOH. (I) is converted by s-C2Me4Br2 in E t20 into the unstable (not isolated) s-tetraphenyldi-(y-methyl-y - ethyl-A“ - pentinyl)ethane (S&jiq - tetraphenyl - y* -dimethyl-yK-diethyl- A00-dodeca- di-inene), which is cleaved by 40% N a-H g to (I), is readily oxidised (a ir ; C r03) to COPh2, and rearranges to the hydrocarbon, C42H46 (III), m.p. 105-6—108° (cf. loe. c it.). (I ll) is not oxidised by 0 2, but with K2Cr20 7 and AcOH gives a neutral com pound, C36H30O2, m.p. 137— 138° [tctrahydro-dci'ivA tivc, m.p. 226-5—228° (corr.)], and a little o-C6H 4Bz-CO,H.(Ill) and 40% Nar-Hg in E taO give a N a alkyl which with C02 affords (II) in a max. yield of 36% [thus indicating th a t half of the mol. of (III) has retained the original structure], H. B.

Action of selen ium dioxide on sterols and bile acids. I. E rgosterol and dihydroergosterol.R. K. Callow and O. R o s e n h e im (J .C .S ., 1933, 387— 390).—Ergosterol, dihydroergosterol (I), lumisterol, calciferol, and a^ocholic acid in E t0 H -H 20 a t room temp, react with Se02 and deposit Se (cf. A., 1932,487). Many other ergosterol derivatives react when heated,

those containing an ethenoid or bridge linking resistan t to catalytic hydrogenation being the more re active (cf. A., 1932, 736, 845). Some cholesterol derivatives react only in AcOH a t 100°. Ergosterol reacts with Se02 in EtO H -C GH g at 18° during 19 hr. to give dehydroergosterol (3 : 5-dinitrobenzoate, m.p. 185— 189°). (I) (3 : 5-dinitrobenzoate, m.p. 206-5—207-5°, [ajjj" —1-8° in C6H 6), prepared by hydrogenating ergosterol (Pd-C), gives with Se02 in EtO H -C6H B dihydroergosterol oxide (II), m.p. 110—111°, [<xjg* —44-3° in CHC13 [+ 5 MeOH, m.p. 99°; Ac derivative (III), m.p. 107— 109°, [a ]f -4 7 ° in CHC1,; Bz derivative, m.p. 118—120°, [aJfJ ! —36° in CHC13;3 : 5-dinitrobenzoate, m.p. 198° (decomp.)]. Crude (I) with A c20 during 10 min. affords a product (m.p. 170—173°) which with N aO H -EtOH gives ergosterol-D. (II) on prolonged boiling with Ac20 containing II2S04 affords ergosterol--B3 acetate, which is formed rapidly a t room temp, from (III) in AcOH containing1 drop of H 2S04. Ergosterol-Z) acetate is not isomerised under these conditions. J . L. D.

Synthesis of perhydrovitam in-4. P. K a r r e r , R. M o re , and K . S ch o pp (Helv. Chim. Acta, 1933,16, 557—561).—E t 8 - 2 : 6 : 6-trimcthyl-A1-c?/c/ohexenyl- (B-methyl-AaV-butadiene-a-carboxylate (A., 1932, 852) is reduced (H2, Pt) to the fully saturated ester, which is then reduced (Na, EtOH) to £ -2 : 6 : 6-trimethyl- c?/cfobexyl-y-mothyi-tt-amyl alcohol. The bromide is converted (malonic ester method) into i-2 : 6 : 6-tri- metliyIcycZohexyl-8-methylheptoic acid, and thence into the chloride, which with ZnMel gives ?-2 : 6 : 6- trimethylc?/cZohexyl-8-methylhexyl Me ketone (semicarbazone, m.p. 114°). This with Zn and CH2Br-C02E t affords E t p-hydroxy-0-2 : 6 : 6-trimethylci/cZohexyl Pi-dimethylnonoate; replacement of the OH by Br and then f i and subsequent reduction (Na, EtOH) givesi-2 : 6 : 6-irimethylcyclohexi/l-yrr dimethyl-n-7ioni/l alcohol (I), b.p. 148—149°/0-15 mm., which is identical with perhydrovitamin-J. (II), b.p. 148—150°/0-15 mm. (A., 1932, 200). The bromides from (I) and (II) are converted (malonic ester method) into « - 2 : 6 : 6- trimethylcyclohexyl-W-dimethylundecoic acid, b.p. 186°/ 0-4 mm., the chloride of which with ZnMel gives k-2 : 6 : 6-trimethylci/cZohexyl-80-dimethyldecyl Me ketone (semicarbazone, m.p. 67°). No details are given. H . B.

Surface film s of cestrin derivatives and of pregnandiol. J . E. D a n i e l l i , G. F. M a r r i a n , andG. A. D . H a s l e w o o d (Biochem. J ., 1933, 2 7 , 311— 320).—Measurements of surface pressure and surface potential indicate th a t the products of reduction of kctohydroxycestrin (I) by Clemmensen’s method and of its semicarbazone by NaOEt are identical; this is supported by direct comparison (mixed m.p.). Similar measurements on other derivatives of cestrin and pregnandiol, and on calciferol and ^-cholesterol, support Butenandt’s formuke for pregnan-diol and -dione (A., 1932, 54) and for (I) and trihydroxycestrin (Z. angew. Chem, 1932, 4 5 , 655), but do not fix the positions of the M e and OH or 10 groups in the latter cases. Hydrogenation of (I) (P t0 2) in EtO H gives dihydroxycestrin, m.p. 174— 176° (diacetate, m.p. 120— 122°; Me ether, m.p. 91—94°), and hexahydrodihydroxy-

60G BRITISH CHEMICAL ABSTRACTS.----A.

ceslrin, in.p. 209—2119, which is obtained in better yield in AcOH. H. A. P.

[Polyterpenes and polyterpenoids. X XIX .] D ehydrogenation of cholesterol and cholic acid.0. D i e l s (Ber., 1933, 66, [B], 487—488).—A reply to Ruzicka and Tliomann (this vol., 278). H , W.

Properties of ergosterol and calciferol. A. L.B a c h a r a c h , E. L. S m it h , and S . G. S t e v e n s o n .—See this vol., 542.

R eactions relating to carbohydrates and polysaccharides. XLV. Polym erisation , under the influence of heat, of com pounds containing the ethylene oxide ring . E. C. J a h n and H . H i b b e r t (Canad. J . Res., 1933, 8, 199-—209).—Phenylglycidc(I), m.p. 26;50, b.p. 134— 135°/4— 5 mm. (phenylurethane, m.p. 87°), prepared from cinnamyl alcohol and B z02H in CHC13 a t 0°, is converted by heating at 140—155° (29 hr.) into a dimeride. This gives a Me2 ether, b.p. 180—185°/0-03 mm., with Mel and Ag20 , bu t a monolrityl derivative, and therefore has only one prim ary OH group. W ith NH 3 the Mc2 ether gives a monoammine, C20H24O4,NH3, and therefore contains only a single ethylene oxide ring. Polymerisation occurs therefore by addition of the ethylene oxide ring to the OH group (cf. Nef, A., 1905, i, 3 et seq.). When heated for a much longer period (32 days) a t 105°, colourless resinous polymerides, which still combine with NH3, and coloured by-products are formed. Methylglycide, b.p. 93—97°/44 mm. (plienylurethane, m.p' 66'5°), similarly prepared from erotyl alcohol, when heated a t 105° for 22 days gives a liquid dimeride (idiphenylurethane, m.p. 78—80°). Oxidation of s-di- propenylethyleno glycol with B z02H gives Ss-dihydroxy-$y-^rrdioxido-octane, b.p. 125—128°/4 mm., which is partly converted into a trimeride during fractional distillation a t 4 mm. The acetate of (I), b.p. 121)— 133°/3 mm. (from CHPh:CH-CH2-OAc), is slowly converted a t 140° into a m ixture of polymerides from which a dimeride, b.p. 140—145°/0-l mm,, and a solid resin were isolated. The Me, ether of (I), b.p. 130— 137°/21—23 mm. (from cinnamyl M e ether, b.p. 92°/5 mm.), is not polymerised by heating alone or with moist KOH or ZnCl2, b lit undergoes complex decomp. with formation of resins. The Me ether, b.p. 107— 110°, of [3-hydroxyethyl vinyl ether is oxidised by B z02H to dimeric glycide [i-mathoxyethyl ether, b.p.118-—119°/0-l mm., which absorbs only 0-16 mol. NH3 and is therefore regarded as the stable dioxan derivative,0Me-[CH2]2-0 -C H < ^i£ H02>CH-0-[CH2]2-0M e^

Chem ical structure and optical rotation. IV. Configurative relationship of d isubstituted acetic and propionic acids containing a phenyl group. P. A. L e v e n e , R. E . M a r k e r , and A. R o th en (J. Biol. Clicm., 1933,100, 589—002; cf. A.,1932, 1028).—The substances previously (A., 1930, 1287) described as (a) p-phenyl-butyric and (b) -valeric acids contained [a) m ostly and (b) much a-phenylbutyric and -valeric acid, respectively, formed by rearrangement during the decomp. of the amine. Since, however, the sec. halides give inactive substituted acetic acids, the correlations previously estab

lished are still valid. They are confirmed by the present observations. a-Phenylethyl bromide and chloride give (3-phenylpropionic acid with the same Jf[a], the same amount of racémisation having taken place in each case. The esters of disubstituted phenylacetic acids are racemised by reduction in PhMe, but not in C6H 6 solution. The rotation of a-cycZohexylbutyric acid previously (loc. cit.) given should be reversed. All rotations (which are not max.) given below are for the homogeneous liquid, unless otherwise stated. a-Phenylpropionic acid, [Üf]î5 +35-1°, is hydrogenated (P t0 2) in AcOH toa.-Q,yc\ohexylpropionic acid, b.p. 103°/3 mm., [a]jf4-5-2°. a-Phenylbutyrie acid, [JÎ]“ +46-7°, gives a-cyclohexylbutyric acid, b.p. 120°/3 mm., [a]$ —0-15°, and a-phenylvaleric acid, [i/Jg +16-0°, a-cyclohexyl- valeric acid, b.p. 140°/3 mm., [a]“ —0-64°. (3-Phenyl-?i-propyl alcohol is resolved by the brucino salt of the 3-nitrophthalate, giving the d -form, b.p. 92°/4 mm., [ajg +9-07°, hydrogenated to p-cycloAexyZ-n- propyl alcohol, b.p. 84°/2 mm., [ajg 0°, giving with PBr3 (3-phenyl-n-propyl brmnidc, b.p. 78°/l mm., [ajg —2-56°, and with PC13 the corresponding chloride,b.p. 72°/l mm., [a]g —2-00°; the halides yield (Grignard) $-phenylbutyric acid, b.p. 127°/1 mm., [ajf? -—10-39° and —10-35°, respectively. p-Phenyl-?i-butyl alcohol, resolved by the strychnine salt of the 3-nitrophthalate, gives the 1 -form, b.p. 86°/l mm., [a]Jf— 1-93°, which led to $-phc7iyl-n-butyl bromide, b.p. 87°/l mm., [a]îj +0-84°, 'i-phenyl-n-valeric acid, b.p. 124°/1 mm., [a]“ -f 7-04° (homogeneous), -¡-4-40° in C6H 6, and $-phenyl-\\-butane, b.p. 68°/20 mm., [a]” -2-13°. E t a-phenylpropionate, [a]g —59-6° (from tho acid, [J i]“ -111-6°). gives $-phenyl-n-propyl alcohol, b.p. 92°/4 mm., [ajg +3-35°, and E t a-plienyl- butyrate, [a]“ —66-8° (from the acid, [4f]S —140-0°), gives p-phenyl-n-butyl alcohol, b.p. 95° 12 mm., [a]“ -2-69°. R. S. C.

M olecular rearrangem ents involving optically active radicals. III. L ossen rearrangem ent of optically active hydroxam ic acids. E. S. W a l l i s and R. D . D r ir ps (J. Amer. Chem. Soc., 1933, 55, 1701—1705).—Tho 0-Bz derivative, m.p. 115-5— 116-5°, [a]“ a +92-1° in 95% EtOH, of ¿-benzyl- methylacethydroxamic acid is converted by tho method previously described (A., 1926, 279) into tho K salt, which when heated in C6H 6 gives a d-carb- imide. This and dry NH3 afford rf-a-benzylethyl- carbamide (I), m.p. 136-5— 137°, [a]^,B +12-1° in COMe2. Possibjo causes of the previous failure (loc. cit.) to obtain (I) are discussed. These results support the conclusion (cf. A., 1931,1053) th a t the asymmetric radical retains its configuration or undergoes complete inversion during its migration from C to N. H. B.

T heory of m eta l hydrate ions, II. P . P f e i f f e r and S. v o n M ü l l e n h e i m (J. pr. Chem., 1933, pi], 137, 9—26 ; cf. A., 1930, 1390).—Salts of aromatic caTboxylic acids are much less suited to tho investigation of co-ordination theory than are those of naphthalenesulphonic acids (loc. cit.). Hexa-aquo- salts have not been obtained, the cryst. salts from H 20 being anhyd. or containing too little H 20 . Salts of the “ six typo ” containing C2H 4(NH2)2 are de-


scribed which frequently contain “ excessivo ” H 20 mols. Tho following salts are described :

Ni(C 02G 10H r a.)2, tetrahydrate and hexa-ammoniatc; [/Vi en2(OH2)2](GO2 C\0H r a)2;

[Ni enA](CQ2'C10Hi-u.)2,2H2O and anhyd .; Ni(C 02'C J0H tetrahydrate and hexa-ammoniatc-,

[JVi c7i2(0H 2)2](C02-G 10H r fi)2;[Ni en^\(G02'CwH ^ ) 2,2H20 ; Ni(0Bz)2,3H20 ;

[Ni en2(OH2)2](OBz)2; [Ni en3](0Bz)2,2H20 ;" Ni(C0,-CcH;-0Me-i 7)2>3H20 ;

[Ni en2(0II2)2](C02-C6Hli-0Me--p),2,2H20 ;[Ni en3](C02'C6Hi '0Me-'p)2,2H20 ;

Cu(C02-C10H r *)2,H20 ; [Cu cn2(0H2)2JC 0 2-C1()H r a) 2; Cu(C02-ClnH r fi)2 ; [C'w en2(O//2)2](C'O2-C'107/7-p)2

(+ 1 H 20 and 3H20 ) ; Cu(0Bz)2,3H20 ; [Ciien2(0 i/2)2](0i?2)2l2 //20 ; Cu(CO2-C8H 4-0Mo)2,3H,0;

[Cu en2(0H 2)2](C02"C6H^0Me--p)2;Zn(C02‘CwIl 1-a)2t2II20 (also tetra-ammoniale) ;

[Zw e?i3](6,0 2-6'jQ//7-a)2; Zn(C02 G10H^-^)2",[Zn ew3](C'03,C?10i i 7-p)2,2 //20 ; [Zw en3](0_C22)2l2 i7 ,0 ;

Zn(G02-G&H ^0M e-V)2 H 20 ;[Zn eno(Ci/i2)2](C02'6,(1/ / 4-0j¥e-p)2;

Cd(CO2-C10~Hr *)2,3HoO; Cd(C02- C 'J i7-p)2;[CcZ ew3](C02*CrloIZ'7-(3)2 (also 2H20 ) ; “

[tfd e?i3](0 & )2,2 //20 ; 3Cd(C0„-C6H 4-0Me-;p)2,4H20 ; [C'rf en2(OH2)2](C02,C(iHi 'OMe-j))2,0-5H20. H. W.

Colour and chem ical reactivity in the cinnam ic series. (M m e .) R a m a r t -L u c a s and R. T r i v e d i (Bull. Soc. chim., 1933, [iv], 53, 178—190).—A more detailed account of work previously reviewed (this vol., 63). H. B.

Reform atsky reaction w ith com pounds of the ethylene oxide type. G. R. C l e m o and J . O r m s t o n (J.C.S., 1933, 362; cf. A., 1932, 848).:—q/cZoPentane- aldehyde, CH2Br-CO,Et, and Zn in boiling CgH,, during3 hr. affords Et $-hydroxy-$-Q.yc\opentylpropionate, b.p. 117°/14 mm. (hydrazide, m.p. 154°, identical w ith the hydrazide of. the product of the Reformatsky reaction on q/cZohexene oxide). Similarly, cycZopentcne oxide or ci/oZopentanone yields E t cyc\opcntan-l-ol-l-acetate, b.p. 108°/18 mm. (hydrazide, m.p. 143°), indicating that reaction is preceded by isomerisation.

J . L. D.Salicylic acid. IV. 4-Sulphosalicylic acid.

N. W. H i r w e and M. R . J a m b h e k a r (J. Indian Chem. Soc., 1933, 10, 47—51).—2-Nitrotoluenor4- sulphonic acid, m.p. 92°, decomp. 245° (K salt), is prepared both from ;p-C0H4Me-SO3H and H N 0 3 (d 1-41) in A c20 a t room temp. (cf. A., 1910, i, 20) and from o-C6H 4Me’N 0 2 and H 2S 04 (cf. Annalen, 1870, 155, 27). I t is oxidised by alkaline K M n04 a t room temp, to 2-nitroA-sulphobenizoic acid (+ 2 '5 H 20), m.p, 111° [dichloride, m.p. 160° (softens a t 145°); diamide, m.p. 226°;' sulphonyl chloride, decomp. 202° (softens a t 192°) (partial hydrolysis of dichloride); mlphonamide (I), m.p. 192°] (cf. A., 1881, 1144). This is reduced by Sn and HC1 to 4-sulphoanthranilic acid (+1H „0) {Ba s a l t ; sulplionamide, m.p. 227—228° [from (I) and (NH4)2S in EtOH]}, which with HNO, gives “i-sulpho-2-diazobenzoic acid, decomp. 163— 164°, converted by boiling dil. HC1 into 4-sulphosalicylic

rd ( + 3H20), m.p. 82°, ( + 2 H 20 ) , m.p. 133°. I»« H (+ 2 H 20), K H, Ba (+ 4 H 20), and Ca salts]. The structure of (I) is confirmed by fusion of its K H

salt with KOH a t 230—240°, which gives (3-resorcylic acid. No evidence is given for tho structures assigned to the half-clilorides and -amides. H . A. P.

P yrolysis of m andelic acid and related com pounds. C. D. H u r d and H . R. R a t e r in k (J. Amer. Chem. Soc., 1933, 55, 1541— 1546).—Mandelic acid heated a t 200° gives0H-CHPh-C0-0[-CHPh-C0-O]n-CHPh-CO2H ( « = 1 - 2 according to tim e of heating), probably some cyclic ester (lactido type), bu t practically no gaseous products. A t 250°, CO, C02, PhCHO, CH2Ph-C02H (I), arid diphenylmaleic anhydride (II) re su lt; dimandelicanhydride (III), 0 < § ^ | | | > 0 , m.p. 152—154°,which gives tho same products a t 250°, is probably an intermediate which decomposes thus : ( I II)— yh 2o+(H ) ; (ii) —* CHPh:c:o (i). 0Na-CHPh-C02E t and CHBrPh-C02E t in E t20 afford 30% of E t dimandelate, 0(CHPh*C02E t)a, b.p. 215— 216°/8m m .; the free acid (+ H 20), softens 120—130°, is dehydrated by Ac20 to (III). Hexahydromandclic acid decomposes a t 250° to CO, C02 (trace), and

anhydride H. B.

hexahydrobenzaldehyde, whilst dilactic similarly gives CO, C02, and MeCHO.

U nsaturated aS-dicarbonyl com pounds. IX. U nsaturated aryl-aS-diketones and -ketonic acids derived from dim ethyl-m aleic and -fum aric acids. R. E . L u t z and R , J . T a y l o r (J. Amer. Chem. Soc., 1933, 55, 1593—1601).—-Dimethylmaleic anhydride (I), .Q§H8, and A1C13 give ciR-fi-benzoyl-a- methylcrotonicacid (II), m.p. 94° (all m.p. are corr.) (Me ester, b.p. 163—164°/9 mm., m.p. 53°), whiist the chloride (III) of E t H dimethylfumarate, CGH B, and A1C13 afford Et tvans-fi-benzoyl-a-methylcrotonale, b.p. 120° (corr.)/2 mm. [ i /c ester (IV), b.p. 141° (corr.)/ 5 mm., prepared similarly], which is hydrolysed (aq. EtOH-NaOH) to tho trans-acid (V), m.p. 119°. (II) could not bo converted into (V) by exposure of a solution in CHC13 containing I or Br to sunlight, but hydrolysis of (IV) with MeOH-NaOMe gives a poor yield of ( I I ) ; possible mechanisms are discussed. Mesitylene, (I), and A1C13 afford trans-p-2 :4 : 6-tri- 7nethylbenzoyl-a.-methylcrotonic acid, m.p. 169-5° (Me ester, m.p. 83°), the f i t ester, b.p. 131—133° (corr.)/ 2 mm., of which is similarly prepared from (III). Dimethylfumaryl chloride, C6H 6, and A1C13 give trans- ^y-dibmzoyl-hfi-butme, m.p. 139-5° (also prepared similarly in poor yield from Zrans-P-benzoyl-P-mothyl- crotonyl chloride), which could not be converted into the cis-form and is reduced (Zn dust, AcOH) to 2 : 5-diphenyl-?,: 4-dimethylfurari, m.p. 116°. trans- Py-Dt-2 : 4 : G-trimethylbenzoyl-^-butene, m.p. 174-5°, is converted partly into the cis-/om, m.p. 149°, by exposure of a solution in C6H e to sunlight; both forms are reduced (Zn dust, AcOH) to 2 : S-di-2 : 4 : 6- trimethylphenyl-3 : 4-dimethylfuran (VI), m.p. 144°, and a little By-di-2 : 4 : Q-trimethylbenzoylbutarie, m.p. 191-5—192° [convertible into (VI) by Ac20-conc. H 2S04]. h . B.

Synthesis of tyrosinephosphoric acid. P. A.L e v e n e and A. S c h o r m u l l e r (J. Biol. Chem., 1933, 100, 583—587).—iY-Formyltyrosine, MgO, and P0C13 in CC14 give ~N -form yltyrosine-0-phosphoric ac id , hydro-


lysed by hot 22V-HC1 to tyrosine-0-phosphoric acid, m.p. 253° (decomp.), [a]?? —2-0° (Ba and Pb salts). The method failed with serine. R. S. C.

Preparation of substituted vanillic acids.L. C. R a if o r d and D. J . P o t t e r (J. Amer. Chem. Soc., 1933, 5 5 , 1682— 1685).— G-Chloro-S-bromo-i-liydroxy- ‘i-methoxybenzaldoxime, m.p. 203—204° (decomp.), and boiling Ac20 give G-chloro-5-bromo-4:-acetoxy-3-meth- oxybenzonitrile, m.p. 165°, which is hydrolysed (GN- KOH) to G-chloro-H-broimvanilUc acid (-f-0-5H20), m.p. 196—197°. The following are prepared similarly : 5-chloro-6-bro77io-4:-hydroxy-3-7nethoxybenzald-oxime, m.p. 203—204° (decomp.) ; 2-bromo-, m.p. 71— 72°, 2 : 6-dibromo-, m.p. 143—144° (which could not be hydrolysed), 2 :5 : 6-tribrorno-, m.p. 174— 175°, 5-chloro-, m.p. 133—134°, 6-chloro-, m.p. 131—132°, 5 : 6-dichloro-, m.p. 143—144°, and 5-chloro-G-bromo-, m.p. 176°, -4:-acetoxy-2>-methoxybenzonitriles ; 2-bromo-, m.p. 163—164°, 5-bromo-, m.p. 231—232° (lit. 221°), 5 : G-dibromo- (+0-5H 20), m.p. 199—200°, 2 : 5 : 6 - tribromo-, m.p. 231—232° (decomp.), 5-chloro-, m.p. 244—245°, 6-chloro-, m.p. 207°, 5 : 6-dichloro-(+0-5H 2O), m.p. 184—185°, and 5-chloro-G-bromo- (+0-5H 2O), m.p. 187— 188°, -vanillic acids. Vanillic acid is prepared from 4-acetoxy-3-methoxybenzo- nitrile. H. B.

Stereochem istry of diphenyls. XXX. P reparation and resolution of 2 : 2'-di-iododi- phenyl-4 : 4'-dicarboxylic acid. N. E. S e a r le and R. Adams (J. Amer. Chem. Soc., 1933, 5 5 , 1649— 1654).—E t 4-iodo-3-nitrobenzoate and Cu-bronze in P hN 02 give Et 2 : 2 '-dinitrodiphenylA : i'-dicarboxylate, m.p. 95—96°, reduced (H2, P t0 2, EtOH) to the2 : 2 '-d iam ino-esteT , m.p. 99—100°, "which is converted by Mascarelli’s method (A., 1909, i, 94) into the Et ester, m.p. 118°, of 2 : 2 '-di-iododiphenylA : 4'- dicarboxylic acid, m.p. 339—341°. This is resolved by brucine into d-, m.p. 339—341°, [cc]D (in dioxan) +51-3°— ^-0°, and Z-forms (I), m.p. 339—341°, [a]D (in dioxan) —47-5°— ->-0° (brucine salts, m.p. 212—224° and 201—212°, respectively, which exhibit m utarotation). The N a salt of (I) racemises more slowly in H 20 than (I) in org. solvents. H. B.

O xidation of 3 : 4-dihydroxyphenyl-AT-m ethylalanine w ith reference to its possib le function as a precursor of adrenaline. R . D. H . H e a r d and H . S. R a p e r (Biochem. J ., 1933, 27, 36—53).—3 :4- Dihydroxyphenylalanine (I) and its N -Me derivative(II) are oxidised in presence of tyrosinase to small amounts of pressor bases (probably aminoacetopyro- catechol and adrenalone), the activ ity of which is greatly increased by subsequent catalytic reduction [adrenaline (III) probably being formed]. W ith Ag20 , Fe, or H 20 2 pressor bases [probably noradrenaline and(III)] are produced, subsequent catalytic reduction not affecting the activity. Form ation of (III) is one of three possible methods of oxidation of (II), and is considered to take place by this route in vivo, although it does not occur when (II) is perfused through the surviving adrenal gland. Side-chain oxidation does not take place when the CO,H group is absent.

R. S. C.Synthesis of d l - 3 : 4-dihydroxyphenyl-iV-

m ethylalanine. R. D. H . H e a r d (Biochem. J .,

1933, 2 7 , 54—57).—Piperonylideneacetylglycine with Me2S04 gives piperonylidcmeacetmethylamidoacetic acid, m.p. 196°, which with red P, I, and boiling HI (d 1-7) in C02 yields dl-3 : i-dihydroxyphenyl-'N-methyl- alanine, m.p. variable, about 280°; M éthylation of piperonylhydantoin is difficult, and produces mainly the Me2 compound. Piperonylidenedimethylhydant- oin is hydrolysed by Ba(OH)2 a t the ethylenic linking. Piperonal condenses with acetylglycine or hippurie acid, b u t not with benzenesulphonylglycine, sarcosine, or acylsarcosines. R. S. C.

Preparation of n itrophthalic anhydrides. M.H a y a s h i and K . K a w a sa k i ( J . Soc. Chem. Ind. Japan, 1933, 3 6 , 121— 123b).—A detailed account of the nitration of 0-CGH 4(C 0 )20 , separation of the 3-, m.p. 211° (decomp.) (44-1% of theory), and 4-, m.p. 164— 165° (39-2% of theory), -nitrophthalic acids, and their conversion into anhydrides by standard methods.

H. A. P.Course of addition of sod ium enolates of m al-

onic and m ethylm alon ic esters to phenyl styryl ketone and crotonic ester. A. M ic h a e l and J. Ross (J. Amer. Chem. Soe., 1933, 5 5 , 1632—1646; cf. A., 1932, 252).—Ph styryl ketone (I) and CHMe(C02E t)2 in E t ,0 containing a little piperidine or NaOEt (0-1 mol.) give 80% of Et 8-benzoyl-y-phenyl- butane-$$-dicarboxylate (II), m.p. 95° (phenylhydrazone, m.p. 130°), which with Na (1 mol.) or NaOEt (1 mol.) in cold E t20 undergoes almost complete retrogression to (I), CNaMe(C02E t)2 (as enolate) (III), and (probably) a trace of CH2Bz-C02E t, thus rendering Holden and Lapworth’s (A., 1931, 1272) mechanism of the reaction between (I) and (HI) untenable. (HI), (I) [or (II)], and N aO Et in E t20 give E t a- methylcinnamate and CH2Bz-C02E t; contrary to Holden and Lapworth (loc. cit.), the production of these has no connexion with the formation of the Na-enolate of E t y-carbethoxy-afi-dimethylglutarate from (III) and CHMe;CH-C02E t, during which additive process migration of Me m ust occur.

(I) and CH2(C02E t)2 in E t20 containing a little piperidine or NaOEt give the E t ester (IV), m.p. 71°, of y-benzoyl-$-phenylpropane-cm-dicarboxylic acid, m.p. 165° (dècomp.), whilst CHNa(C02E t)2 (1 mol.) and(I) (2 mois.) in E t20 afford Et 2-benzoyl-l : 3 : 5 tri- phenyl-A1-cyciohexene-!i : i-dicarboxylate. (V), m.p. 235° (which arises by loss of H aO from E t as-dibenzoyl-fSS- diphenylpentane-yy-dicarboxylate), E t yz-dibcnzoyl- fà-diphenÿtyentane-oux-dicarboxylate (VI), m.p. 197°, Et 4 : Q-dibenzoyl-'.i : 5-diphenylcyc\ohexanone-2-carboxylate (VII), m.p. 187° [formed by loss of EtOH from(VI)], and (IV). The production of (V) is favoured by an excess of NaOEt and prolonged reaction time ; the enolate of (VII) is formed from (I) and (IV) in presence of < 1 equiv. of NaOEt.: (VI) and (VII) are interconvertible (as enolates) by NaOEt ; in these r e a c t i o n s a little (V) is produced. M éthylation (Mel, EtOH- NaOEt, EtOAc) of (VII) or (VI) gives Et 4 : 6-dibenzoyl-3 : 5-diphenyl-2- ( VIII), m.p. 170°, and -6-, m . p . 175°, -methylcyc\ohexanone-2-carboxylates, Et yz-dibenzoyl-{iS-diphenylhexane-xv.-dicarboxylate, m .p . 237°, and E t SZ-dibenzoyl-ys-diphenylheptane-Pp-dicarboxylate, m.p. 210°; the open-chain c o m p o u n d s predominate. (VIII) and E tO H -N aO Et in cold E t20


give El a.y-dibenzoyl-$$'-diphenyl-a.'-methylpimelate, in .p. 188°, and a stereoisomeride, m.p. 210°; in the hot, EtOBz and E t yrbenzoyl-$$'-diphenyl-x-methylpimelale, m.p. 154°, result. H. B.

Usnic a c id .' I. D erivatives of m ethylphloro- glucinol. P. H. Cu r d and A. R o b e r t so n (J.C.S., 1933, 437—444).—Interaction of CHMeiCOaEt^COCl(I) and C0(CH2,C02E t)2 (II) (Na derivative) in E t20 during 1 hr. affords E t hexane-2 : 4-dione-I : 3 : 5-tri- carboxylate, b.p. 165—168°/1 mm., which cyclises with NaOEt to Et methyljMoroglucinoldicarboxylate (III), m.p. 92—93° (A c3 derivative, m.p. 99°), hydrolysed and decarboxylated to methylphloroglucinol. CHMe(C02E t)2, (II), and NaOEt a t 160° during 1 hr. afford some (III), bu t mainly E t 4 : 5 : 7-trihydroxy- coumarin-6( or 8)-carboxylate (A., 1917, i, 277). (I)with E t sodioacetoacetate affords a dione which does not cyclise to (III). The diazonium compound of2 : 6-dinitro-p-toluicline and boiling aq. CuS04 afford2 : Q-dinitro-Tp-cresol, m.p. 154— 155° [Me ether (IV), m.p. 103—104°]. Reduction of (IV) with Sn and hot HC1, followed by prolonged boiling of the reduction product with H 20 , affords methylphloroglucinol a-Me ether (cf. A., 1898, i, 578). The orientation of the P-Me ether (Herzig and Wenzel, A., 1902, i, 463) follows. (IV) with H 2S in E tO H -N H 3, Na2S2, or SnCl2 affords Q-nitro-4-methoxy-o-toluidine, m.p. 82— 83° (Ac derivative, m.p. 171—172°), which when diazotised and treated with boiling H 2S04 yields b-nitroA-methoxy-o-cresol, m.p. 126° [Me ether (V), m.p. 93°]. (V) is reduced by Na2S, and the amine(Ac derivative, m.p. 146°) isolated as the sulphate when diazotised and treated with boiling H 2S04 affords methylphloroglucinol a-Me2 ether (VI) (cf. A., 1898, i, 578), thus confirming the structure of the latter. Phloroglucinaldehyde and Mel in COMe2 containing K 2C03 during 3 hr. afford 2-hydroxyl : 6- dimethoxy-m-tolualdehyde, m.p. 168—-169° [Ac derivative (VII), m.p. 123—124°] [also formed by methyl- ating methylphloroglucinaldehyde, and from (VI) and HCN according to the Hoesch procedure], converted by acetylanisole and HC1 in EtOAc into 5 : 7 : 4'-trimethoxy-8-methylflavylium chloride (ferrichloride, m.p. 196—197°). Similarly, Me phloroglucinolcarb- oxylate with Mel affords Me 2-hydroxy-4 : 6-dimethoxy- m-toluate (VIII), m.p. 144—145° (and some Me2 : 4 : 6-trimethoxybenzoate), also obtained from Me2 : 4-dihydroxy-6-methoxy-m-toluate and Mel. Me 2 : 4 : 6-triliydroxy-wi-toluate with Mel and COMe2 affords (VIII) and Me 2 : 4 : Q-trimethoxy-m-toluate, m.p. 80—82°, hydrolysed and decarboxylated to methylphloroglucinol Me3 ether (Ur2-derivative, m.p. 102—103°) or gently hydrolysed to the acid, m.p. 182° [also obtained by oxidising (VII) followed by hydrolysis], decarboxylated to (VI). Methylphloroglucinol and MeCN with ZnCl2 and HC1 in E t20 affords methyl- phloracetophenone, m.p. 211—212° (Ac3 derivative, m.p. 111°), m ethylated to 2-hydroxyA : 6-dimethoxy- ‘•’’-mathylacetophenone (IX ), m.p. 141— 142° (Ac derivative, m.p. 86—87°) [also obtained from phloracetophenone and Mel, or from (VI) with MeCN, ZnCl2, and HC1], which condenses with anisaidehyde to give2-hydroxy-4 : 6 : 4'-trimethoxy-3-methylchalkone, m.p. 134r—135° (Ac derivative, m.p. 148°), cyclised by

II2S04-E t0 H in 15 hr. to 5 : 7 : 4'-tritnethoxy-8-methyl- fiavanone, m.p. 144°. (IX) with jp-hydroxybenz- aldeliyde affords 2 : 4’-dihydroxy-4 : (i-di/mtfwxy-3- methylchalkone, m.p. 199—200° (Ac,, derivative, m.p. 135°), and with CH2Br-C02E t, COMe2, and K ,C 03 affords Et 2-acetyl-.i : 5-dimethoxy-Q-methylphenoxy- acetate, m.p. 70°. J . L. D.

B ile acids. XXXVIII. Can the Van Slyke m ethod of am ino-nitrogen determ ination be applied to derivatives of bile acids? M. S c h e n c k and J . R e sc h k e (Z. physiol. Chem., 1933, 2 1 6 , 81— 90; cf. this vol., 274).—The Van Slyke method gives untrustw orthy results with NH2-acids of the bile acid group. Thus the aminoketotetracarboxylic acid C27H 370 9N gives vals. for N 230 and 290% of theoretical after 3 and 21 hr., respectively. High N vals. are probably due to liberation of N2 from H N 0 2. Inversion, products A and B from the oximinoamino- acid C24H 380 9N2 give larger amounts of NH 2-N than corresponds with one NH2 group, but titration with and without CH20 indicates th a t A is a lactam- amino-acid. The substance obtained by boiling A for 6 hr. with 20% HC1 gives low Van Slyke N ; tho lactam ring probably remains intact. J . H . B.

B ile acids. L. Complete structure and nature of ring D . H. W i e l a n d and E. D a n e (Z. physiol. Chem., 1933, 2 1 6 , 91—-104; cf. A., 1931, 841).—The ketodicarboxylic acid (I), C23H3fl0 5, with Br in AcOH gives a bromoketodicarboxylie acid (II), m.p. 182° (decomp.), which with 0-lAr-KOH affords a hydroxyketodicarboxylic acid (III), C23H 36Or>, m.p. 204—206°, and the unsaturated ketodicarboxylic acid(IV), C23H m0 5, m.p. 214—217°. W ith KOH in MeOH, (II) gives tho Me ether, m.p. 158—162°; of(III). Oxidation of (III) with Cr03 in AcOH yields the ketotricarboxylic acid (V), C23H 360 7, m.p. 196°. W ith H N 0 3, (V) affords a trims-tricarboxylic acid (VI), Ci3H 20O6, m.p. 187°, [a]D -27-3° [anhydride (VII), m.p. 145—146°]. Hydrolysis of (VII) gives the cis- tricarboxylic acid (VIII), m.p. 136°, [a]D +36-4°, which regenerates (VII) on distillation. Bromination of the enol acid C24H 360 4 (cf. A., 1931, 841) gives, a bromo-

0Q Me 4H 8-CO,H C02H x Mo C4H 8-C02H

Mo C02H/CO

CH,

COoHx

(III.) (V.)

diketocholanic acid (IX), m.p. 130—133° (decomp.), which in boiling C5H 5N gives the unsaturated enol acid (X), Co4H...04, m.p. 160°.

r u rn t i T h e C a n d D r i n S s of the Me s vMaf*- sterols and bile acids are thusconnected in the trans-position. The present evidence supports the most probable constitution of the bile acids,

particularly as to the 5-membered ring D and the positions of the Me groups and side-chain.

J . II. B.Condensation of certain y-ketonic esters w ith

arom atic aldehydes. II. C. F . H. A l l e n , G. F .

COoH(VI.)


F r a m e , J . B. N o r m in g to n , and C. V. W il so n (Cañad. J . Res., 1933, 8 , 137— 141).—Me, m.p. 103°, and E t a-phenyl-, m.p. 41°, and E t a-p-anisyl-3-benzoyl- propionato condense with PliCHO in presence of alkali to give ay-diphenyl- (I), m.p. 145° (yield 85%) [oxime, m.p. 181°; chloride (II), m.p. 79°], oxidised to Ph CH2Ph diketone, and y-phenyl-x-p-anisyl-P- benzoylcrotonic acid (III), m.p. 136° (cf. A., 1932, 1030). (I) a t 230—240° yields a-benzylidene-^-phenyl- propiophenmie, (IV), m.p. 48° (2 : 4-dinitrophenylhydrazone, m.p. 1S9°), oxidised by K M n04 to BzOH, by C r03 to CH2Ph-COPh, and gives PhCHO with 0 3i The similar product (oily) produced from (III) gives 2>:OMe-C6H 4-CHO with 0 3. (IV) with HC1 in MeOH gives isomerides of fi-chloro-fi-júenyl-a-benzylpropio- plienone, m.p. 126° and 132°, also obtained from the interaction of benzylacetophenone, PhCHO, and HC1.(I) reacts with 2 mols. of Grignard reagent giving 1 mol. of CH4, whilst (IV) reacts with 1 mol. without ovolution of gas. (II) with AgÓAc gives the acet- anhydride, m.p. 126° [also obtained from (I) with Ac20 and H 2S 04], and with the appropriate aniline the p- bromo-, m.p. 179°, and p -iodoanilide, m.p. 200° (also with 1 mol. of C6H 6), of (I). A. A. L.

Structural changes produced in the selenium dehydrogenation m ethod. I. R ing changes in •s-piro-compounds. G. R. Clem o and J . Orm sto n (J.C.S., 1933, 352-—353).—2-Ketocí/ctohexanos;p¿ro- c?/c/opentane (I), b.p. 102—103°/20 mm. (modified prep.; semicarbazone, m.p. 189—190°), and cyclo- hexanes^iVoc¿/c?opentane, b.p. 75°/20 mm. [prepared from (I) by Clemmensen reduction], w ith excess of Se a t 280—320° give C10H g (poor yield). R. S. C.

D ecom position of co-chloroacetophenonesemi- carbazone. A . P. J . H o o g e v e e n an d C. W . v a nH o o g str aten (Rec. trav . chim., 1933, 52, 378—384). —CH2Cl-CPh:N*NH-C0-NH3 (I), m.p. 149° (lit. m.p. 156°), is converted by H 2S in E tO H into the discmicarb- azone, m.p. 228°, of (COPh-CH2-)2S. W hen boiled -with NaHCOginaq. EtOH, (I) affords a substance, C17H 17ON3, m.p. 221 -5°, converted by heatingwith NaOEt in EtOH a t 160° into 3 : &-diphenyl-?>: 4 : 5 : G-tetrahydropyrid-azine, CHP1i<^q^ .q ^ ^ C H P I i , m.p. 159°, which isoxidised by B r-H 20 to 3 : 6-diphenylpyridazine, identical with a specimen prepared by boiling an EtOH solution of the dihydro-compound obtained from (COPh-CH2-)2 and N„H4 (Paal and Dencks, A., 1903, i, 289). “ J . W . B .

Absorption spectra of ox im es. J . M e i s e n - h e im e r and O. D o r n e r (Annalen, 1933, 502, 156— 174).—The characteristic band of the CO group in COMe2 and cycZohexanone disappears in the curves of the corresponding oximes. CHPhlN-OH, CPh2'.N-OH(I), and CPhMeiN-OH show bands characteristic of the C6H 6 nuclei, but the band due to the original CO again disappears or is markedly diminished. Isomeric oximes generally show great similarity. Comparison of the spectra of (I) and its j)-Cl-, jj-OMe-, and p-OH- derivatives confirms Wolf and Herold’s (A., 1931, 996) rule regarding displacement towards the red; the 3>-N02 group has, however, the max. effect. The hydrochlorides of aromatic oximes show stronger

absorption than the oximes themselves, whilst the curves of the 0-Mo ethers are either identical or parallel (displaced somewhat towards the red) with those of the corresponding oximes, thus indicating th a t the free oxime exists mainly in the C!N-OH and

NHnot the C<^q fo rm ; the absorption of the ethersis unaffected by HC1. The N -Me ethers show stronger absorption than their hydrochlorides or the original oximes; the curves resemble those of the alkali salts of the related oximes. Differentiation of the stable and labile forms of oximes is possible, since the latter show stronger absorption in the region of longer wavelengths. The following data are reported : a-, m.p. 129° (lit. 133°), and ¡3-, m.p. 177° (lit. 184°), -jj-nitro- benzaldoximes; a-, m.p. 158—159° (lit. 156°), and ¡3-, m.p. 97° (lit. 95°), -;p-chlorobenzophenoneoximes; a-, m.p. 146° (lit. 138°), and f - , m.p. 118° (lit. 116°), -p-methoxybenzophenoneoximes:; ■ a-, m.p. 159° (lit. 152°), and ¡3-, m.p. 83° (lit. 81°), -p-hydroxybenzo- phenoneoximes. H. B.

Preparation of 4-fluoro- and 4 : 4'-difluoro- benzophenone. R. D. D u n l o p [with J . H . Ga r d n e r ] (J. Amer. Chem. Soe., 1933, 55, 1665— 1666).— PhF, BzCl, and A1C13 give 66% of 4-fluorobenzo- phenone, m.p. 48-2—48-7° (lit. 52°). 4 :4 '-Difluoro- benzophenone, m.p. 107-5—108-5° (oxime, m.p. 137— 138°, rearranged by PC1B in E t20 to fj-fluorobenz- ;p-fluoroanilide, m.p. 183-5— 184-2°), is prepared in 62% yield from j>-C6H 4F*C0C1, PhF, and A1C13; a little of the 4 : 2'-isomeride is also formed. H . B:

G rignard reaction in the synthesis of ketones.II. Preparation of m ono- and di-chlorodeoxy- benzoins. S. S. J e n k i n s and E. M. R ic h a r d s o n (J . Amer. Chem. Sod., 1933, 55, 1618— 1621; cf. this vol., 394).—CH2Ph-MgCl (I) and o-C6H 4Cl-CO-NH2 (II) in E t20 and H 2 give o-chlorophenyl benzyl ketone, b.p. 176—178°/5 mm. [anti-oxime, m.p. 131-5—132-5° (all m.p. are corr.), rearranged by PC15 in E t20 to phenylacet-o-chloroanilide, m.p. 120°]; o-CcH4Cl-CH2-MgBr(III) and N H 2Bz afford Ph o-chlorobenzyl ketone, m.p. 70-5° (anti-oxime, m.p. 85—-86°, rearranged too-CGH4Cl-CH2-CO-NHPh); (III) and (II) yield o- chlorophenyl o-chlorobenzyl ketone, b.p. 195—210°/6 mm. (anti-orm e, m.p. 103-—104°, rearranged to Q-chlorophenylacet-o-chloroanilide, m.p. 159-5°; syn- oxime, m.p. 145—146°, rearranged to N-o-cHoro- benzoyl-o-chlorobenzylamine, m .p, 111°);. (I) and j)-C0H 4Cl-CO-NH2 (IV) furnish ^-chlorophenyl benzyl ketone, m.p. 107-5° (anti-oxime, m.p. 122-5:—123-5°, rearranged to phenylacet--p-chloroanilide, m.p. 168°) ; j)-CGH4C1 • CH2• MgBr (V) and NH2Bz give Ph p -chlorobenzyl ketone, m.p. 138° (anti-cmme, m.p. 95—96°, rearranged to p-CGH4Cl-CH2*CO-NHPh); (V) and (IV) afford p -chlorophenyl ip-chlorobenzyl ketone, m.p. 114° (anti-cm'wie, m.p. 124-5— 125-5°, rearranged to p- chlorophenylacet--p-chloroanilide, m.p. 190°); (III) and(IV) yield j)-chlorophenyl-o-chlorobenzyl ketone, m.p. 108-5° (anti-oriwe, m.p. 105— 106°, rearranged too-chlorophenylacet-Tp-chloroanilide, m.p. 184°); (V) and(II) furnish o-chlorophenyl -p-chlorobenzyl ketone, m.p. 65° (anti-cmme, m.p. 88—89°, rearranged to p -chlorophenylacet-o-chloroanilide, m.p. 171°). The above

ORGANIC CHEMISTRY. 6 1 1

anilides are also prepared by the usual method. The yields of ketones are 70—80%. H. B.

Dehydration of the a-form s of r- and (+ )-o - and -jn-tolylhydrobenzoins. R . R o g er and W. B. McK a y (J.C.S., 1933, 332—336; cf. A., 1932,1251).— r-m-Tolylhydrobenzoin (a-form) with boiling dil. H 2S04 in 3 hr. affords v-m-tolyldeoxybenzoin (I), m.p. 83—84°, whilst cold cone. H 2S 04 affords a mixture of (I) and m-tolyl CHPh2 ketone (III), m.p. 97°. Further action of H 2S04 on (I) affords a product, m.p. 173—174°, which contains S. Similarly, (+)-m-tolylhydrobenzoin (a-form) with dil. H 2S 04 as well as with boiling HoC20 4,2II20 during 8 hr. affords (I). (I) is prepared from r-jihenyl-m-lolylacelonilrile, m.p. 38-5—39°, and MgPhBr in E t20 . Interaction of wz-C0H4MeBr, Mg, and CHPh^CN in E t20 during 4 hr. affords (III). r-o-Tolylhydrobenzoin (a-form) (II) with boiling dil. H2S04 affords diphenyl-o-tolylacetaldchyde (IV), m.p. 163—164° (which w ith K O H -EtO H gives diphenyl-o-tolylmethane, m.p. 82—83°), and r-o-tolyldeoxybenzoin (?) (V), m.p. 56—57°. (II) with cold conc. H 2S04 affords o-tolyl GHPli2 ketone (?) (VI), m.p. 47— 8°, and (V). (IV) is further acted on by cold conc. H2S04 to give (VI) and (V). (+)-o-Tolylhydro- benzoin (a-form) with boiling dil. H 2S04 affords (IV) and (-\-)-o-tolyldcoxybenzoin (?), m.p. 79-5—80-5°, Ms«« +202-5° in CHC]n, rapidly racemised by 0-5JY- KOH-EtOH to (V). The significance of the preceding reactions is discussed. J . L. D.

Nitration of chalkone. R. J . W. L e F e v r e , P. J. Ma r k h a m , and J . P e a r so n (J.C.S., 1933, 344— 346).—4-Nitrochalkone (I) (A., 1902, i, 379) and 3'-nitrochalkone are both converted by HNOs (d 1-5) below 0° into 3 : 4-dinitrochalkone (II), m.p. 204— 205° (lit., about 225°). Chalkone (III), contrary to Goldschmidt (A., 1895, i, 422), is dinitrated by H N 03- H2S04 to (II). Goldschmidt’s “ o-nitrobenzylidene- acetophenone ” is mainly an oxidation product, as it affords only traces of 2-phenylquinolinc on reduction. Interaction of (III) and K N 03-H 2S04 a t —10° affords (I). " J . L. D.

Constitution of the chlorination products of henzanthrone. R. S. C ahn, W. O. J o n e s , and J . L. Sim onsen (J.C.S., 1933, 444—449).—Chlorination of benzanthrone (I) by dichloroamine-T in AcOH affords 13-chlorobenzanthrone (II), m.p. 182—183° (cf. A., 1929,1304). Interaction of 5 : 8-dichloro-l-naphthoyl chloride, C6H G, and A1C13 during 8-5 hr. affords Ph 5 : 8-dichloro-ct-naphthyl ketone, m.p. 93°, which failed to cyclise to (II). F urther chlorination of (I) or (II) affords 6 : 13- and 8 : 13-dichlorobenzanthrone, oxidised [as is 6-chlorobenzanthrone (III)] to 6-chloro- [.Me ester, m.p. 190—191°; acid chloride, m.p. 234— 236° (decomp.)] and 8-ehloro-anthraquinone-l-carboxylic acid [Me ester, m.p. 124—125°), respectively, the latter acid being synthesised from S-chloro-1- aminoanthraquinone, m.p. 225—227° (Ac derivative, m.p. 223—225°), through the nitrile. Similarly,5-chloro-l-aminoanthraquinone (Ac derivative, m.p.218—220°) is converted into 5-chloroanthraquinone-1 -carboxylic acid, m.p. 306° (decomp.) [Me ester, m.p. 181°, identical with the ester prepared from Butescu’s a-chloroanthraquinone-l-carboxylic acid (cf. A., 1913, i, 273)]. 7-Chlorobenzanthrone (IV) is oxidised to

s s

7-chloroanthraqui?ione-l-carboxylic acid, m.p. 262— 264° (Me ester, m.p. 193—194°), previously obtained, although not oriented, by Butescu. Interaction of m-CgHjChCOCl and C10H 8 (cf. A., 1922, i, 258) affords m-chlorophenyl fi-naphthyl ketone, m.p. 143° [dinitrophenylhydrazone, m.p. 264—265° (decomp.)], and m-CgH4Cl a-C10H 7 ketone, m.p. 86° (lit., 77—79°) (dÀnitrophenylhydrazone isolable in two forms, m.p. 247° and 198—200°), which readily cyclises to (III). Similarly, îj-C6H4C1-COC1' and C10H 8 afford a m ixture of a- and [3-C10TI7 derivatives (a-ketone purified) which cyclises to (IV), further chlorinated to 7 :13 -dichlorobenzanthrone, m.p. 251—252°. J . L. D.

H ydroxylam ine derivatives of phenyl styryl ketone and dibenzoylm ethane. K. v o n A itwers and H. Mü l l e r (J. pr. Chem., 1933, [ii], 137, 57—80). —Treatm ent of CHPhlCH-COPh (I) with N H20H,HC1 (2 mois.) in E tO H containing 1 drop of conc. HC1 or in anhyd. EtOH w ithout HC1 gives the normal oxime(II), m.p. 115—116°. Free NH 2OH (III) in absence of other alkali and in cold solution gives primarily P-hydroxylamino-P-phenylpropiophenonc (IV) (not isolated), which in presence of excess of (I) yields the compound, (CH2Bz-CHPh)2N-OH, m.p. 190°. If excess of (III) is present, (IV) yields y-liydroxylamino- ay-diphenylpropanoneoxime (V), m.p. 147°. A th ird possible transform ation is the oxidation of (IV) to CHjBz'CPhlN-OH, m.p. 165°. Correspondingly, (IV) is oxidised to CH2(CPh!N-OH)2, m.p. 209°. Production of (II) is subsidiary. In hot solution the amount of (II) increases as, to a still greater extent, does th a t of diphenylisooxazoline, m.p. 75°, particularly when free alkali is present. The extent of its oxidation to diphenyh'sooxazole depends on experimental conditions. H. W.

O xidative processes. VII. Preparation, racém isation , and autoxidation of the optically active 2 : 2 /-diethoxybenzoins. A. W e iss b e r g e r and E. D ym (Annalen, 1933, 502, 74—85 ; cf. th is vol., 161).—o-OEt-C6H4-CHO (in Et-20) and K C N + NH4C1 (in H 20) give o•ethoxymandelonitrile, m.p. 86— 89°, hydrolysed (E t20 -E t0 H -H C l and then H 20) to d\-o-ethoxymandelic acid (I), m.p. 102-5—103-5° [Me ester, m.p. 71—72°; amide (II), m.p. 102-5—103-5°].(II) and o-OEt-CgHj'MgBr afford dl-2 : 2'-diethoxy- benzoin. (I) is resolved by cinchonine into (—)-, m.p. 126-5—127-5° (corr.), [a]i? -144-9° in E tO H [Me ester, b.p. 84—86°/0-02 mm., m.p. 30—31°; amide (III) m.p. 125-5—126-5° (corr.)], and (-f)-forms, m.p.> 125-5— 126-5° [amide (IV), m.p. 124-5—125-5°]. (—)-d- and (+)-Z-2 : 2'-Diethoxybenzoins, m.p. 58-5— 59-5°, [ajn —30° and +30° in EtOH, respectively, are prepared (as above) from (III) and (IV), respectively. Racémisation and autoxidation of these under the conditions previously described (A., 1931, 844) occur a t almost identical rates ; steric hindrance by the OEt groups involves ionisation or énolisation (and subsequent dissociation) bu t not oxidation of the ion R-CO'iCO'-R. H. B.

Potentiom etric studies on sem iquinones. L. Mic h a e l is and E. S. H ill (J. Amer. Chem. Soc., 1933, 55, 1481—1494; cf. A., 1931, 1130, 1309).— Analysis of the oxidation or reduction curves of 2>NH2-C6H4-NMe2) p. C6H 4( N l le 2)2, p-N H 2-C6H4-NEt2,


2;-CGH4(NEt2)2, j)-C6H4(NHPh)2, 4 : 4'-dipyridyl and its dimethochloride, and phenazine shows th a t the semiquinonoid form differs from the holoquinonoid by one electron w ithout change of mol. size. Semiquinonoid compounds are radicals in which one electron is shared by two atoms each possessing a septet. H. B.

Anthraquinone derivatives. I. Chloroam ino- anthraquinone. M. H ay asiu , K . K aw asak i, and A. N a k a y a m a (J. Soc. Chem. Ind. Japan , 1933, 36, 123—127b).—Interaction of 4-nitrophthalic anhydride, PhCl in excess, and A1C13 a t 120— 130° gives 4'-c7iZoro-4(or 5)-nitro-, m.p. 198° [Me ester, m.p. 150— 150-5°; i\r.H2-compound, m.p. 192° (decomp.) (Ac derivative, m.p. 222-5—223°)] (3S% of theory), and 4:'-chloro-5(ov 4)-nitro-2-benzoylbenzoic acid, m.p. 194— 194-5° [Me ester, m.p. 109—109-5°; iV7J2-compound, m.p. 225-5—226° (decomp.) [Ac derivative, m.p. 224-5—225°)] (16-5% of theory). Both N H2-compounds w ith H 2S 0 4 a t 150— 155° give 2-chloro-G(or 7)-, m.p. 284—-284-5°, and -7(or §)-aminoantliraquinone, m.p. 295—296°, and an unidentified compound, m.p. 300°. H. A. P.

Structure of sim ple nucleic acids. III. Yeast- and m uscle-adenylic acid. H. S t e u d e l (Z. physiol. Chem., 1933, 216, 77—80; cf. A., 1931, 1317).— Yeast- and muscle-adenylic acids differ in a during acid hydrolysis and in their pentose content. The Cu salts do not differentiate the two forms.

J . H. B.Plant-grow th substances. V. Phytohorm one

of cell elongation. C hem istry of crystalline auxin. F . K ogl, H. E r x l e b e n , and A. J . H a a g e k - S m it (Z. physiol. Chem., 1933, 216, 31— 44; cf. this vol., 435).—Auxin (I), C1SH 320 5, and its lactone show m utarotation, final vals. [a']„ —3-19° and —3-44° in EtOH , respectively. (I) forms a M e ester, m.p. 148°, Mi? —3-77°, tri-m.-dmitrobenzoyl derivative, m.p. 168°, p -phtnylphcnacyl ester, m.p. 166°, dihydro-dcrivative, m.p. 199°, final [ajg —3-14° in EtOH , and dihydrolactone, m.p. 191°. On keeping, (I) gives a m ixture of various physiologically inactive isomerides differing in a but not showing m utarotation. The mixture on hydrogenation gave a product, m.p. 198°. (I) is amonocyclic singly unsaturated tricarboxylic acid.

J . H. B.Constitution of hederagenin and oleanolic acid.

IV. Z. K it isa t o and C. S o k e (Acta Phytochim., 1933, 7 ,1 —26; cf. A., 1932,1035).—Bromohedragone lactone, prepared by Beckmann’s m ixture (50) from bromohederagenin lactone in cold AcOH, is accompanied by bromohedragenonedi-acidlactone, C2oH430 5Br, m.p. 192—193° (decomp.) [oxime, m.p. 258° (decomp.)], the Me ester, m.p. 195° (decomp.) [oxime, m.p. 236— 237° (decomp.)], of which with Br in MeOH gives the Me ester, m.p. 183° (decomp.), of dibromohedragenonedi- acid laitone, and with Zn dust and AcOH yields the Jieester (I), m.p. 1S1— 182° (decomp.), of hedragenonedi- acid (II), the Me2 ester, m.p. 159—160°, of which is obtained from (I) by CH2N2. Hedragenetri-acid has m.p. above 300° (Me ester, m.p. 149°). (II) and KOBr give a product which w ith Br in MeOH yields bromohedratri-acid lactone and its Me ester (III), -fO-66MeOH, m.p. about 200° (also -j-AcOH) [Me2

ester, CgoH^OgBr, m.p. 187° (decomp.)]. (I ll) , Zn dust, and hot AcOH afford hedratri-acid, C28H 42Ofi, m.p. 240° (decomp.), and its Me ester, m.p. 122—124°.(I ll) and K O H -EtO H give y-ketohedrairi-acid, C28H 420 7,-)-H20 , m.p. 255° (decomp. 272°) (Me ester, m.p. 164°). Ketohedragone lactone and KOBr led to e-ketohedragenetri-acid, m.p. 288—289° (decomp.) (Me ester, m.p. 164°). Ketohederagenin lactone [Br derivative, m.p. 235° (decomp.)] and K O H -EtO H give z-ketohederagenin (IV), C30H 46O5, m.p. 290° (decomp.), which by Me2S04 and subsequent acétylation gives the M e ester, m.p. 237°, of the ylc2 derivative of (IV), which yields the Me ester, m.p. 220°, of (IV) by hydrolysis. Keto-oleanolic acid lactone and K O H -EtO H give s-keto-oleanolic acid, C30H 4r)0 4,+0-5H 20 , m.p. 268—269° (decomp.), giving similarly the M e ester, m.p. 200° (Acç derivative, m.p. 236—238°). The above and previous results are held to prove formula(V) for hederagenin and formulae are assigned to many of its degradation products. (VI) is, however, also possible; further, all these compounds may contain one C atom more than given above. Hedragonedi-acid is re-named hedragenetri-acid and deoxydehydro- hedrabetulin becomes hydragenylene.

H,C CH,

orHO-HC CH CH,

0H'CHj>i " A " iff C H |

H,C Me ÇH Ç d CH,H 2C c CH C-C02H

DAH

C02H -Ç e

(V.)

H 2C HO „ QMe2 ‘ H ,à E CH “

c /-Me

(VI.) H,H ,

CH" CH,CO,H

or DMe H,C

H,

H CH C e CH

CMe, CO,H R. S. C.

Oleanolic acid (guagenin). III. Oxidation of acetyloleanolic acid and oleanolic acid with chrom ic acid. W . S c h ic k e and E . W e d e k in d (Z. physiol. Chem., 1933, 215, 199—206; cf. A., 1931, 1100).—Oxidation of acetyloleanolic acid with Cr03 in AcOH a t 80° gives, in addition to 8-ketoacetyl- oleanolic acid lactone (Kitasato and Sone, A., 1932, 1035), a dicarboxylic acid. C27H 40O7, m.p. 293—294°, which Avas deacetylated to an acid, C25H38OG, ni.p. 292°. Oxidation in boiling AcOH afforded a keto-acid C30H 46O3, m.p. 187° (oxime, m.p. 299°), identical with. Prelog’s product (A., 1930, 1044). J . H. B.

A ctive principle of A tra c ty lis g u m m ife ra . T.A je l l o (Gazzetta, 1933, 63, 99—102).—For K


atractylate the new formula C™ILsOiaSoK<> is suggested (cf. A., 1924, i, 195). E. W. W.

P yrolysis of m enthoglycol and isopulegyl acetate. J . D ceuvre (Bull. Soc. chim., 1933, [iv], 53, 170—177).—W hen menthoglycol is passed over glass wool in a Pyrex glass tube a t 540°/30—40 mm. a t the rate of 10 g. per hr., COMc, and 3-methylc?/cZo- liexanone (I) are the main p roducts; some dehydration to isopulegol [which is then largely transformed into citronellal (cf. A., 1930, 893)] also occurs. 3-Methyl- q/cfohexanol {p-dipihenylylcarbamate, m .p. 106—107°) and cyc/ohexanol similarly give (I) and cycZohexanone, respectively. isoPulegyl acetate a t 540—550°/50 mm. affords AcOH and approx. equal amounts of A2:8®. ancl A8-s<9)-p-mentliadienes, b.p. 171—173° '(corr.)/750 mm., [a]“g +133-5°, and b.p. 182—184° (corr.)/750 mm., [a]“s +118-33°, respectively.

H. B.Camphor and terpenes. IX. Transform

ation of cam phor and optically active system s of the cam phor series into their spatial antipodes.J. H o u b e n and E. P f a n k u c h (Annalen, 1933, 501,219—246; cf. A., 1932, 62).—D-Camphor, PC13, and PC15 give (cf. Meerwein and Wortmann, A., 1924, i, 188) a lsevorotatory m ixture of (mainly) D-l-2 : 2-dichlorocamphane (a-D-camphor dichloride) (I), varying smaller amounts of 2 : 4-dichlorocamphane (L-d- 4-chloroisobornyl chloride) (II), and probably a little D-l-chlorocamphene hydrochloride (III). Treatm ent of the mixture with KOAc and PhOH gives (cf. Zoc. cit.) 1-chlorocamphene [from (I) and (III)], 4-chlorocamphene [from (III)], and a little chlorotricyclene [from (II)]. The production of (II) is considered to occur thus : (I)— ->-(III)— >L-4-chlorocampbenohydrochloride (IV)— >-(II). The changes (I)— > (III) and (IV)— >-(11) involve ring isomerisation, whilst the change (III)— >(IV) occurs through migration of Cl and Me (cf. A., 1931, 1300; Nametkin and Briissov, A., 1928, 182) and effects a transformation of the D- into the ¿-series. Related transformations are studied.

Impure ¿-camphor, PC13, and PC15 give a 2 : 2-dichlorocamphane, [a]™ +15-2° in E t20 , convertible into ¿(Z-a-chlorocampheno, [a]',“ +18-8° in EtOH, which is reduced (Na, EtOH) to a camphene, [a]" —68° in EtOH. Rearrangement of (I) w ith SnCl4 in PhMe (cf. Zoc. cit.) affords ¿-4-chloroisobornyl chloride (p-camphor dichloride), [a]\5 +18-25° in E t20, convertible into ¿-Z-p-chlorocamphene, [oc]g —53° in EtOH. D-a- Chlorocamphene (V) and HBr-AcOH a t 5—10 °givo D-l- 1-chlorocamphene hydrobromide (VI), m.p. 140— 145° (decomp.), [a]5? -11-2° in E t20 , converted by dry Ag20 in E t ,0 + N a 2S04 into jj-l-l-chlorocamphme,b.p. 72—73°/12 mm., m.p. 3—5°, [a]f5 -12-9° in EtOH, which is reduced (Na, EtOH) to ¿-camphcne, m.p. 45—46°, [a]“ +97-5° in EtOH. (VI) rearranges in m-cresol into L-dA-chloroisobomyl bromide, m.p. 156—158°, [#]g +51-5° in EtO H [a small amount of which is formed with (VI) (above)]; treatm ent of tho solution (in m-cresol) with C5H 5N gives L-l-4-cAZoro- camphene, m.p. 132—133°, [a]1,? -1 0 8 ° in EtOH, which is reduced (Na, EtOH) to ¿-Z-camphene (VII), m.p. 51° (sinters a t 4S°), [a]1,» -104-7° in EtOH. (VII) and HC1 in E t20 give ¿-d-isobornyl chloride, [aJJJ +60°

in EtOH. (V), AcOH, and 50% H 2S 04 afford 4- chloroisobornyl acetate, b.p. 129—130°/13 mm., [a]® +51-5° in E tO H ; the yield and rotation of the acetate vary considerably. (V) and CC13'C 02H a t 50—60° give i-chloroisobornyl trichloroacetate, m.p. 67—68°, [a]}? +41-5° in EtOH (which is partly racemised by CC13-C02H), hydrolysed (MeOH-KOH) to a partly racemised alcohol; pure ¿-(Z-4-chloroisoborneol, [ajjl +32-8° in EtOH, is more sol. than the r-form in light petroleum and is thus separable. D-Z-4-Chloroiso- borneol, [<x]D —23-1°, prepared from L-camjjhor by way of £-a-chlorocamphene, is reduced (Na, EtOH) to D-Z-isoborneol, [a]® —23-7° in EtOH, which is oxidised (Cr03, AcOH) to jD-camplior, [a]y! +31-8° in EtOH. LA-Chlorocamphorhydrazone, m.p. about 120° [hydrochloride, m.p. 230—235°; Ac derivative, m.p. about 250° (decomp.)], and HgO in EtO H give 4-clilorotri- cycleno, m.p. 135—136°. H. B.

R esin. II. E xtension of the Lieberm ann colour reaction for abietic acid. W . A. L a L a n d e , jun. (J. Amer. Chem. Soc., 1933, 55, 1536—1540).— Factors influencing the colour produced in the Liebermann test arc discussed. The use of anhydrides (other than Ac20) and acyl chlorides is investigated; the most brilliant colorations (greenish-brown— >-greenish-blue—-> indigo-blue— ¿»purple— >dull brown) are observed with BzCl and conc. H 2S04. Most of the compounds of known structure which give blue or violet colorations with Ac20 and conc. H 2S04 are ?»-menthadienes containing the •CMoICH, group (I) or wz-mcnthonols which can give (I) by dehydration. Abietic acid m ay contain tho Ar:8(9)-m-menthadieno grouping. H. B.

Preparation of 5-m ethylfurfuraldehyde. I. J .R i n k e s (R c e . trav . chim., 1933, 52, 337— 338).— Details of the prep, of 5-methylfurfuraldehyde (70 g.) by the action of HC1 (d 1-163) a t 50°, rising to 72°, on crude sucrose (1 kg.) are given (cf. A., 1931, 95).

J . W. B.Preparation of 5-brom ofuroic acid. R. M.

W h it t a k e r (Rec. trav. chim., 1933, 52, 352—356).— Tho yields of 5-bromofuroic acid (I) obtained by bromination of furoic acid (II) in various solvents and with different catalysts are tabulated. The best yield (41%) is obtained by slowly adding B r to (II) in CHC13 (+ red P). Any dibromofuroic acid is romoved by purification of the Ba salt. An improvement of tho method of Shepard et al. (A., 1930, 923) for decarboxylation of (I) is described. J . W . B.

A nthoxanthins. XIV. u-H ydroxyphloraceto- phenone and certain derivatives. Synthesis of galangin under m ilder conditions than those used heretofore. J . J . C havan and R . R o b i n s o n (J.C.S., 1933, 368—370).— w : 2 : 4 : 6-Tetrabenzoyloxyaceto- phenono (I), m.p. 142-5°, prepared from w-benzoyloxv- phloracetophenone, is dehydrated by KOAc-EtOH toO-tribenzoylgalangin, m.p. 177°, or by Ac20-N a0A c to galangin. Acetoxyacetonitrilo and phloroglucinol yield co-hydroxyphloraceXophenone, m.p. 224°, which is benzoylated to (I), and is acetylated to co : 2 :4 : 6- tetra-acetoxyacetoplienone, m.p. 106-5°. F . R . S.

Synthesis of pyrylium sa lts of anthocyanidin type. XX. M orin din chloride. Cyanom ac-


lu r in . E. H. C h a r l e sw o r t h , J . J . Ch a v a n , and R . R o b in so n (J.C.S., 1933. 370— 374).— Rosorcinol and acetoxyacetonitrile form lo-acetoxyresacetophenone, m.p. 164-5° (phenylKydrazone, m.p. 152°; w-acetoxy-2 : 4-dibenzoyloxy-, m.p. 151-5°, and w : 2 : 4-triacetoxy- acetophenone, m.p. 93-5°), hydrolysed to <o : 2 : 4-tri- hydroxyacetophenono (fisetol) (osazone, m.p. 204-5°; Bz~ derivative, m.p. 140°). Eisetol and 2-O-benzoyl- phloroglucinaldehyde afford mainly 5-0-benzoyl- morinidin chloride, hydrolysed to morinidin chloride (colour reactions described), of which the reduction products (Pt—MeOH) do not closely resemble cyano- maclurin (I). The constitution of (I) is discussed (cf. Kuhn and W interstein, this vol., 72). F . R . S.

Synthetical experim ents in the isoflavone group. VIII. L im itations of the phenacyl aryl ether cyanohydrin m ethod. W. B ak e r , W. M. M o r g a n s , and R . R o b in so n (J .C .S ., 1933, 374—375).—<ji-Diazo-\)-acetylanisole, m.p. S3—84°, is obtained from anisoyl chloride and CH2N2. 3 : 4 : 5-Trimeth- oxyphenyl^-methoxyphenacylether,m.ip. 110—111°,prepared from p-mothoxyphenacyl bromide and antiarol, forms with difficulty a cyanohydrin, m.p. 126—127° (which does not undergo ring closure), and is dehydrated by P 20 5 to 4 : 5 : 6 : 4 ' -tetrametJwxy-3-phenyl- coumarow, m.p. 104— 105°. (o-Diazo-3 : 4 : 5-trimeth- oxyacetophenone, m.p. 97—98°, gives with H Br 3 : 4 : 5 -trimethoxyphenacyl bromide, m.p. 51—52°, which with antiarol and NaOH forms 3 : 4 : 5 -tri- methoxyphenyl 3 : 4 : 5-trimethoxyphenacyl ether, m.p. 135— 136°, dehydrated by P 20 5 to 4 : 5 : 6 : 3': 4 ': 5'- hexameihoxy-3 : 3-diphenylcoumarin, m.p. 112—113°.

F. R . S.Synthesis of daidzein and of 7-hydroxy-4'-

m ethoxyisoflavone. F. W e s s e l y , L . K o r n f e l d , and F. L e c h n e r (Ber., 1933, 6 6 , [5], 685— 687).— 4-Mothoxybenzyl 2 : 4-dihydroxyphenyl ketone with Xa in H C 02E t gives formononetin (I ; A, R =M e),

0 m.p, 257°. Analogously,4-hydroxybenzyl 2 : 4 -

¡¡CH / — x diliydroxyphcnyl ketone ic —\ yO R affords daidzein ( I I ; A,

yU R = H ), m.p. 323° afterdarkening a t 300° (cf.

' ■' Baker et ah, this vol.,510). (I) or (II) with CH2N 2 or Mel yields methyl- formononetin, m.p. 162—164°. H. W.

Colouring m atter of “ Awobana." II. C.K u r o d a (Proc. Im p. Acad. Tokyo, 1933, 9, 94— 96).— A co-pigment (¿1, pale yellow) was isolated, which gave J3-0 H-C6H 4-C,0 2H and O H -C 6H 4-COMe. Details are given of the isolation of the pure pigment (B ) from Awobana p ap e r; alkali fusion gives phloroglucinol and gallic acid, and B is considered to be a monoglucoside of dolphinidin. (Cf. A., 1931, 777.) P . G. M.

Styrylpyrylium sa lts . XIV. Colour phenom enon associated w ith benzonaphtha- and di- naphtha-sp /ropyrans . I. M. H e il b r o n , R. N. H e sl o p , and F . I r v in g (J.C.S... 1933, 430—434).—l-Methoxy-2-ethylchromone, m.p. 141— 142° (from 2- hydroxy-4-methoxyacetophenone, P r20 , and NaOPr) and PhMgBr form '¡-methoxy-i-phenyl-'I-ethylbenzo- pyrylium ferrichloride, m.p. 1 1 0 —1 1 1 °; from the

corresponding carbinol base, p-naphthol-1 -aldehyde, and HC1, 1 -methoxy-‘i ' ■methylbenzo-Z-napMhasçiro- pyran, m.p. 165—166°, is obtained. 2-Ethylchromone, m.p. 116°, gives <i-phenyl-Z'-mcthylbcnzo-$-naplitha- s^vropyran, m.p. 153—154°, through 4-phenyl-2-ethyl- benzopyrylium perchlorate, m.p. 207—209° (decomp.) ; 7-methoxy-3-methyl-2-ethylchromone, m.p. 85—86°, 7- methoxyA-phenyl-3-methyl-2-ethylbenzopyryliuin perchlorate, m.p. 203—205° (decomp.), and 1-methoxyA- phe?iyl-,i-?nethylbenzo-^-?ia2)hthasinvopyran, m.p. 198— 199°, are similarly prepared. 4-Phenyl-, m.p. 193— 194° [4-phenyl-2-methyl a-naplithapyrylium perchlorate, m.p. 197—199° (decomp.)], 4-phenyl-3'-methyl-, m.p. 188— 190° [2-ethyl-a.-naphthachromone,m.'p. 199— 200°, and 4-phenyl-2-ethyl-a-naphthapyrylium perchlorate, m.p. 221° (decomp.)], 4-phenyl-3-methyl-, m.p. 181—182° [4-phenyl-2 : 3-dimethyl-a-naphthapyrylium perchlorate, m.p. 223—224° (decomp.)], and4-plienyl-3 : 3'-dimethyl-a.^-dinaphthasçivopyran, m.p.181— 182° [3-methyl-2-ethyl-v.-naphthachromone, m.p.102— 103° ; 4-phenyl-3-methyl-2-ethyl-a-naphthyl-pyrylium perchlorate, m.p. 228—230° (decomp.)]; 4 ' -phenyl-3' -methylbenzo-a.-naphthasçvcopyran, m.p.115—116° ; 3 : 3'-dimethylenedi-, m.p. 245—246°, and3 : 3' - (p - methyllrimethylene)di - 3 - naphthasrpiropryran, m.p. 253—254°, are also described. The colour reactions described are not accounted for by the “ chelate ” hypothesis of Dickinson and Heilbron (A.,1927,884). F. R. S.

Vegetable fish poisons. I I . Constitution of peucedanine and oreoselone (from P e u c e d a n u r t i o f f i c i n a l e ) . E. S p a th and K . K la g e r . I I I . Constitution of osthol (from I m p e r a t o r i a o s t r u t h - iu m ). E . S p a th and 0 . P e s ta (Ber., 1933, 66, [£], 749—754, 754—760; cf. A., 1931, 1298).—II. T reatment of oreoselone (I) w ith NaOH-IvOH a t 220° yields resorcinol and P-resorcylic acid. Similar treatm ent of dihydro-oreoseione affords 7-hydrodihydrocoumarin, m.p. 134°, thus establishing the coumarin structure of(I). Oxidation of (I) by H 20 2 in alkaline solution smoothly yields wobutyric acid. Tetrahydropeuced- aninc loses MeOH when distilled in high vac. and the product is hydrogenated to deoxydihydro-oreoselone, C14H 160 3, m.p. 117-5°, reduced by P and H I probably w ith opening of the hydrogenated furan ring to a phenol, converted by H 20 2 in alkaline solution into tsohexoic acid. (I) when dissolved in conc. H 2S04, poured into H 20 , and oxidised with KM n04 yields a-hydroxyz,sovaleric acid, m.p. 81— 83°. isoD ihydro- oreoselone, C14H 140 4, m.p. 178-5—180°, is prepared from dihydro-oreoselonic acid by Cu powder in quinoline a t 240—245°. The formulæ A and B are thus established for peucedanine and (I).

cx> CO—/ Pr^CH (B)

II I . Oxidation of osthol (I) by K M n04 in COMe2 gives 2-hydroxy-4-methoxybenzoic acid, m.p. 154-— 155°. (I) is hydrogenated" (Pd-C) in AcOH to tetrahydro-osthol, b.p. 145—150° (bath)/0-006 mm., which is not immediately sol. in 20% NaOH, is oxidised by


conc. HNOg a t room temp, to succinic acid and by H20 2 in alkaline solution to isoliexoic acid (phenyl- hydrazide, m.p. 144—145°). COMe2 is obtained from

C<tt (I) and CrOg-AcOH. Ostholicacid (ButenandtandM arten, A.,

V ÇH 1932, 751) is decarboxylated byOMeL 11 /C O Cu powder in boiling quinoline

■ to 7-methoxy-8-methylcoumarin,CMe2:CH-CH2 0 m.p. 136—137-5°, the consti

tution of which follows from its oxidation to 2-hydroxy-4-methoxy-3-methylbenzoie acid, m.p. 214-5—215-5°, which is transformed by PH4I and H I .(d 1-7) into 2 : 6-C6H 3Me(OH)2, m.p.119—121° (Bz2'derivative, m.p. 106—107-5°). (I) has therefore the constitution A. H. W.

Crystalline colouring com pounds in redwood extract. E. C. S h e r r a r d and E. F. K u r t h (J. Amer. Chem. Soc., 1933, 55, 1728—1732).—Details are given for the isolation of sequoyin (I), C30H 38O10, m.p. 214° (octa-acetate, m.p. 104—106°), from the heartwood of Sequoia sempervirens. isoSequein, red, m.p. 1S8°, has also been isolated from two specimens of the green wood ; i t is apparently present in most redwood liquors. (I) is hydrolysed (5% H 2S04) to sequeinol, C16H 180 4, m.p. 242° (decomp.) (tetra-acelate, m.p. 176— 177°), which is unaffected by fusion with KOH a t 220°, and sequein (II), C20H 20Ô6, m.p. 190°.(II) gives a bright red colour with alkalis, is phenolic,affords hexa-acetates, m.p. 114° and 124° [which are not hydrolysed to (II)], and is considered to contain the2-hydroxypyran grouping (which undergoes fission during acétylation). H. B.

Action of erepsin and trypsin-kinase on prolyl polypeptides. E. A b d e r h a l d e n and H. N ie n b u r g (Fermentforsch., 1933, 13, 573—596).—The following were prepared from the corresponding a8-dibromo- valeryl (I) compounds (A ., 1932, 1064) : dl-prolyl- leucine, m.p. 207°, from (J.)-di-leucine, m.p. 100—130° ;1- (II), m.p. 217°, [a]î> —2-9°, and d-prolyl-l-tyrosine(III), [ajg +1-92°, from (I)-l-tyrosine-, 1- (IV), m.p. 247°, [a]“ -57-02°, and d -prolyl-l-leucine (V), m.p. 207°, [ajfj +9-59°, from (I)-1-leucine. Tyrosine E t ester hydrochloride with benzylamine a t 37° for 70 hr. yields 1 -tyrosylbenzylamine, m.p. 172°, which with CH2C1-C0C1 affords X-chloroàcetyl-, m.p. 175—177°, and" l&O-dicliloroacetyl-l-tyrosylbenzylamine, m.p. 208°. '&-Benzylcarbonato-l-proline, from /-proline in aq.NaOH with benzyloxycarbonyl chloride (A., 1932, 935), is converted into the corresponding chloride by PC15 and treated with glycine in aq. NaOH to give N -benzylcarbonato-\-prolylglycine, which w ith P d -H 2 yieldsl-prolylglycine, m.p. 236°, [a]™ —22-77°. Similarly are prepared ~&-benzylcarbonato-\-prolyl-\-tyrosine and its Et ester, N-benzylcarbonato-l-prolyl-l-proline (VI), m.p. 186— 187°, JS-berizylcarbo7ialo-l-prolyl-l-leucine, and N O-benzylcarbonato-l-tyrosine E t ester, m.p.103—104°. Erepsin (VII) hydrolyses dl- and Z-prolyl- glycino, (II), (IV), and dZ-prolylglycylglycine, but not(III), (V), (VI), and Z-proline anhydride. Trypsin (VIII) hydrolyses only (II). This confirms the presence in preps, of (VII) of a sp. enzyme, prolinase, which attacks the prolyl group probably a t the NH linking. Chloroacetyl-¿-tyrosine on condensation of

the C02H and OH groups or of the C02H group alone with benzylamine is no longer hydrolysed by (VIII).(VII) is far more readily inactivated by H 2S than is(VIII). P . O. H.

Catalytic dehydrogenation of pyrroline, and conversion of pyrroline into a m ixtu re of pyrrole and pyrrolidine in presence of a platinum catalyst. J . P. W ib a u t and W. P ro o st (Rec. trav. chim., 1933, 52, 333—336).—Pyrroline (I) is converted by passage over Pt-asbestos a t 160° into pyrrole (II) and H, some of which further reduces (I) to pyrrolidine (HI). At 200° (II) can be detected, but secondary reactions occur. In the presence of freshly-reduced P t in N., boiling (I) is converted into a m ixture of (II) and (III), but a t 50° only (II) and unchanged (I) can be detected. J . W. B.

Cinchom eron[hydr]azide. G . G h e o r g h iu (Bull. Soc. chim., 1933, [iv], 53, 151— 157).—Cincho- meronhydrazide (I) (Meyer and Mally, A., 1912. i, 514) \Ag2 salt (+ 2 H 20 ) ; Ac2 derivative, m.p. 146— 147°] titrates as a monobasic acid and does not condense with aldehydes; Me derivatives could not be prepared. The extinction curve of (I) is analogous to those of phthal- and quinolin-hydrazides (A., 1930, 1191) and does not differ appreciably from those of4-aminophtlialhydrazide and the Na salt of 4-nitro-phthalhydrazide (cf. loc. cit.). H. B.

Anhydro-bases from phenacylpyridinium halides. P. K r o l l p f e if f e r and A. M ü l l e r (Ber., 1933, 66, [B ], 739—743).— '¿-Bromoacetyl-i-ethylthiol- toluene, m.p. 69—70°, which gradually passes when preserved into 5 : 5'-dimethylthioindigotin and yields3-hydroxy-5-methylthionaphthen when distilled with steam, is readily converted by C5H 5N into 3-ethylthiol-5-metfoylphenacylpyridinium bro7nide (I), m.p. 201—203° (decomp.). Treatm ent with 2JV-NaOH a t 100° converts (I) into methylpyridinium salt and 2-ethylthiol-5-methylbenzoic acid (il), m.p. 136-5—137-5° (the2-methylthiol acid, m.p. 140—141°, is obtained analogously from 2-methylthiol-5-methylphenacylpyridin- ium bromide, decomp. 220°). Treatm ent of an aq. solution of (I) with excess of 2iV-NaOH yields the anhydro-base (III), C1(!H 17ONS, m.p. 129—131° after darkening, immediately converted by dil. acid into the pyridinium salt. Boiling H 20 rapidly transforms(III) into the methylpyridinium salt of (II). W ith MeOH and EtOH, respectively, (III) yields the Ale, m.p. 36—37°, and Et, m.p. 20—22°, ester of (II). (HI) and CS2 almost immediately yield a yellowish- red, cryst. product. H. W.

Reaction betw een indoles and S c h iffs bases.M. P asserenti and T. B o n c ia n i (Gazzetta, 1933, 63, 13S—144).—This reaction occurs readily to give the following: 3-a-anilino-, m.p. 154°, 3-a-p-toluidino-, m.p. 147—148°, Z-u.-$'-naphthylamino-, m.p. 80—82°, and 3-a-anilino--p-met}ioxy-, m.p. 85—87°, -benzyl-2- methxjlindole; and 2-a-anili?iobenzyl-3-methyli7idole, m.p. 155—156°. These are hydrolysed by HC1 to amine, aldehyde, and benzylidenedi-indole; for 2 : 2'- benzylidene-3: 3'-dimethyldi-indole the new m.p. 160—161° is given. Indole and NPhlCHPh form a product, m.p. 75—85°. E. W. W.


Doebner reaction. XI. R. Ci u s a and L. M u s a jo (Gazzetta, 1933, 63, 116—119; cf. A., 1930, 222).— Polemical against Carrara (A., 1931, 1429).

E. W. W.Condensation of anthranilic acid w itb 4-chloro-

quinaldine and w itb 2-chlor olepidine . 0 . G.B a c k e b e r g (J.C.S., 1933, 390—391).—4-Chloroquin- aldine and anthranilic acid afford 4 - o-carboxyphenyl - aminoquinaldine, m.p. 309—310° (decomp.), which with H 2S 04 gives 7-keto-Q-methyl-'l: 10-dihydro-8 : 9- benzquinoquinoline, m.p. 295—296° (decomp.) (sulphate), converted by distillation with Zn into G-methyl- 8 : Q-benzquinoquinoline, m.p. 137° (chloroplatinate, m.p. >325°). A7-(2-lepidyl)anthranil [hydrochloride, m.p. 222° (decomp.)], obtained by Ephraim (A., 1892, 1488), with NaOH gives 2-o-carboxyphenyl- aminolepidine, m.p. 202°, which does not form the acridone. F. R. S.

Preparation of 5-am inouracil and derivatives. M. T. B o g e r t and D . D a v i d s o n (J. Amer. Chem. Soc., 1933, 55, 1667— 1668).—Addition of H N 03 (d 1-5) to the hot solution of uracil obtained by Davidson and Baudisch’s procedure (A., 1926, 1154) gives 5-nitrouracil (47—51%), which is reduced (Na2S20 4, aq. NHS) to 5-aminouracil. 5-Nitro-6-methyluracil and K 5-nitrouracil-6-carboxylate are similarly reduced. 5 :6-Diaminouracil is prepared from 5-nitroso-6-aminouracil. H. B.

Substituted dialuric and bydurilic acids. I.H. A s p e l u n d (J. pr. Chem., 1933, [ii], 136, 329— 344).—5-Ethylbarbituric acid (I) [5-/j/--derivative (II), m.p. 202°] is oxidised (3% H 20 2; 0-5AT-K2Cr20 7 and AcOH) to 5-ethyldialuric acid (III), m.p, 216—217° [a small amount of which is formed during the prep, of (I) bv (essentially) vonM erkatz’s method (A., 1919, i, 355)]'(0-^4 c derivative, m.p. 177°), which is hydrolysed (aq. NaOH) to ethyltartronic acid, m.p. 115— 116°. Oxidation (KMn04, aq. H2S 04) of (I) gives(III) and some 5 :5 ' -diethylhydurilic acid (+ H 20)(IV), m.p. > 310° (decomp.), also formed from (H)and the Na salt of (I) in CHC13, which is hydrolysed by conc. KOH to a substance, m.p. 261—262°, and by conc. HC1 a t 210—240° to the s-diethylsuccinic acids. Oxidation (aq. K M n04) of (I) affords (IV) and a substance, C12H 140 6N4,3H20 , m.p. about 200° (decomp.) (according to ra te of heating), m.p. (anhyd.)165— 170° (becoming yellow) (decomp, about 200°), which is a strong acid and is oxidised (KM n04, dil. H 2S 04) to (III) and (IV). A substance, m.p. 175— 17S°, is formed from the N a salt of (I) and aq. KM n04.5-Benzyldialuric acid (+ 2 H 20), m.p. 214—215° (O-^lc derivative, m.p. 202°) (hydrolysed to benzyltartronic acid, m.p. 145—146°), and 5 : 5'-dibenzylhydurilic acid (+ 2 H 20), m.p. about 315° (decomp.), are obtained by similar oxidation of 5-benzylbarbituric acid (5-Br- derivative, m.p. 168°); a by-product in the oxidation with aq. KM n04 is a N compound, m.p. 87—88°, hydrolysed (conc. KOH) to a-hydroxy-[3-phenylpropionic acid. H. B.

Hydro-orotic acid. M. B a c h s t e z and G. Ca v a l - l i n i (B e r ., 1933, 66, [B], 681—6S3; cf. A., 1930, 781). —Condensation of maleie acid with CO(NH2)2 a t 132°affords hydro-orotic acid (I), N H ^ q q J ^ I ^ C H 'C O ^ ,

m.p. 247—249° (corr.) (K, Ag2, Pb, and Cu salts), which could not be esterified by HC1 and EtO H or dehydrogenated to orotic [uracil-4-carboxylic] acid. Oxidation of (I) by KM n04 a t room temp, affords CO(NH2)2, H 2C20 4, y-methylhydantoin, and (?) the oxime of oxalmonoamide, m.p. 157— 158° (decomp.).

H. W.[Isolation of] bases by m eans of Reinecke ’s sa lt,

H. W . D udley (Biochem. J ., 1933, 27, 157).—This salt with C0Me2 gives di- and tri-acetonamine under the conditions used for the isolation of bases from natural sources. R. S. C.

Production of am ines from am ino-acids. M.W ada (Biochem. Z., 1933,260,47—51).—Hydantoins prepared from NH2-acids yield the corresponding amines (e.g., CH2P lrN H 2, tyram ine, NH2Me, isoamyl- amine, histamine, putrescine, cadaverine, indolethyl- amine, aminoethyl disulphide, pyrrolidine, (3-alanine, y-aminobutyric acid) in good yield (usually 70—S4%) when treated w ith acid (H2S04, HC1) or alkali [Ba(0H)2, NaOH], " W . McC.

P yrim id ines. CXXXII. Synthesis of thym ine. W. B ergm ann and T. B. J ohnson (J. Amer. Chem. Soc., 1933, 55, 1733— 1735).—a-Cyanoprop- ionylcarbamide (I), m.p. 192°, from CO(NH2)„ CN-CHMe-COoH, and Ac20 a t 100°, gives N H3 and thym ine when reduced (H2, Pt-black, H 20). (I) isconverted by cold aq. 20% NaOH or MgO in boiling aq. solution into ‘i-aminothymine (4-amino-2 : 6-dihydroxy-o-mcthylpyrimidine), m.p. 355°. H. B.

Behaviour of aspartic acid w ben beated in g ly c e r o l; supposed cyciodipeptides of asparagine. C. R avenna and R . N uccorini (Gazzetta, 1933, 63, 103—109).—Previous work (A., 1930, 627;1931, 1430) is confirmed. Aspartic acid in glycerol a t 160—170° remains largely unaltered; by use of Pb(OAc), a substance, Cn H 180 9N2 (?), is obtained, regarded as a diaspartic ester of glycerol, whilst on prolonged heating a substance, Cu H 160 8N2, results. The former is also obtained from NH4 aspartate. The view of Shibata (A., 1927, 891) th a t cyclodi- peptide condensation occurs through the C02H group is thus not confirmed. E. W. W.

2 - P b e n y l - l ' : 2 /-n a p h th im in a z o le . F . Galim- ber t i (G azzetta, 1933, 63, 96—99).—Benzoyl-o- phenylenediamine is dehydrated when heated to2-phenylbenziminazole. l-Nitro-2-benzoylnaplithal- ide is reduced (Zn+H Cl in EtOH) to 2-phtnyl-V : 2'- naphthiminazole, m.p. 296°. A modified method of prep, of the 1-Ph isomeride is described.

E. W. W-4-N itro-5- (3-pyridyl )pyra2 ole , a new oxidation

product of nicotine. III. Confirm atory synthetical experim ents. G. A. C. Gough and H. K in g (J.C.S., 1933, 350—351).-4-Amiiio-5-(3-pyridyl)pyrazole (cf. A., 1932, 68; this vol., 76) is deamin- ated to 5-(3-pyridyl)pyrazole (I) \picrate (+ H 20), m.p. 194— 195°; jlavianate (-f2H 20), m.p. 229° (decomp.); methiodide, m.p. 217-5°; methopicrate, m.p. 185°]. E t nicotinate, COMe2, and Na afford [3-pyridoylacetate, which with N2H 4,H2S 04 forms 3-methyl-5-(3-pyridyl)- pyrazole (+1-5H 20), m.p. S I—83°, and 137—138°(imonopicrate, m.p. 202—203°; hydrochloride, m.p.


214—216°), oxidised with KM n04 to 5-(3-pyridyl)- pyrazole-3-carboxylic acid, m.p. 30S—310° (efferv.) (picrate, m.p. 242—245°). The acid is decarboxylated to (I). F. R. S.

Chlorophyll a . H . F i s c h e r (Annalen, 1933, 5 0 2 , 175—200).—A lecture. . H. B.

Synthesis of acenaphthene-peri-m -thiazines and of dyes derived therefrom . M. T. B o g e r t and R. B . Co n k l in (J. Amer. Chem. Soc., 1933, 5 5 , 1705— 1710).—4-Nitroacenaphthene-3-sulphonyl chloride is reduced (SnCl2, AcOH-HCl) to 3-amino A-thiolaca- naphthene chlorostannate, which when treated successively with NaOAc-AcOH a t 90° and to-N02‘C6H4‘C0C1 gives the 'NS-di-m-nitrobenzoyl derivative (I), decomp, about 235-5° (all m.p. and decomp, are eorr.), of 3-amino-4-thiolacenaphthene(II). The N -p-nitrobenzoyl derivative, decomp. 246— 247° (turning dark red), of (II) and 2-p-nitrophenyl- p'eri-m-thiazine, decomp. 253-7°, are obtained similarly using ^-NOg-CgH^COCl, whilst with BzCl, 2-phenyl- acenaphthene--peTi-m-thiazine (III), m.p. 142-3° (shrinks

and softens a t about 128°), results. (I) heated with NaOAc-AcOH gives 2-m- nitrophenylacenaphthene - peri - m - thiazine, m.p. 190-3—191-3° (decomp.) (shrinks a t about 189°). Dyes of the Columbia-yellow type are prepared from 2-m-, m.p.176-7— 177-7° (decomp.), and 2-p-, m.p.214-8—215-S° (decomp.), -aminoplienylace- naphthene--peri-m-thiazines; their dyeing properties are compared with those from the analogous^erinaphtho-m-thiazines (A.,

H. B.

CPh

CH2 c h 2(HI.)

1932, 176).Sopliora alkaloids. I. Alkaloids of the foliage

of S. pachycarpa. A. O re k h o v , M. R a b in o v itsc h , and R . K o n o v a lo v a . II. A lkaloids of Therniop- sis lanceolata. A. O re k h o v , S. N o rk in a , and H. G tjre v itsc h (Ber., 1933, 6 6 , [5], 621—625, 625— 630).—I. Percolation of th e finely-divided foliage of S. pachycarpa w ith E tO H containing 2% of AcOH removes abou t 3% of to ta l alkaloid, divisible into portions sol. in E t20 and CHC13, respectively. The E t20 ex trac t yields an alkaloid C15H 2j.N2, b.p. 138°/2 mm., [ajg +5-54° or +16-3° in E tO H , provisionally named pachycarpine, b u t probably rf-sparteine. The following derivatives are d e sc rib ed : mono-, m.p.234—235°, [a]9 - f 9-8° in E tO H , and di-, m.p. 255— 257° after softening a t 250°, -hydriodide', picrate, m.p. 199—200°; chloroplatinate, m .p. 240—241° (decomp.) after darkening a t 235°; chloroaurate, m.p. 192— 193° (decom p.); methiodide, m .p. 236—238°, [a]D +24-5° in H 20 , and its hydriodide, m .p. 223—224° (decomp.) and, after re-solidification, m .p. 234— 235°.

II . The foliage of T . lanceolata, R. B. (syn. S. lupinoides, Pall), is percolated w ith EtOH containing 2% of AcOH, the percolate evaporated to dryness, and the residue treated with 3% HC1. The acid solution is rendered strongly alkaline with NH3 and extracted with E t20 , to which it yields 0-53% of crude alkaloids (I) (calc, on dried material). The aq. solution is treated w ith NaOH and extracted successively with E t20 and CHC13, to which it yields 0-34% and 0-23% of alkaloid, respectively. From (I) are isolated : (A) thermopsine, C15H 20ON2, m.p. 205—206°,

[oc]j? —159-6° in EtOH, highly unsaturated bu t not hydrolysed by acid or alkali. I t yields a picrate, m.p.208—209°, chloroplatinate, decomp. 254—256° after darkening a t 250°, hydriodide, m.p. 306—308° (decomp.), and methiodide, m.p. 241—242° (decomp.). The second N atom and the O atom are indifferent. Catalytic hydrogenation (P t0 2 in JV-HC1) yields tetra- hydrothermopsine, m.p. 75-5—76-5°, [a]D -52-23° in EtOH [dihydriodide (-(-3MeOH), m.p. 296—298° (decomp.) after softening a t 290°; picrate, m.p. 143— 144°; chloroplatinate, m.p. 241—242° (decom p.)]; (B) pachycarpine, identified with th a t described above by direct comparison of hydriodides and methiodide hydriodides; (C) alkaloid I I I , a pale yellow, very viscous liquid which yields a very hygroscopic hydrochloride, picrate, m.p. 217—218°, and methiodide, m.p. 226—229° (decomp.). H. W.

A lkaloids of fum araceous p lants. III. A new alkaloid, bicuculline, and its constitution.R . H. F. M a n s k e (Cañad. J . Res., 1933, 8,142— 146). —The alkaloid a (this vol., 105), now called bicuculline

pxr (annexed formula), m.p. 177°,a 2 and 196° (two forms) [hydro-

p rr Y QH2 chloride, m.p. 259° (slight2<"0-l Jv ,N M o decomp.)], is found in Cory-

OH dalis sempervirens and Adlu-j j q __q miafiaujosa, Greone, and has

| probably been isolated from/ y C O other sources. HydrolysisI JOMe gives hydrastinine and

2-carboxy-3:i-methylenedioxy- benzaldehyde, m.p. 155°, which

gives an imide, m.p. 270° (sublimes), with NH2OH,AcOH, is reduced to 3 : 4-methylenedioxy- phthalide, m.p. 227°, and after oxidation gives 3 : 4- methylenedioxyphthalethylimide. Bicuculline m ethiodide after conversion into the hydroxide gives N-methylbicuculleine, m.p. 246°, with hot H20.

A. A. L.S trych n o s alkaloids. LXXIII. Oxidation by

chrom ic acid of brucine- and strychnine-sulphonic acids I and II and fission by hydrogen- aton of the ether groups in the acids C16H 20O7N 2SI an d II. H. L e u c h s , G. S c h l e m p p , and A. D o r n o v (Ber., 1933, 66, [£], 743—749; cf. A., 1932, 953).— Strychninesulphonic acid I (’.GHPh derivative, [a]g —250°/d in 0-05i\7-NaOH) could not be satisfactorily hydrogenated (P t0 2) in H 20 , H 20 -N H 3, H20-alkali, or H20-A c0H . Brucinesulphonic acid I (purification described) behaves similarly. The acid C17H 20O8N2S (4) (semicarbazone, [a]'g —192°/d in H 20) is reduced by N a-H g to the acid C17H 220 8N2S (B), [a]i? —101-6°/d in H 20 , which could not be catalytically hydrogenated. A in presence of P t0 2 yields the substance C17H 220 8N2S, fajfj — 74°/cZ, with minor amounts of B. The acids CiGH 20O7N 2S I (C) and I I are hydrogenated (P t0 2) to the isomeric acids C16H 230 4N2,S03H I, [a] ; — 25°¡d in H 20 , and II , [a]“ —62-6°/d, reaction being considered to be accompanied by fission of the ether groups. Oxidation of C w ith B r-H B r in H 20 gives the products C16H 20O8N2S, [a]“ —136-4°¡d in H 20 , and C16H 20O8N2S,HBr, [ajfj — 130°/d!. Brucinesulphonic acid I I (D) is hydrogenated to the acid C23H 280 7N2S, [a® +140°/d in 0-OSAr-NaOH. D is


oxidised with less Cr03 to the acid 0 lnH 210 GN2-S03H, [a]“ —90-5°/d in NaOH, analogous to the Haimsen C19 acid, and by more C r03 to the acid C16H 190 4N2-S03H I I (E), [a]5 + 1 9 2 °/d in H 20 . E is obtained in larger yield from strychninesulphonic acid I I through the A70 2-compound C21H 210 7N3S, [ajj? —28-9°, and the iVi/2-compound, C21H 230 5N3S, which is oxidised,with Cr03-H 2S 04. H. W.

Lupinine. K . K rieg (Diss., Marburg, 1928; Bied. Zentr., 1932, 3, A, 51).—Oxidation of anhydro- lupinino and of lupinine (I) and the Hofmann decomp, of lupinan indicate the generally accepted formula of(I) to be untenable. The side-chain is not in the a-position w ith respect to N. A. G. P.

R otatory pow er of quinine sa lts in aqueous solution . C. L a p p (Compt. rend., 1933, 196, 970—- 971).—The [a] of quinine increases with acidity, the [a]—p,r curves showing inflexions a t p a 4-6—6-5 and< 2, corresponding w ith the neutral and acid salts, respectively. Vais, of [a] for different X are given, on which is based a polarim etric method of determining quinine a t p B 5-5. A. C.

Sinom enine. XXXV. (—)-Sinom enic acid and (—)-l-brom osinom enilone from thebaine.K. G oto and H. S h is h id o (Annalen, 1933, 501, 304— 308).— (—)-l-Bromosinomeninone (I) (Schopf dal., A.,1932, 290) is oxidised (H20 2) (cf. ibid., 62S) to ( — )-l-bromosinomenic acid, m.p. 251°, [a]'fi —70-8° in H 20 , which is debrominated (H2, Pd-B aS 04, PdCl4, AcOH) to (-)-sinomenic acid, m.p. 289° [a]ff —90-24° in H 20. (—)-l-Bromosinomenilic acid (II), m.p. 290—293° [the (-f)-acid (ibid., 760) has m.p. 290—293°, and not 285°], [a]'$ —91-4° in dil. NaOH (Ac derivative, m.p. 165°), best prepared by reduction (Na-Hg in H 20 and C02) of (—)-l : 1-dibromosinomenilic acid, m.p. 226°, M u -79 -5° in dil. NaOII [obtained with a little (II) from (I) and B r in AcOH], is converted by oleum (cf. ibid., 720) into (—)-l-bromosinomenilone, m.p. 182°,[a]1,? —246-04° in EtOH. The following ¿¿-compounds are prepared from their ( + )- and ( —)-forms : 1- bromosinomenic acid, blackens a t 251° (sinters a t 190°, decomp, a t 200°); sinomenic acid, m.p. 286°;1-bromosinomenilic acid, m.p. 293°; 1 : 7-dibromosinomenilic acid; 1-bromosinomenilone, m.p. 155— 158°. H. B.

Aldehyde oxidation of tolylarsin ic a c id s . H. M.P a r m e l e e and C. S. H a m il t o n (J. Amer. Chem. Soc.,1933, 55, 1463—1469).—Oxidation of the appropriate C6H 4Me-As03H 2 with Mn20 3 (or M n02) and H 2S04 (40—96%) a t 80—100° and treatm ent of the diluted solutions with j>-N02-Cr,H4'NH-NH2,HCl give benzaldehyde--p-nitrophenylhydrazone-2- (I), m.p. 201-5° (corr.), -3-, m.p. > 250°, and -4- (II), m.p. > 250°, -arsinic acids. (I) and (II) are also prepared by oxidation w ith C r03, AcOH, Ac20 , and H 2S04 (cf. A., 1930, 1601). Benzaldehydej)heiiylhydrazone-o-arsinic acid has decomp. 130— 137° (according to ra te of heating) (darkens a t 105°). 4 : Q-Dinitro-6-tolylarsinic acid, m.p. 201—203° (NHi salt), from the 4-N 02-acid, HNOa (d 1-6), and oleum (20% S03), is reduced [Fe(OH),] to 4 : 6-diamino-o-tolylarsinic acid (Na salt), and with jj-NO’CgHj-NMe, and N a2C03 in M eOH+ EtOH gives the ji-dimethylaminoanil of 4 : 6-dinitro-

benzaldehyde-2-arsinic acid. A modification of the method (B., 1930, 348) of determining As is given.

H. B.Action of chlorine on p-tolylarsinic acid under

the influence of ultra-violet ligh t and its chlorination w ith hypochlorous acid. C. S. H a m il t o n and W. N. K i n g ( j. Amer. Chem. Soc., 1933, 55, 1689—1692).—Chlorination of ;p-C6H 4Me-As03H , (I) in C2C16 a t 185—190° or of i >-C6H4Me-AsCl4 (II) in C2C1B a t 140° gives (after treatm ent with 6Ar-NaOH) iJ-CgH4Cl-C02H (III). Chlorination of (II) a t 90— 100° under the influence of ultra-violet light affords AsCl3 and jp-C6H4McCl and then (III). (I) and HOC1 give 2-chloro-Tp-tolylarsi7iic acid, m.p. >250°, which is oxidised (alkaline K M n04) to ?>-chloroA-carboxy- phenylarsinic acid, m.p. 233°. Dichloro-2-chloro-^- tolylarsine and Cl a t 100° in ultra-violet light yield (as above) 2 : 4-C6H 3Cl2-C02H. H . B.

Isom erism of hydroxyphenylarsinic acids.G . G il t a (Bull. Soc. chim. Belg., 1933, 42, 119—126; cf. A., 1928, 1146).—p-0H-C6H4-As03H 2 prepared from diazotised |j-OH-C6H4-NH2 is identical with tha t prepared by arsenical fusion of PhOH. The following salts are described : Na H (+ 5 H 20 ); K H (anhyd., + 2 H 20 , + 3 H 20 ); Rb H (anhyd., + 2 H 20 ) ; Cs H (+ 2 H aO); N H 4 H ( + 3 H 20 ); N a2 (+ 3 H 20 , + 4 H 20, + 5 H 20 ) ; 0 N a,C6H 4-As03Na2 (hydrated, bu t unstable). W ith a few exceptions these were obtained from both forms of the acid. The Ba salt from the “ fusion ” acid is anhyd., but the “ diazotisation ” acid gives a Ba salt (+ 2 H 20), readily dehydrated to a new anhyd. salt, and converted into the “ fusion ” isomeride by heating in aq. EtOH. H. A. P.

A rylarsin ites of thiophenols [phenylthiol- arsines] and their com plex m ercuric sa lts . G.S c h u s t e r (J. Pharm . Chim., 1933, [viii], 17, 331— 334).—PhSH and the appropriate chloroarsine in EtO H afford aryldi(flienylthiol)arsines, AsAr(SPh)2, in which Ar is i-chloro-3-nitrophenyl-, an oil, o-, m.p. 83° (220°), m-, an oil (200°), and p-nilrophenyl-, m.p. 26—27° (m.p. 196°), p-chlorophenyl-, an oil, p-awiino- phenyl-, m.p. 127° (230°), o-, an oil (140°), and p -tolyl-, an oil (200°), and diphenyl-, an oil (260—270°). The temp, in parentheses are the approx. tomp. a t which the complex salts w ith 4HgCl2 sublime. The arsines and their Hg salts are quantit atively oxidised by I-to arylarsinic acids and Ph2S2. R. S. C.

Derivatives of benzaldehyde-p-arsinic acid.C. S. G ib s o n and B. L e v in (J.C.S., 1933,352).—Benz- aldchyde-_p-arsinic acid gives the following: with CH2(C02H)2 ji-arsonobenzylidencnialonic acid, m.p. > 300°; with CN-CH2-C02H, cinnamonitrih-y-arsinic acid, m.p. > 300°; benzaldehydc-y-dichloroarsine, m.p. 105°, -p-arsenious oxide, m.p. 232°, and 4 :4 '-di- aldehydoarsenobenzene, decomp. 240°. F. R. S.

Additive com pounds of phenylboric acid with bases. D. L . Y a b r o f f and G . E. K. B r a n c h (J. Amer. Chem. Soc., 1933, 5 5 ,1663—1665; cf. A., 1932,836).— Compounds of the type N R 3-BPh(0-BPh-0H)2, derived from 3 mols. of PhB(OH)2 and 1 mol. of base by elimination of 2H20 , are prepared from N H E t2, NEtg, N H ,Pr, C5H 5N, and piperidine; they have m.p. 85“, 39°," 140—143°, 148—149°, and 213°, respectively.


NH 2Ph, N H Ph2, MeCN, PhCN, CH2Ph-CN, and CH2Ac2 and its Na salt do not form stable additive compounds. H. B.

Interconversion of arylm ercuric halides and m ercury d iaryls. II. R. W. B e a t t ie and P. C. W h it m o r e (J. Amer. Chem. Soc., 1933, 55, 1567— 1571).— \-ChloronaphthaleneA-, m.p. 111°, -5-, m.p. 121°, -6-, m.p. 127— 128°, -7-, m.p. 128-5—129°, and-8-, m.p. 105°, and 2-chloronaphthalene-l-, m.p. 87°,-6-, m.p. > 300°, -7-, m.p. 134°, and -8-, m.p. 127°, -sulphinic acids are prepared by reduction (Na2S03, aq. NaOH) of C10H bC1'SO2C1 ; in many cases them.p. increases > 100° when the acids are kept.These aro converted by aq. HgCl2 into 4.-chloro-l- naphthylmercuric chloride, m.p. 252° (bromide, m.p. 251°; iodide, m.p. 233°), 5-chloro-l-naphthylmercuric chloride, m.p. 244° (bromide, m.p. 231-5°; iodide, m.p. 221-5°), 5-chloro-2-naphtliylmercuric chloride, m.p. 307° (bromide, m.p. 316°; iodide, m.p. 276-5°), 8-chloro-2- naphthylmercuric chloride, m.p. 223° (bromide, m.p. 247°; iodide, m.p. 257°), S-chloro-l-naphtht/lmercuric chloride, m.p. 214° (bromide, m.p. 195-5°; iodide, m.p. 156-5— 157-5°), 2-chloro-l-naphthylmercuric chloride, m.p. 215° (bromide, m.p. 204°), 6-chloro-2-naphthylmercuric chloride, m.p. 260° (bromide, m.p. 260°; iodide, m.p. 298°), l-chloro-2-naphlhylmercuric chloride, m.p. 295° (bromide, m.p. 288°; iodide, m.p. 272°), and 7-chloro-l-naphthylmercuric chloride, m.p. 232-5° (bromide, m.p. 226°; iodide, m.p. 192-5°), respectively. Tho chlorides are converted into HgAr2 by E tO H -N al; the following aro described : llg d i-4-, m.p. 275-5°, -5-, m.p. 223-5°, -8-, m.p. 215-5—216-5°, -2-, m.p. 293-5°, and -7-,'m .p . 273-5°, -chloro-l-naphthyls; E g di-5-, m.p. 246°, -6-, m.p. 260°, -7-, m.p. 299°, and -8-, m.p. 230-5°, -cliloro-2-naphthyls. HgPhCl and EtOH-NaCN (1 mol.) give HgPh-CN, bu t with excess of NaCN, HgPh2 resu lts ; Hg di-p-tolyl (I), Hg(C10H v-P)2, m.p. 247—248° (II), and the above HgAr2 are similarly prepared. HgArCl is also converted into HgAr2 by EtO H -K O H or Alk-OH-NaOAlk; HgPh2, (I), and {II) are thus prepared. H. B .

Form ation of a heterocyclic ring closed through m ercury atom s. III. L. V e c c h io t t i and C. S il v e s t r i n i (Gazzetta, 1933, 63, 110—111).—o- C6H4(CH2Br)2 treated in petroleum (b.p. 150—160°)with Na^Hgy gives a compound, C6H4< ^ ^ 2 H jg (?).

E2. W. W.A rylselenium halides. II. 0 . B e h a g h e l and

H. S i e b e r t (Ber., 1933, 66, [J3], 708—717; cf. A.,1932, 762).—m-Chlorophenyl selenocyanate, b.p. 150— 152°/13 mm., m.p. 53°, is obtained from m-C6H 4Cl,N H2 through the diazo-compound. 2 : 2'-Dinitrodiphenyl diselenide is derived from NaOMe and o-nitrophenyl selenocyanide in MeOH in 98-2% yield. The following Searyl bromides have been prepared: o-C'c/ / 4-iY02, m.p. 64—65°, which does not add Br, is very stable to H20, and converted by alkali into the diselenide; p-C'6# 4*j\r0 2, m.p. 92°, converted by H 20 or Na2C03 into 4 : 4 '-dinitrodiphenyl diselenide, m.p. 177°. Tho following Se aryl tribromides have been p repared : mi-, decomp. 114°, and p -G6Hi-N 02, decomp. 107— 108°; o-, decomp. 107°, m-, decomp. 107—108°, and p-, decomp. 123—124°, -C'0/ / 4C'Z; 2)-C6H 4Me, m.p.

115— 116°. Se Ph chloride, m.p. 59—60°, and Seo-nitrophenyl chloride, m.p. 64°, are derived from the diselenides and S 02C12 or SOCl2, respectively. T reatment of the requisite selenocyanates or diselenides in CHC13 with Cl2 or with S02C12 in slight excess leads to the following Se aryl trichlorides’, m-, decomp. 132° (indef.), and p -06Hi wN 0 2, decomp. 183—184°; o-, decomp. 162°, m-, decomp. 150°, and p-C'G/ / 4C/, decomp. 172°. Hydrolysis of the trichlorides or tribromides with H 20 yields tho following arylsoleninic acids: Ph, m.p. "122°; o-, m.p. 184°, m-, m.p. 156°’ and p-CV/j-iYO,, m.p. 214—215°; ^-C0H.4Me, m.p. 169—170°; o-, m.p. 160°, m-, m.p. 155°, and p- C6H4C1, m.p. 179—180°. SePhBr is transformed by M gEtBr in E t ,0 into Ph E t selcnide, b.p. 102—104°/ 20 mm. Se o-nitrophenyl bromido (chloride, tr i chloride) and NPhMe, in boiling E t20 afford 2-nitro- 4 '-dimethylaminodiphenyl selenide, m.p. 169° (hydrochloride,, decomp. 180° after blackening a t 174°). 4-Nitro-4:'-dimethylaminodiphenyl selenide, m.p. 180°, yields a hydrochlorido and (?) tribromide, decomp, (indef.) 97°. Se o-nitrophenyl bromide (I) is transformed by KCN in boiling CHCl3-AcOH into o-nitrophenyl selenocyanate. Hydrolysis of (I) by KOH in E t0 H -H 20 leads through a violet compound to tho diselenide. H. W.

Preparation of tri-jp-tolylselenonium chloride by m eans of the Friedel-Crafts reaction w ith selenium dioxide. J. H. Cr o w e l l [with W. E. B r a d t ] (J. Amer. Chem. Soc., 1933, 55, 1500—1502). —PhMe, Se02, and A1C13 give tri-p-tolylsolenonium chloride (+ H 20), m.p. 160° (corr.) [isolated in 77% yield as its additive 2 : 1 -compound, m.p. 235°, with ZnCl2], which when heated to 200—235° affords 2>CfiH4MeCl and So(CcH 4Me-^)2. The compound, 2SePh3Cl,ZnCl2, has m.p. 273-5—274°. H. B .

Isolation of m ethionine and ergothioneine.N. W. P i r i e (Biochem. J ., 1933, 27, 202—205).— Methionine is best obtained from the enzymic hydro- lysato of caseinogen (or ovalbumin) by pptn. with Hg(OAc)2 and phosphotungstic acid, followed by fractionation with EtO H and pptn. with HgCL. Ergothioneine is best obtained from aq. ergot extract by forming the Cu1 derivative and dissolving the ppt. in H 20 . R,. S. C.

Preparation and fractionation of the a- naphthylcarbim ide com pound of plastein . S. J.F o l l y (Biochem. J ., 1933, 27, 151—-152).—Pptn. of a feebly alkaline solution of tho compound of purified plastein and a-naphthylcarbimide first by C02 and then by AcOH gives fractions of different basicity, further subdivided by extraction with hot and cold EtOH. R. S. C.

Polarographic studies w ith the dropping m ercury cathode. XXXI. T est for proteins in presence of cobalt in am m oniacal am m onium chloride solutions. R. Brdicka (Coll. Czech. Chem. Comm., 1933, 5, 112-—128).—When protein (I) is added to an ammoniacal solution of a cobaltammine salt the max. in the current-voltage eurvc due to the deposition of Co vanishes and two new waves appear; their form, magnitude, and position depend on the (I) content and the Co, NH4‘, and N IL concns.


In all cases the waves rise to a limiting height with increase of the (I) concn. Their appearance is related to tho presence of cystino (II) in the (1) mol., since no wave is produced by other N H 2-acids or by gelatin and silk. (II) itself a t low concns. (2 x lO^iY) produces a wave 500 times > would bo expected from simple reduction, and it therefore appears th a t the effect is due to catalysis by (II) of the H deposition. H . F. G.

P rim ary and secondary reactions of proteins w ith acids and b ases. G. V. S c h u l z and G. E ttisc h (Z. physikal. Chem., 1933, 164, 97— 120; cf.A., 1932, 465).—The reaction of casein and serum- albumin and globulin with acid or alkali consists of an instantaneous ionic reaction followed by a secondary reaction which continues for about 20 hr. In the prim ary reaction, which m ay bo represented as R-C02'+ H -= R -C 02H, or R-NH3,+ O H '= R -N H 2+ H 20 , the amount of alkali fixed rises and tends to a saturation val. w ith rise in tho equilibrium alkali concn., and tho amount of acid or alkali taken up byI g. of protein is independent of tho protein concn. The acid and alkali titration curves of albumin can be successfully calc, by applying the mass law to tho above equations and assuming tha t between p a 1-2 and 12-8 three alkali-binding and two acid-binding groups are active. The dissociation consts. of these groups have been calc, and identified with those of certain amino-acids. In the secondary reaction, which for acids is only feeble, tho amount of alkali taken up increases continually with the alkali concn. Above p nII this reaction consists principally in an irreversiblebreaking up of protein mols. with release of new activo g roups: R -C 0-N H R '+ N a0H = R -C 02N a+ R '-N H 2,R -C 0-N H R '-fH C l+H 20 = R -C 0 2H + R '-N H 3Cl. Below p a 11 similar, b u t reversible, changes occur.

R. C.B arley-husk protein. H. L u e r s and W. H u t-

TDiGER (Woeh. Brau., 1933, 50, 97—102).—E xtraction of Moufang’s “ testinic acid ” (B., 1931, 217), with COMe2 removes the tannin (A), leaving the protein (B). The cystine, tryptophan, tyrosine, and histidine in B were determined colorimetrically. B resembles the albumins : acid hydrolysis reveals a high proportion of N H 3-, proline-, cystine-, asparagine-, histidine-, and arginine-xY. A contains gallic and ellagic acid and glucosidically bound sugar. I t may be separated into a H 20-, E t20-, and COMe2-sol. group. The tannin isolated by another method" (A.,1931, 777) contains phloroglucinol and ^-hydroxy- benzoic acid, but no ellagic or gallic acid. R. H . H."

A ction of alkali on collagen. I. W ater- and alkali-soluble non-collagen proteins and collagen degradation products. II. Influence of nature and concentration of alkali and state of the collagen on solub ility of non-collagen proteins. III. Effect of alkali treatm ent on insoluble collagen residue. A. K u n t z e l and J . P h i l i p s (Collegium, 1933, 193—206, 207—212, 213—229).—I. Only6-7% of the to tal N of a H 20 extract of collagen (I) is protein-N (pptd. by CC13-C02H), as compared with 47% for a NaOH extract and 66-5% for a Ca(OH)2 extract. A concn. of 5% CC13-C02H ppts. some protein degradation products as well as protein itself. The (I)-protein contains 17-6% N, th a t from the H20

extract 10-6%, and the alkali extract 12-3%. Purified (I) contains 18% of arginine (gelatin, 14-7%).

II . Ca(OH)2 is a better solvent for tho non-(I) proteins of frcsli (I) than N a2S or NaOH, but the last two are more effective on tho dried product.

I I I . The conversion : (I) -— y gelatin is promoted more by Ca(OH)2 than by NaOH and N a2S; the reverse is true for (Ï) degradation. D egradations aided by an increased temp. (1 day a t 40°) and conversion into gelatin by increased time (30 days a t 20°).

P. G. M.Phosphorus - containing am ino - acid from

caseinogen. F. L ip m a n n (Naturwiss., 1933, 21, 236—237).—When caseinogen is hydrolysed with2-5ÎV-HC1, 60% of the to tal P is in org. combination in the hydrolysate. This gives a Ba salt, sol. in H 20 but insol. in 40% EtOH, from which, by further hydrolysis, an N H 2-acid is obtained with N : P ratio 1 :1 (Ag salt, 61-2% Ag; serinephosphoric acid salt requires 63-8% Ag). P. G. M.

P rolysin , a-am ino-8-hydantoinvaleric acid, a n ew decom position product of protein. I. M.W a d a (Proc. Imp. Acad. Tokyo, 1933, 9, 43—46).— Prolysin, C8H 130 4N3 (I), has m.p. 222° (decomp.) (Cm salt, m.p. 260° ; 'picrate., m.p. 122°). The isolation of (I) from the products of tryptic digestion of caseinogen and by hydrolysis of gelatin w ith HCl-saturated 60% aq. EtO H as the xanthyl derivative and the Ag salt, respectively, is described. (I) on hydrolysis with conc. HC1 or NaOH gives lysine; w ith aq. H I, oc-aminopimelic acid; with Ba(OH)2, a-uramino-a'- aminopimelic acid (II) ; with H 2S04 and BaC03, (II), and w ith H N 0 3, parabanic acid. Condensed with C0(NH2)2, (I) gives ay-dihydantoinpropane, which with Ba(OH)2 is converted into cadaverine. From these observations (I) is believed to be a-amino-o- hydantoinvaleric acid. Colour reactions of (I) are described. A. L.

Internal structural changes of ovalbumin during dénaturation. A. v o n K û t h y (Biochem. Z., 1933, 259, 432—435).—Tables show the total-, amide-, basic, humiri-, NH 2-, and non-NH2-N of native albumin and after dénaturation with KCNS, CO(NH2)2, urethane, EtO H, PrOH, COMe2, and by heat. Considerable increaso in humin-, basic, and non-NH2-N and decrease of N H 2- and amide-N are recorded. Tho results show th a t heat- and EtOH- denaturation are analogous processes and are explained in terms of ring closure and the formation of inner anhydrides. P. W. C.

Action of ether and alcohol on solid protein.G. E t t isc h and G. V. S chulz (Biochem. Z., 1933,259, 418—419).—Whereas EtO H denatures solid protein in the same way as protein in solution, E t20 has little effect. P- W. C.

Interaction of caseinogen and nicotine. I. S.J aitschnxkov (Biochem. Z., 1933, 259, 381—383).— 1 g.-mol. of nicotine unites with 2000 g. of caseinogen, or, assuming th a t the mol. w t. of the la tter is 12,000, with 1/6 mol. of caseinogen. T h is corresponds with the figure 2000 which is usually given as the equiv.


Electrolyte-free proteins. XI. E lectrochem ical com position of h ighly purified protein solutions. D. v o n K l o b u s it z k y and W. P a u l i (Bio- chem. Z., 1933, 260, 201—212).—Further support is provided for the view th a t in solutions of highly purified proteins [ovalbumin (I), seralbumin (II)] the dissociated protons are distributed over the whole protein mol., this distribution giving rise to the production of positively and negatively over-charged, together with neutral hybrid ions. W ith electropositive pseudoglobulin no such distribution occurs and i t is less pronounced with (II) than with (I).

W. McC.Acropeptide from caseinogen. Structure of

polypeptide chains in relation to enzym ic hydrolysis. A. F o d o r and S. K u k (Biochem. Z., 1933,259, 331—339).—The octapeptide D x (mol. wt. 913) obtained by the degradation of caseinogen in glycerol (A., 1931, 1436) on treatm ent with olV-lactic acid at 37° for several days gives a quant, yield of a product mol. wt. 467, total N (Kjeldahl) 13-53% (Dx 13-80%), the same NH 2-N as D l: half the C02H titration, and

—65-19° (Dj -63-38°). The results are discussed in relation to the structural changes.

P. W. C.Comparative fission of triglycylglycine by

norm al sodium hydroxide and erepsin at 37°.E. A b d e r h a l d e n and A . N e u m a n n (Fermentforsch., 1933, 13, 459—466).—When triglycylglycine (I) is hydrolysed by iV'-NaOH a t 37° a terminal glycyl group is first eliminated yielding diglycylglyeine; no fission occurs a t the middle of the mol. (cf. A ., 1932, 935). The action of erepsin on (I) is similar but less rapid; the jhi optimum is 7-S a t the beginning, but changes during the course of hydrolysis. F. 0 . H.

Action of crystalline trypsin on pentaglycyl- glycine, tri- i-alanyl- i-alanine, and tetra-di- alany 1-di-alanine. J . H. N o r t h r o p and M. K u n it z (Fermentforsch., 1933, 13, 597—600).—The polypeptides are not hydrolysed to any significant extent.

F . O. H.General applicability of the micro-Kjeldahl

determ ination. A. F r ie d r i c h (Z. physiol. Chem., 1933, 216, 68—76).—N2 loss in Kjeldahl determinations on hydrazine, NQ2-, NO-, and azo-derivatives is obviated by preliminary reduction with HI. Volatile substances or those yielding volatile N compounds m ust be heated in a sealed tube with H I. Antipyrine under these conditions gives trustworthy figures. Diazo-compounds m ust first be coupled with a phenol. The process is generally applicable to all compounds containing organically bound N, but not to N 0 3'. J . H. B.

D eterm ination of arsenic in organic com pounds by the calorim etric bom b. F . G a r e l l i and B. Ca r l i (Annali Chim. Appl., 1933, 23, 129— 132).—Use was mado of a Kroeker type bomb of V2A steel. W ith cacodylic acid and therapeutic arsonicals good results were obtained. T. H. P.

Determ ination of phosphorus in organic com pounds by the calorim etric bom b. F . G a r e l l i and B. Ca r l i (Annali Chim. Appl., 1933, 23, 124— 128).—The substance, mixed with PhMe or decahydronaphthalene, is burnt in a quartz crucible in

the bomb, which contains 10 c.c. of H 20 . After 30 min., the P 20 5 is determined as Mg„P20 7.

T. H. P.Colorim etric determ ination of sm all quant

ities of lead in organic m atter in presence of tin .M . A. M a c h e b c e u f , H. Ch e f t e l , and J . B l a s s (Bull. Soc. chim., 1933, [iv], 53, 190—196).—Org. m atter is destroyed by heating with H 2S04 and H N 03, a paste of CaS04 is added followed by a large quantity of HoO containing H 2S04 and EtOH, and the whole is washed by centrifuging and filtered. The process is repeated and the residue washed with EtO H and dissolved in hot aq. NH4OAc. The vol. is reduced by evaporation and Pb pptd. as PbS in presence of gelatin and determined colorimetrically. 0-2 mg. of Pb may be determined with an accuracy of approx. 6%. The error may be reduced to 1% by using a photo-electric cell and suitable coloured screens. The accuracy is unaffected when 0-1—0-5 mg. of Pb is determined in presence of 5 mg. of Sn, 0-5 g. of sugar, or 1 g. of meat. Bi and Hg have no effect, bu t Ag gives too high a val. when present in excess of 0-1 mg.

M. S. B.Duclaux m ethod [for determ ination of volatile

acids]. J . B. M cN a ir (J. Amer. Chem. Soc., 1933, 55, 1470—1474).—Mixtures of four volatile aliphatic acids are analysed by determining one (or more) by chemical methods and the remainder by Gillespie and W alters’ graphic method (A., 1917, ii, 549; cf. Duclaux, A., 1875, 188). H. B.

Refractom etric determ ination of organic acids.(M m e .) G. A l l a r d (Compt. rend., 1933, 196, 937— 938).—This method (A., 1932, 632) has been extended to the higher aliphatic dibasic acids. The errors in determining azelaic acid, its N a salt, and Na sebacate in dil. solution are —5, +2-5, and +2-5% , respectively. The to tal acidity of mixtures of these with H 2C20 4 and CH2(C02H)2 is determined with similar accuracy, but the individual vals. show greater errors.

A. C.Volum etric analysis of anthranilic acid and its

sa lts. H. F u n k and M. D it t (Chem.-Ztg., 1933, 57, 334; cf. this vol., 244).—Anthranilic acid and its salts are tetrabrom inated by direct titration with bromide-bromate solution in about 42\T-HC1 to the yellow change with an indigocarmine-styphnic acid indicator, the slight excess of B r being determined by addition of a few c.c. of 0-2JV-KI and titration of the I with Na2S20 3. E. A. F .

N ew reagent for identification of alkaloids.M . S. M o k r a g n a t z (Bull. Soc. Chim. Yougoslav, 1932, 3, 171—177).—A solution of 0-05 g. of K R e04 in5 c.c. of H 20 , diluted to 100 c.c. with cone. H 2S04, gives characteristic colour reactions with morphine, codeine, brucine, cryptopine, hydrastine, hydrastin- inc, narcotine, quebrachamine, stypticine, yohimbine, boldine, chelidonine, apomorphine, and bulboeapnine. Many other alkaloids either give identical colour reactions with H 2S04 alone, or give no reaction.

B,. T.Determ ination of m orphine. B . K l j a t s c h k i n a

and E. S t u b e r (Arch. Pharm ., 1933, 271, 217—219). —A method of determining morphine (I) (in small or large quantities) is based on the extraction of its


hydrochloride from approx. 2% aq. HC1 by P hO H - CHCI3 (1 :4). The base can be recovered by extraction of the CHCU solution with H 20 , concn., and

pptn. by NH3. Aq. NH 3 (ps 9-1) dissolves 1-3 mg. of (I) per c.c., this figure being confirmed by the above method of determination. R. S. C.

B iochem istry.Apparatus for determ ination of oxygen uptake

of sm a ll an im als. F. R a p p a p o r t and F. G o t t - d e n k e r (Biochem. Z., 1933, 258, 460—466).—An apparatus is described which differs from the usual self-registering one in th a t the 0 2 uptake is determined not by the vol. decrease of an 0 2 reservoir serving as spirometer, bu t by the vol. decrease of the whole system, which is sealed and provides for the absorption of C02. In th is way the experiment is finished in 6 — 8 min. and m any of the usual errors (change of H 20 vapour tension etc.) are avoided or may be disregarded. P. W. C.

M icro-respiration apparatus. E. T. N i e l s e n (Biocliem. Z., 1933, 260, 226—229).—The apparatus, which is fixed in a paraffin-oil bath, consists of a 1 c.c. pipette (graduations 0 -0 0 2 c.c.) to which are sealed, in T-form, two glass-stoppered vessels (capacity< 2 c.c. each) containing respectively anhyd. N a,S 0 4 and soda-lime. A second apparatus is used for control. Measurements are made a t const, vol. and at const. H 20 v.p., absorption of 0 2 being recorded. W. SlcC.

O xygen consum ption of fasting w hite m ice. J . E . D a v is and PI. B. V a n D y k e (J. Biol. Chem., 1933,100, 455—462).

P igm en t of Ila lla partheriopea, an accessory respiration catalyst. E. A. H. F r i e d h e i m (Biochem. Z., 1933, 259, 257—268).—Electrometric ti tra tion shows th a t the pigment of H. partheriopea (hallochrome) forms a reversible two-stage oxido-reduction system. The pigment in M /90,000 solution increases by several hundred % the respiration of unfertilised sea urchin’s eggs, of fertilised eggs of Ascaris suis, and of rabbit’s red blood-corpuscles. The properties of hallochrome as to range of potential and consts. of the two-stage oxidation agree fairly closely with those of pyocyanin. P . W. C.

Elem entary com position of various hsemocyanins. F. H e r n l e r and E. P h i l i p p i (Z. physiol. Chem., 1933, 216, 110—119).—Hsemocyanins from Helix pomatia, Busycon canaliculatum, Octopus vulgaris, Loligo pealei. Limulus polyphemus, and Homarus americanus isolated by various methods were analysed after drying a t 105°. They showed close agreement in elementary composition. The mollusc product contained 0-25% and the arthropod product 0-18% of Cu. ' J . H . B.

Do haemocyanins contain other m etals besides copper? A. G a t t e r e r and E. P h i l i p p i (Z. physiol. Chem., 1933, 216, 120— 1 2 2 ).—All lisemo- cyanins examined contain no metal in the mol. other than Cu. Traces of other metals found are due to im purity. J . H. B.

Iron-containing com ponent of blood-pigm ent. Its com bination w ith globin to g ive haemoglobin.

A. H e r z o g (Biochem. Z., 1933, 260, 213—214).—A cryst. compound (hsematin), CaiHggO5N4Fe, obtained from coagulated blood yields' a cryst. “ reduced lucmatin,” C34H 330 4N4Fe. These substances and also clilorohicmin (I), oxyhajmoglobin, and CO-hoemo- globin (II) yield a cryst. compound (III),CWH30(°i' H 31)04N4Fe, which can be reconverted into the precursors. (I ll), which is probably the prosthetic group of haemoglobin, combines with globin to give a product convertible into methoemoglobin and(II). I t follows th a t the 34th C of (I) is introduced during its prep, and th a t cetioporphyrin has 31 C.

W. McC.E quilibrium betw een carbon m onoxide-hsem o-

globin and potassium ferricyanide. H. S c h u l e r (Biochem. Z., 1933, 259, 475).—Acknowledgment of Conant’s earlier work (A., 1926, 1050; 1928, 315).

P. W. C.D etection of a com plex com pound of carbon

dioxide and haemoglobin in blood. 0 . M. H e n r i - q u e s (Biochem. Z., 1933, 260, 58—71; cf. A., 1928, 13S9, and Margaria, J . Physiol., 1931, 73, 311).— Theoretical considerations and further experimental evidenco confirm previous results pointing to the existence in blood of a complex C0 2-ha3moglobin compound (I). The extent of combination is 2%, 40%, and 0% a t p a 6-5, 7-2, and 8-0, respectively. As regards the Donnan equilibrium in blood, the predominating factor is the concn. of basic compounds of metals. In (I) the C02 is probably attached to an OH or NHo group giving a complex acid stronger than H 2C03: W. McC.

A bsorption of ligh t by carbon m onoxide- hsem oglobin. V. S e b e s t a (Biochem. Z., 1933, 260, 187— 191; cf. A., 1926, 314).—The absorption of light by CO-hsemoglobin (horse, ox) as shown on a curve (I) where sp. extinction coeffs. are plotted against X exhibits max. a t 566 and 537-5 mix and a min. a t 551 m|t. As compared w ith the corresponding curve for oxyhcemoglobin (I) shows less absorption a t the max. (but not a t the min.) and lies nearer to the violet for the most p art of its course, the shift for the 566 mu, max. being > for the other.

W. McC.R elative value of clin ical b lood-tests. T. F-

B l o e m (Biochem. J ., 1933, 27, 121— 131).—The min. concns. of oxyhemoglobin and its derivatives detectable by a given spectroscopic technique (I) were investigated and the results applied to the quant, determination of these substances in urine, fseces, and dil. blood. (I) is more sensitive than tests d e p e n d e n t 011 the benzidine reaction (A., 1932, 1151) and is comparable with the acid luematin method.

F. 0 . H.Generic and specific identification of blood by

the G anassini reaction. D. G a n a s s i n i (Arch. 1st.

BIOCHEMISTRY. 623

Biochim. Ita l., 1933, 5 ,11—20).—A reply to criticism. The reaction depends on the catalytic action of haemoglobin and Fe. Differences in the reaction of foetal blood observed by Nicoletti are within the experimental error. R. K. 0.

Spectrum analysis of the m itogenetic radiation from the blood of liv ing anim als. K. P.G o l is c h e v a (Biochem. Z., 1933, 260, 52—57).—The complete (1900—2500 Â.) spectrum of the m itogenetic radiation from the blood circulating in the vena saphena of the rabbit has been examined and the various bands observed have been referred to processes (glycolysis, hydrolysis of peptides arid of creatine phosphate, phosphatase action, oxidation) which give rise to them. W. McC.

Perinuclear granules and reticulum . III. Chemical nature o f the granules. G . V a g i (Trans. Japan. Path. Soc., 1931, 21, 24S—251).—The substance in the granules and reticulum o f white and red blood-cells is a basic nucleoprotein. Ch . A b s .

Perm eability of erythrocytes to chloride. M.M a iz e l s (Biochem. J ., 1933, 27, 33—35).—When erythrocytes (I) are placed in solutions containing permeating anions (II) (e.g., Cl') and other anions or non-electrolytes (III) which permeate less easily (e.g., P 0 4"' or glucoso), the amount of (II) diffusing across the positively-charged membrane of (I) depends on the external p n and on the to tal osmotic pressure of(III), provided th a t a certain abs. quantity and min. concn. of (II) is exceeded. The concn. of (II) in the cell may greatly exceed the equilibrium concn. in the external phase. F. 0 . H.

Iron. VI. D eterm ination and properties of the “ easily elim inated ” iron in blood. VII. Behaviour of inorganic iron on addition to blood.G. B a r k a n (Z. physiol. Chern., 1933, 216, 1—16, 17—25; cf. A., 193Ô, 1304).—VI. The determination of the readily eliminated Fe is modified by the use of E t20 containing peroxide. Previous results are confirmed.

VII. Inorg. Fe11 salt added to blood differs from fraction E of the readily eliminated Fe in not shoving inhibition by CO and in occurring only in blood fluid. I t has, in common with E, a relatively high rate of dissolution in dil. acid. J . H . B.

Pancreatic am m oniophaneresis. M. P o l o n o v - s k i , P . B o u l a n g e r , and G. B iz a r d (Compt. rend., 1933, 196, 1147— 1149).—The NH3 content of pancreatic venous blood (I) is > th a t of arterial blood in dogs. Intravenous injection of (NH4)2C03 causes a further increase in (I) to vais. > those for the renal and femoral veins. A. C.

B lood-sugar content as an index of condition of cattle. H . y o n T e ic h m a n (Arch. Tierernahr. Tierzucht, 1932, 7, 532—570).—The blood-sugar content of cattle is influenced by age, body-wt., period of lactation, milk yield, and pregnancy. Vais, obtained showed considerable variation in the individual during a 12-hr. period. To produce definite increases in sugar level, glucose m ust be given in solution at the rate of 1 pt. per 250 pts. body-wt. No correlation between blood-sugar curves and the condition of the animals was observed. A. G. P.

A nalysis of serum w ith the ultra-centrifuge.P. v o n M u t z e n b e c h e r and T. S v e d b e r g (Naturwiss., 1933, 21, 331).—Ultra-centrifuge measurements made on dil. horse serum show the presence of mols. of four species with sedimentation consts. respectively 4-4 x 10~13, 6-6 X lO-13, 9 x 10“13, and 18 X10~13, the first representing the albumin, the last three the globulin. Paraglobulin prepared by electrodialysis contains all three species, whilst eu- and para-globulin prepared by salt pptn. both contain the type with sedimentation const. ISX 10"13, but neither of them th a t with const. 9X10-13. W. O. K.

Union of colloids. I. Supposed albu m in - globulin com pound in serum . State of com bination of calcium in serum . W. M. B e n d i e n and I. S n a p p e r (Biochem. Z., 1933, 260, 105— 114; cf. A., 1929, 110).—The protoins of blood-serum (1) can be subjected to fractional ultra-filtration (II) by means of membranes (III) prepared by a modification of MacBain’s method. Since the ratio of albumin(IV) to globulin (V) in the ultra-filtrates (VI) differs, in some cases greatly, from th a t in (I), it is probable th a t (IV) and (V) arc not united in complex combination in (I). (II) probably takes place also through the membranes of the body in diseases (e.g., albuminuria) where body-fluids (e.g., urine) have a high (IV) to (V) ratio. Analyses of (VI) and of the residue which does not pass through the (III) indicates th a t all the combined Ca of (I) is united to the (IV).

W. McC.State of com bination of calcium in the blood-

plasm a of the hen. M. L a s k o v sk i (Biochem. Z., 1933, 260, 230—240).—During the laying period the Ca and inorg. P contents of the blood-plasma of hens increase (average Ca and P per c .c .: laying, 0-208 and 0-045 m g.; not laying, 0-135 and 0-029 mg.). In non-laying hens (I) almost all the inorg. P in the plasma is ultra-filterable, in laying hens (II) only half, bu t the concn. (I ll) of ultra-filterable Ca in the plasma is the same in (I) and (II). All the additional Ca in the plasma of (II) most probably forms p art of a colloidal Ca-P-complex and cannot be ultra-filtered. When CaCl2 is added to plasma of (I) or (II), (III) increases to the same extent as does th a t (IV) of the total Ca, and intravenous injection of CaCl2 into (II) results in increase in (III) in the blood. In the normal hon (III) is independent of the sexual state and of the changes in (IV) related to it. Only in the healthy living hen does regulation of (III) occur. W. McC.

Variations in the concentrations of m agn esium , calcium , and inorganic phosphorus in rabb it’s serum . R. W. B r o o k f ie l d (Biochem. J ., 1933, 27, 173—182).—W ith rabbits on a mixed diet, and especially during the period of intestinal absorption, the serum-Ca level (I) fluctuates in a manner directly opposed to th a t of the Mg level (II), the actual vals, of both (I) and (II) being influenced by the composition of the diet. The existence of an inverse relationship between (I) and the inorg. P 0 4 level (III) is confirmed. Hence (II) follows a course parallel with th a t of (III). Mg does not diffuse from erythrocytes into the serum unless the time of keeping is > 4 hr. The balance of bivalent cations in the blood is discussed. F . O. H.

6 2 4 BRITISH CHEMICAL ABSTRACTS.----A.

Serum -album in and heparin. P. v o n M u t z e n - b e c ii e r (Naturwiss.. 1933, 21, 331).—The mol. wt. of serum-albumin is not altered by treatm ent with highly active heparin, which it has been suggested changes it into globulin (cf. Fischer, A., 1932, 73). Serum treated with heparin shows no increase in its albumin fraction. W. 0 . K.

Antiprothrom bin and globulins. I. P. E a r l e and P. E . H o w e (Science, 1933, 77, 213—214).— Fischer’s observation th a t heparin produces in serum a combination pptd. a t approx. p a 5-0, bu t not the conclusion th a t this combination is eu- or pseudo-globulin, is confirmed (cf. A., 1932, 636, 870; this vol., 296). L. S. T.

Fractional specificity of serum -album in . T.A s a b a (Arb. Med. Univ. Okayama, 1932, 3, 314— 346).—The different fractions of bovine serum manifest a definite fractional specificity. The behaviour of the various fractions is described. Globulin E obtained by electrodialysis contains chiefly eu- and pseudo-globulin and little albumin. In immunisation w ith bovine serum the globulin antibody appears prior to the albumin antibody. C h . A b s .

Com bining and inhibition zones in im m uno- reactions and colloidal reactions. K . O h t a h a r a (Arb. Med. Univ. Okayama, 1932, 3, 255—278).—The immuno-reactions, particularly the pptn. reaction, behave with regard to optimal flocculation and inhibition of flocculation similarly to oppositely charged dyes. Ch . A b s .

R ole of lip ins in F orssm an antigens. M.A r m a n g u e , P. G o n z a l e z , and S. R o m e r o (Amer. J . Hyg., 1933,17, 277—286).—In sheep cells, horse and guinea-pig kidneys the common antigenic factor appears to be the EtOH-sol. lipin. The proteins in th e Forssman antigen appear to act as carriers. The lipins have better antigenic qualities when united with adsorbents. Proteins present in Forssman an tigens produce strictly sp. antibodies. Sp. antisera acting on the proteins of the kidney of the guinea-pig prove toxic for this an im al; the same holds for sera produced against the heterophile lipins. Ch. A b s .

Effects of various non-specific adsorbents on the h em a g g lu tin in s of the rabbit im m unised w ith goat red-blood ce lls. M. H o m m a (Japan. Z. Mikrobiol. Path ., 1932, 26, 1033—1062).—The h e m agglutinins are adsorbed by kaolin or Al(OH)3.

C h . A b s .Com ponents of hasmolytic com plem ents. B.

M i t s u s e (Japan. Z. Mikrobiol. Path ., 1932, 2 6 ,1702— 1751).—A component stable on boiling a t 100° for 2 hr. was obtained by extraction with petroleum benzine. v Ch . A b s .

The crystals of the liv in g body. (S i r ) W . B r a g g (Proc. Roy. Inst., 1933, 27, 606—624).—A lecture.

C om position of som e fatty m ateria ls found in ancient E gyptian tom bs. A. B a n k s and T. P. H il d it c h (Analyst, 1933, 58, 265—269).—Analyses of four fats (1350—3000 B.C.) are given, and the general conclusions of Chapman and Plenderleith (B., 1926, 986) are confirmed. Glycerides and small amounts of oleic acid (together with its normal oxid-

ation scission products, azelaic and nonoic acids) were present. The saturated acids were mainly intact, and large quantities of palmitic and stearic acids were obtained in proportions which, in a t least two cases, indicate th a t the origin of the specimens was the body-fat of an animal (probably an ox). The unsaponifiable m atter, however, provided no confirmation of this. J . G.

Chem ical com position of cerum en. S. N a k a - shima (Z. physiol. Chem., 1933, 216, 105—109).— Cerumen contains fa tty acids 0-85%; fats 12-4%; cholesterol 2-5%; cerotic acid (?) 1-9% ; neurostearic acid (?) 0-35%; a b itte r substance, m.p. 123°, trace; a substance CgH 140 5iSr, m.p. 204°, 0-8%; protein (of high lysine and low cystine content) 43-2%; ash (mainly Na2S 04) 3-45%. J . H . B.

M icro-determ ination of cholesterol and phosphatides in tissu e and blood. W. M i l b r a d t (Z. physiol. Chem., 1933,216,181— 188).—The cholesterol is determined colorimetrically by the Tschugaev- Bernoulli reaction (A., 1932, 510) in the hydrolysed extract of 0-1 c.c. of htemolysed blood, phosphatides by the method of Fiske and Subbarow (A., 1926,443). Tissue (0-1—0-2 g.) is extracted w ith E t,0 -E t0 H .

J . H. B.E xam ination of cholesterol by u ltra-violet

rays. H. Ma r c e l e t (Bull. Soc. Chim. biol. 1933,15, 379—384).—The liver oil of Orthagoriscus viola is very rich in cholesterol ( I ) ; the purified (I) gives a homogeneous mauve fluorescence (II) with filtered u ltraviolet rays. Specimens from placenta}, ovaries, and calculi gave similar (II), whilst older samples from different sources stored in the dark gave impure ( I I ) ; recrystallisation of one gave an improved (II). The m.p. of (I) varies with time. H. D.

Glutathione content and reductive power to w ards cystine of desiccated organs. L. W urmsee (J. Pharm. Chim., 1933, [viii], 17,327—331).—Various desiccated animal organs contain small amounts of compounds possessing the SH group (always < the fresh organ), have autoreductive power, and reduce cystine. R. S. C.

Preparation of lactacidogen and adenylic acid from m uscle-ju ice. A. H a h n and M . D ü r r (Z. Biol., 1933, 93, 490).—The statem ent by Steudel (A.,1932, 1273) th a t ox-flesh (I) is not a suitable source of adenylic acid is refuted. From 1 kg. of (I) 0-7 g. of crude Ba salt was obtained, whilst 10 kg. yielded1-6 g. of the pure acid (cf. A., 1931, 860). The efficiency of the method is shown by its application „ to the prep, of the pure acid from blood (A., 1931, 1080). F. 0 . H.

Colloidal behaviour of m uscle-proteins. IV. M ol. w t. of m uscle-protein and the active volum e (Vein der W aals) of m yogen particles. H. H.W e b e r and R. S t o v e r (Biochem. Z., 1933,259, 269— 284).—The mean mol. wt. of dialysed myogen is 81,000, the hydrate vol. of 1 g. is 1-98 c.c. W ith myosin in Edsal’s solution, the mol. wt. is 0-6— 1-2 X 10®. The hydrate vol. of myogen agrees with the viscosity vol. when calc, by E instein’s formula. Cone, solutions of urea decrease the mol. wt. of myogen to 34,000 and of myosin to 100,000, whilst conc. NH 4CNS

BIOCHEMISTRY. 625

increases th a t of myogen to > 300,000. Muscle press- juice contains about 7% of muscle-protein which is almost exclusively myogen. The myogen of the purified solution appears to bo identical with th a t of the muscle press-juice. P. W. C.

Calcium content of m uscle. C. M . B u r n s (Biochem. J ., 1933, 27, 22—32).—The normal muscle- Ca (I) of rats, cats, and rabbits varies considerably (cf. A., 1926, 431). W ith diets containing normal amounts of Ca, (I) does not increase with increased content of vitamin-D or of Ca. A state of hyper- excitability or active tetany induced by injection of guanidine, by feeding of phosphates or irradiated ergosterol to rachitic animals (A., 1931, 254), or by parathyroidectom y (A., 1929, 1332; 1931, 1327) is not accompanied by any appreciable change in (I).

F. O. H.Com position of bones of vegetarian and

om nivorous rats. S. W a n (Chinese J . Physiol., 1933, 7, 23—34).—No significant differences were found in the contents of ash, org. m atter, Ca, P, and C02. F. O. H.

Phosphorus content of Crustacea of the B elgian coast. M. L. C o m p e r n o l l e (Natuunvetensch. Tijds., 1933, 15, 83—84).—The P 0 4" ' content of eight varieties, calc, as P, ranged from 0-005% to 0-016%; it varied considerably from one specimen to another and with the season and locality. H. F. G.

Determ ination of inorganic iodine in desiccated thyroid gland. W. L a w s o n (Biochem. J., 1933, 27, 112— 115).—Aq. extraction of the gland extracts I compounds other than inorg. to an extent dependent on the protein denaturation which has occurred in the gland during treatm ent for analysis. Exhaustive extraction with E tO H or MeOH removes only dialysable I, together with a trace of I combined with fat. For rapid determinations, 0-2—0-3 g. of the powdered gland is shaken with 20 c.c. MeOH a t room temp, for 2-5 hr., the extract filtered and evaporated, and I determined in the residue.

F. 0 . H.D etection of chitin in the w in g residues of

Coleoptera of the upper m iddle eocene (found at G eiseltal). E. A b d e r h a l d e n and K. H ey n s (Biochem. Z., 1933, 259, 320—321).—The wing residues of Coleoptera (age 25 X 10° years) contain chitosamine isolated as the phenylhydantoin, m.p. 210°, [aJS +72-4° (synthetic, m.p. 210°, [ajg +76°).

P. W. C.Acetylcholine in the hum an platenta. P.

H a u p s t e i n (Arch. Gyn., 1932,151, 262—280; Chem. Zentr., 1933, i, 246).—Placentas a t various periods of pregnancy contain 59—280 mg. of acetylcholine per kg. Relatively large amounts were found in immature placentas. A. A. E.

Determ ination of glycogen. C. A. G o o d , H. K r a m e r , and M. S o m o g y i (J. Biol. Chem., 1933,100, 485—491).—A modification of the Pfiiiger method permits the determ ination to be made in a few hr. For the initial hydrolysis, treatm ent w ith 30% aq. KOH is sufficient. The glycogen is then pptd. a t the b.p. with 1 vol. of 95% EtOH, and after centrifuging is hydrolysed for 2 hr. with 0-6iV-HCl or tf-H 2S04. A. L.

Celluloid im pressions of the surface structure of anim al fibres. J . M a n b y (J. Roy. Micros. Soc., 1933, 53, 9—12).—Modifications of H ardy’s method of studying the surface structure of animal fibres are described. H. G . R.

Practice of fixation for an im al tissu es . P.G r a y (J. Roy. Micros. Soc., 1933, 53, 13—19).—A guide to the choice of the most suitable fixative. The use of ten aq. and two alcoholic “ basal fixative solutions ” is recommended, as m any fixatives are unstable. “ H. G . R.

H istological applications of triphenylm ethane and diphenylnaphthylm ethane dyes. I—III. S.H a sh tm o to (Japan. Z. Mikrobiol. Path ., 1932, 26, 1075—1100, 1101—1114, 1115—1128).—The electric charge, diffusibility, colouring, lipin-solubility, carbinol reaction, and toxicity were studied. In general, basic dyes have lipin-solubility, whilst acid dyes have not. The basic dyes are the more toxic. The vital staining of protoplasmic granules is closely related to the electric charge and diffusibility. Ch . A b s .

Application of triphenylm ethane and diphenylnaphthylm ethane dyes in m orphological studies.IV—VI. S. H a s h im o t o (Japan. Z. Mikrobiol. Path ., 1932, 26, 1527— 1533, 1631— 1641, 1642— 1650).—Chromazurol S (G) is adsorbed electrically and is chemically combined w ith NH 2-acids or proteins in the staining of tissues. Ch. A b s .

V ital sta in ing w ith diam ine dyes. K. F u j it a

(Trans. Japan. Path . Soc., 1931, 21, 206—208).— Most of the effective dyes are acid dyes. Ch . A b s .

Relation betw een the intensity of the sta in ing reaction of cell granules and the com position of the fixing solution. Y. K o n and K . T a k e d a (Trans. Japan. Path. Soc., 1931, 21, 233—235).

C h . A b s .R elationship betw een the chem ical reaction of

fixative solution and the basophilic granules in stained tissu e. K . K a t o h (Trans. Japan. Path. Soc., 1931, 21, 236—237).—Diffuse staining was usually accentuated by fixation in alkaline solution.

Ch . A b s .R eticiilo-endothelial system . II. Secretion

of specific substances. G . O b o (Trans. Japan. Path . Soc., 1931, 21, 324—328).—A non-protein substance, not a true lipin, which stimulates the reticuloendothelial system and accelerates the detoxication of morphine, is present shortly after the injection of India ink into rabbits. Ch. A b s .

Chem istry of the liquor am nii. J . F. D.S h r e w s b u r y (Lancet, 1933, 224, 415—416).—D ata are recorded. Cholesterol is absent and the Ca level is slightly lower th an for normal serum-Ca.

L. S. T.Fractionation of A ustralian snake venom s.

II. V enom s of the tiger snake (N otechis scu t- a tis), black tiger snake (N otechis scu t at is uirjer), and black snake (Pseudechis p o rp h yria cu s).H . F. H o l d e n (Austral. J . Exp. Biol., 1933,11 ,1—7). —Ultra-filtration through pyroxylin or gelatin membranes was not satisfactory for the separation of the constituents of snake venoms. Of various adsorbents.


freshly prepared BaC03 was most efficient. I t adsorbs thrombin, bu t not “ neurotoxin.” W. 0 . K.

Secretion and oxygen consum ption in isolated salivary glands of A plysia . T. N i (Chinese J . Physiol., 1933, 7, 71—78).—Electrical stimulation of the salivary glands of A . punctata and A. limaeina increases the flow of saliva (I) and the 0 2 consumption (II) (from 1-2 to 2-5 c.mm. per min.) of the glands. NaCN inhibits (II), b u t does not always inhibit (I) or depress the secretory excitability (III). Following treatm ent with NaCN, methylene-blue restores (II) w ithout affecting (III). From the concn. equivs. of the saliva (1-61J/) and hsemolymph (1-OSiJf) it follows th a t the osmotic work performed during the secretion of 1 litre of saliva is 24-3 kg.-m.

F. 0 . H.Influence of b ile sa lts on sa lt excretion in

liver-bile. II. E lim ination of phosphoric acid through bile acids after adm inistration of glucose. Y. K a w a d a (Arb. Med. Univ. Okayama,1932, 3, 163—171).—The ash and to tal solid contentof fistula bile from dogs is decreased after administration of glucose; after th a t of bile salts i t is unaltered or only slightly lowered. The elimination of P 0 4 is decreased after oral adm inistration of glucose, b u t unaltered or only slightly lowered when bile salts are given simultaneously. Ch. Abs .

B ilirubin. VIII. D eterm ination of bilirubin in body-fluids. Q uantitative extraction process. W. K erppola and E. L eikola (Acta Med. Seand., 1932, 78, 24— 41; Chem. Zentr., 1933, i, 94).— The bilirubin is extracted with CHC13 before and after acidification and determined colorimetrically. The diazo-method is subject to interference by substances present in body-fluids. The colour of 0-0075 mg. of bilirubin in 1 c.c. corresponds with th a t of 0-05% aq. K 2Cr20 7. Methods for the determination of bilirubin in urine, bile, and serum are described. A. A. E.

Sugars of hum an m ilk . M. P olonovski and A. L espagnol (Bull. Soc. Chim. biol., 1933,15, 320— 349).—40 litres of 95% EtO H are added to 7 litres of human m ilk ; after concn. and removal of fats the solution is filtered. A t 0° crystals separate. By recrystallisation of the la tter from MeOH, a//olactose,[a]D +25°, is obtained pure. The reducing group of th is disaccharide is aldeliydic. I t gives an osazone ( I ) ; on hydrolysis it gives glucose (II) and galactose and it is hydrolysed by emidsin. On oxidation withI and subsequent hydrolysis (II) is obtained. Hydrolysis of (I) and treatm ent of the product with phenyl- hydrazine gives galactosazone. Hcnce it is assumed th a t a?/olactose is a {i-cZ-galactosido-cZ-glucose. The possibility of its identity with the synthetic 6-p- galactosidoglucose is discussed. The mother-liquors from the original crystals are separated into two fractions by pptn. with MeOH. The ppts. obtained by repeating the process show decreasing reducing powers, whilst the fractions more sol. in MeOH have const s. closer to those of gynolactose. H. D.

Endocrine glands and excretion of m ilk . Q.Calabro and F . F antozzi (Arch. 1st. Biochim. Ital.,1933, 5, 79—96).—A study of the effect of injection of thyroid, parathyroid, and ovarian extracts on the

quantity , d, f .p., dry residue, and fa t content of goat’s milk. R. K. C.

Influence of copper on the peroxidase reaction of m ilk . K. J esc h k i (Milch. Forsch., 1933, 15, 110—114).—The presence of Cu in milk produces a positive peroxidase reaction although the milk has been heated. If the peroxidase reaction be positive after the test sample has been boiled the presence of Cu or other metal m ay be deduced. E. B. H.

Effect of light on the oxidation-reduction potential of m ilk . E. Ma r tin i (Biochem. Z., 1933,260, 153— 160).—A rapid fall of potential is produced by the action of light on milk in which the enzymes have been destroyed by heat. H. W. D.

Specific influence of sugar-beet leaves and tops on the quality of m ilk . G. Z w a g e r m a n n (Intern. Mejerikongr., 1931, 274—284; Bied. Zentr., 1932, 3, A, 99).—The feeding of sugar-beet tops and leaves does not increase the fa t content of milk and it produces therein an unpleasant taste and odour. The la tter is ascribed to the presence of NMe3 derived from the betaine of the leaves. The odour can be removed from bu tter by washing w ith H 20 acidified with lactic, citric, or tartaric acids. B utter is less affected if the cream is pasteurised. Use of fresh sugar-beet tops produces a hard, crumbly butter. Appropriate stall feeding minimises the odour.

A. G. P.Influence of feeding and the condition of m ilk

ing an im als on the vitam in content of their m ilk .M. Schieblich (Tierarztl. Rundschau, 1931, 37 , 860; Bied. Zentr., 1932, 3 , A, 88).—The vitamin-^4 content of milk is affected by the amount supplied in the ration. Vitamin-7? is synthesised internally by bacteria and is independent of external supplies. This is not the case with non-ruminants. Although the vitamin-C content of milk is closely related to th a t of the ration, some internal synthesis m ust be assumed. The low vitam in-0 content of winter milk is attributed to the customary shortage of green food, bu t m ay be remedied by the use of silage. Pasture grazing and ultra-violet radiation increase the vitamin-D content of milk. The la tte r is maintained during winter by the use of silage and hay or of irradiated foodstuffs, e.g., yeast. Cod-liver oil has little effect on plant- eating animals owing to its poor digestibility.

D estruction of citric acid in m ilk by bacteria.J . Mussill (Milch. Forsch., 1933, 15, 42—49).—A micro-centrifugal method is suitable for the determ ination of citric acid in milk. The citric acid conten t is unaltered by sterilisation or by keeping after sterilisation and decreases only under the influence of bacteria. Proteolysis and citric acid breakdown have no relationship; thus B. coli rapidly destroys citric acid, scarcely affecting proteins. A cid formation does not necessarily follow citric acid destruction.

E. B . H .Calculations relating to transport of m aterial

in the organism . R. F ü r t h (Kolloid-Z., 1933, 63,215—220).—The energy required for electro-osmotic transport of liquid in the organism is calc, to be only 0-00001 of th a t actually furnished by the observed bio-electric currents. The osmotic work done in the

BIOCHEMISTRY. 627

kidney during secretion of urine is about 0-1 of th a t corresponding with the local e.m.f. In general, bioelectric sources of energy are more than adequate to account both for transport of material and for the maintenance of differences of concn. across membranes. F. L. U.

Intracellular hydrogen-ion concentration studies. V II. Secreting cells of the m esonephros in the chick. R. C h a m b e r s and G. Ca m e r o n (J. Cell. Comp. Physiol., 1932, 3, 99—103). —Columnar cells of the walls of the proximal convoluted tubule in the chick have the property of favouring unidirectional passage of sulphonephthalein indicators through the cytoplasm. Intracellular p n for healthy cells is 6-8+0-2 and in certain unhealthy tubules 5-2 (approx.). A. G. P.

M icro-analysis of urine and blood by the step photom eter. IX. Determ ination of am m onia in urine. C. U r b a c h (Biochem. Z., 1933, 259, 351— 357). P. W. C.

Is blood-protein am ide-nitrogen a source of urinary am m onia? III. Question of the synthesis of protein am ides from am m onia. E. F. W il l ia m s , jun., and T. P. N a s h , jun. (J. Biol. Chem., 1933, 100, 515—524).—After injection of aq. (NH4)2C03 into the femoral artery of dogs there is no significant change in the protein amide vals. of the plasma and whole blood. A. L.

Secretion of urea in the frog. E. K. M a r s h a l l , jun. (J. Cell. Comp. Physiol., 1932, 2, 349—353).— The am ount of urea excreted by the frog’s kidney is much in excess of th a t accounted for by the glomerular filtrate as measured by xylose. Urea is largely excreted by tubular secretion. A. G. P.

Unknown nitrogenous substances in urine.V. Occurrence of y-butyrobetaine in dog's urine. H. R e i n w e i n (Z. physiol. Chem., 1933, 216, 26—30).—y-Butyrobetaine was isolated from normal dog’s urine and is therefore not necessarily a symptom of metabolic disturbance. J . H. B.

Relationship of urinary com position to acid - base equilibrium . VI. M echanism of the origin of acid and alkaline urine. S. M. Neu- sc h l o sz (Biochem. Z., 1933,259,322—330).—Mathematical treatm ent of the usual Cushny theory of filtration a t the glomerulus and back absorption in the kidney tubules leads to a formula permitting the calculation of the NaHC03 concn. of the reabsorbed fluid ( ~ B 0) and experiments with 24 healthy men gave a practically const, val. for B0 (mean deviation4-8%). The excreted urine is more acid or alkaline than the blood as the NaHCO, concn. in the blood- plasma is lower or higher than B0. P. W. C.

Composition of the urine of w hite m ice. I. A.P a r e e n t j e v and W. A. P e r l z w e ig (J. Biol. Chem., 1933, 100, 551—555).—The average composition of normal mouse urine as determined using pooled samples from 20—100 animals is as follows : total N4-15, urea 5-70, protein 1-52, allantoin 0-92, NH3 0-36, creatinine 0-10, creatine 0-09, liippuric acid 0-28, NH2- acid (as glycine) 0-09, uric acid 0-04, purine bases (as guanine) 0-01, indican 0-005, to tal S 0-27, total S04-S

T T

0-20, inorg. S 04-S 0-15, inorg. P 0-43, Cl 0-62%; d 1-059, pn 5-3; to tal base 3810, to tal acidity 1820 mol. equiv. per litre. The protein probably belongs to the chondromucoid group. A. L.

Com position of the urine of cow s. A. T. D a n n (Austral. J . Exp. Biol., 1933, 11, 53—58).—Analyses are given. Acid diet (hrewer’s grains) reduces the p a and increases the to tal N, NH3-N, and creatinine contents. W. O. K.

Copper content of urine of norm al individuals.I. M. R a b in o w it c h (J. Biol. Chem., 1933,100, 479— 483).—Cu was found in human urine ranging in amounts from traces to 0-4 mg. per litre. H. D.

B iological chlorophyll degradation. III. Iso lation of chlorophyll derivatives from elephant and hum an faeces. H . F i s c h e r a n d A. H e n d - s c h e l (Z. p h y s io l . C h em ., 1933, 216, 57—67; c f . A., 1932,659).—E le p h a n t faeces c o n ta in p r in c ip a lly p h y llo - c r y th r in , a n d , in s m a ll a m o u n ts , tw o g r ee n p ig m e n ts w ith h ig h e r HC1 v a l . , o n e o f w h ic h h a s a n Et e s te r , rn.p. 222°. H u m a n (v e g e ta r ia n ) faeces c o n ta in p r o to - p h o rb id e a \ s h e e p faeces c o n ta in r h o d o p o rp h y r in -y - c a r b o x y lic a c id . J . H . B.

N ature of the calcium and phosphorus com bination in the excreta of the non-laying pullet.F. K n o w l e s , J . E. W a t k i n , and F. W . F. H e n d r y (J. Agric. Sci., 1933,2 3 ,196—203).—Normal excretion of Ca is not in the form of Ca3(P 04)2, bu t conforms closely in composition with a m ixture of CaC03 and C aHP04. A. G. P.

[Optical] rotation of b lood-serum before and after hydrolysis and its clin ical significance. G.S a n t (Pharrn. Weekblad, 1933, 70, 425—433, 443— 449).—Scrum (2 c.c.) is diluted with 16 c.c. of physiological saline and a determined. Hydrolysis is effected by adding 2 c.c. of serum to 16 c.c. of 28% HC1 and observing a as rapidly as possible before reflocculation and decomp, commence. The difference in a x l0 0 divided by the original a is the hydrolysis no. (I) and is a measure of the serum-albumin. (I) for healthy persons is >100. In cases of sickness (eclampsia) it falls as low as 26. There is no relationship between(I) and the urea content or the CH.,0 titration.

S. C.E tiology of beri-beri. H. Y. O h (Korean Med.

J ., 1932,2,113).—Blood-Ca was diminished in Korean patients, who improved on adm inistration of Ca preps.

Ch . A b s .Rabbit carcinom a produced by nicotine. S.

K a t s u n u m a (Trans. Japan. Path . Soc., 1931, 21, 244—247). Ch. A b s .

Independence of grow th and type of m etab olism in m alignant cells. F. E ic h h o l t z , W. K e i l , and L. K ltjge (Biochem. Z., 1933, 260, 139— 142).—In white ra ts inhibition by X -ray irradiation of the growth of tumour cells is not accompanied by any change in their lactic acid content (I). Administration of prolan has no effect on (I) or on other properties of the sarcoma. From these and previous results it follows th a t the growth of such cells is independent of the type of metabolism which occurs in them. W. McC.


Glutathione content of the blood in cancer. R.W il l h e im and K . S t e r n (Biochem. Z., 1933, 260, 180—186; cf. A., 1930, 493).—Blood from cancerous persons contains less glutathione than does th a t of healthy persons. The difference is more pronounced when related to the no. of erythrocytes. W . McC.

Phosphatases of hum an uterine tum ours. M . M o r u and Y. T a k a b a t a k e (Arb. I l l Abt. anat. Inst. Univ. Kyoto, 1932, C, No. 3, 46—51).—Carcinoma : In lymphoglandular metastases a very active phosphatase was present. No phosphatase was present in normal lymph glands or in myoma. Ch . A b s .

Cathepsin and peptidases in carcinom atous and sarcom atous an im als. E. M a s c h m a n n andE. H e l m e r t (Z. physiol. Chem., 1933, 2 1 6 ,161— 172). —The cells of liver, spleen, and kidney of normal and carcinomatous or sarcomatous animals contain much more cathepsin than those of mouse carcinoma or mouse and fowl sarcoma. Muscle tissue and embryonic cells contain even less. In necrotic material from mouse carcinoma, catheptic proteinase is almost absent, and the dipeptidase content is reduced to 1/3. The peptidase content of organ and tissue extracts is about the same. Dipeptidase is absent from serum and fowl muscle. The liver-cathepsin of normal is< th a t of carcinomatous anim als; the enzyme seems to accumulate in the spleen of the diseased animals.

J . H. B.B utyric acid in the treatm ent of cancer. J.

W a t s o n (Lancet, 1933, 224, 746—748).—PrC 02H has a destructive action on cancerous bu t not on normal tissue. L. S. T.

Treatm ent of coccidiosis in rabbits by injection of o il-thym ol-carbon tetrachloride m ixtu res.M oussu (Compt. rend. Acad. Agric. France, 1933,19, 133—136).—Successful results of subcutaneous injection of preps, of olive oil, thymol, and CC14 are recorded. A. G. P.

Calcsemia in derm atoses. J . L. Ca r r e r a (Rev. sudamer. endocrinol., 1932, 15, 893—928).—In dermatoses only slight deviations from normal vals. were found. Ch . A b s .

H igh carbohydrate d iets in d iabetes. J . E a s o n and D. M. L y o n (Lancet, 1933, 224, 743—745).— Considerable reduction of fa t in the diet makes possible an increase in carbohydrate without an increase in insulin requirement, bu t a lower calorific intake generally results. F a t appears to make demands on the supply of natural or administered insulin. L. S. T.

E ffect of galactose feeding on depancreatised d ogs. J . H. R o e and R . F. Ca h o o n (Science, 1933, 77, 331—333).—Galactose is not converted into glucose by depancreatised dogs. About one half of the administered galactose is retained and apparently utilised. Galactose is used preferentially to glucose by the depancreatised dog. Galactose feeding prevents or suppresses some of the consequences of pancreatectomy. L. S. T.

Changes in the distribution of m uscle-phosphorus and -glycogen in fasting cats and in cats w ith experim ental diabetes m ellitu s w ith or w ithout adm inistration of insu lin . V . M . V e s s e l -

k i n a (Z. ges. exp. Med., 1932, 85, 463—476; Chem. Zentr., 1933, i, 449—450).—In hunger the total, lipin, and acid-sol. P are unchanged, bu t in the acid-sol. P the hexose-phosphoric (I) and creatine-phosphoric acid (II) are diminished. In diabetes the to tal P is unchanged, and the lipin-P is increased a t the expense of the acid-sol. P ; the (I) is diminished and (II) is increased. When insulin is given to depancreatised cats with normal blood-sugar (sugar being administered) all P fractions become norm al; in insulin hypo- glycaemia (I) rises; in all cases the glycogen remainslow. A. A. E.

Glucose equivalent of insulin . W. F a l t a and R. B o l l e r (Wien. med. Woch., 1932, 82, 1296— 1300; Chem. Zentr., 1933, i, 449).—In the diabetic individual the glucose equiv. is not const. A. A. E.

Influence of callikrein (padutin) on blood- sugar in diabetes m ellitus. A. W. E l m e r and M. S c h e p s (Klin. Woch., 1932,1 1 ,1993— 1994; Chem. Zentr., 1933, i, 450).—Large doses (35—70 units) given perorally have practically no effect. A. A. E.

Em otional glycosuria in Chinese students. W . H. A d o l p h , T. Y. W a n g , and P. C. W a n g (Chinese J . Physiol., 1933, 7, 1—4).—Glycosuria, accompanied by hyperglycemia, was detected in only one amongst 76 students sitting for examinations. F . O. H .

Interm ediary carbohydrate m etabolism during experim ental fever. K . A d a c h i and S. K a s a i (Tohoku J . Exp. Med., 1932, 20, 191—210).—Prolonged tying down of rabbits causes a fall in body temp., prolonged hypoglycemia, and a temporary increase in blood-lactic acid. During naphthylamine fever the blood-sugar shows irregular variation, and blood-lactic acid rises after the max. temp, has been attained. During fever induced by medullary puncture the blood-glucose and -lactic acid rise after the max. temp, has been attained. Ch . A b s .

Interm ediary m etab olism of m uscle in fever.I. Gas and carbohydrate. II. Phosphoric and uric acids. K. A d a c h i (Tohoku J . Exp. Med., 1932,20, 93—106, 107— 122).—I. Experimental fever in dogs causes a transient increase in 0 2 consumption by muscle. Blood-sugar falls temporarily, and sugar utilisation by muscle usually increases. In very high fever the blood-lactic acid a t first rises and then rapidly becomes normal. Blood-C02 is considerably decreased, and C 02 formation in muscle is a c c e l e r a t e d .

II . Dogs’ arterial and venous blood normally contain, respectively, 3-81 and 3-92 mg. inorg. P per 100 c.e. In fever the blood-inorg. P usually increases, and the amount formed in the muscle decreases. Normal uric acid vals. are 0-76 and 0-79 mg. per 100 c.c. In fever, blood-uric acid increases considerably, partly due to lcucocytosis, and formation in muscle is also increased. Ch . A b s .

G rass-pollen antigen for hay-fever desensitisation. J . F r e e m a n (Lancet, 1933,2 2 4 ,573—574). E xtracts from all the various grass-pollens yield the same antigen for desensitisation to hay-fever.

L. S. T.B rain-cholesterol and -lip ins of m ental de

ficients. P. L a u r i e (Bull. Soc. Chim. biol., 1933, 15, 418—425).—No significant difference between the

BIOCHEMISTRY. 6 2 $

normal and mentally deficient is observed with regard to the brain-total-P, -fatty acids, and -cholesterol either in the grey or in white m atter. H. D.

G astric secretion during h igh intestinal obstruction. S. K im (Korean Med. J., 1932, 2, 86— 92).—In dogs the acidity, [Cl], and amount of the gastric juice increased. Similar changes follow the injection of histamine. Ch . A b s .

Oxygen consum ption and nitrogen m etabolism . II. In leucaemia. C. W. B a l d r id g e and A. B a r e r (Arch. In t. Med., 1933, 51, 589—615).— Increased 0 consumption following X-ray treatm ent of the spleen in leucseinia is accompanied by an increase in protein catabolism (increased uric acid excretion). A secondary phase follows in which 0 consumption is decreased and is accompanied by N retention. P. G. M.

Kidney-phosphatase in experim ental nephritis.S. T o m ik a w a (Arb. I l l Abt. anat. Inst. Univ. Kyoto,1932, C, No. 3, 62—67).—The quantity is greatly decreased. Most of the phosphatase is present in the cortex. Ch . A b s .

Factors in the developm ent of deform ing leg w eakness in chickens. R. T. P a r k h u r s t and M. R. M cM u r r a y (J. Agric. Sci., 1933, 23, 311—327). —Perosis in chickens is associated with the feeding of excessive amounts of m eat and bone meal. The level of protein feeding and ra te of growth were without influence on the appearance of the deformation. Feeding of ground limestone did not produce slipped tendons. A. G. P-

I. Cause of m ottled enam el in hum an teeth.M. C. S m i t h , E. M. L a n t z , and H. V. S m it h . II. M ottled enam el in Arizona and its correlation with the concentration of fluorides in w ater supplies. H. V. S m it h and M. C. S m i t h . III. Experim ental production of m ottled enam el. M.-C. S m it h and E. M. L a n t z (Arizona Agric. Exp. Sta. Tech. Bulls., 1931, No. 32; 1932, No. 43; 1933, No. 45).—I. Mottled enamel of human teeth is associated with a relatively high F content in drinking- H.,0 supplies.

II. Observations in a no. of areas indicate th a t no injury results from H 20 containing < 2 p.p.m. of F. No relationship was apparent between the F content of H 20 and the nature of the source of supply. Sensitiveness to F injury is probably affected by dietary factors.

III. Mottling of ra ts ’ teeth is induced by ingestion of NaF in H 20 or foodstuffs and by subcutaneous or intramuscular injection. A return to normal conditions followed the cessation of F administration.

A .G .P .Blood-brom ine in psychom otor excitation.

W. K l im k e and B. H o l t h a u s (Deut. med. Woch.,1932, 58, 1558—1560; Chem. Zentr., 1933, i, 450— 451).—Blood-Br is diminished. A. A. E.

Glycuronic acid in scurvy. A. J . Q u ic k (J. Biol. Chem., 1933, 100, 441—444).—The scorbutic guinea-pig synthesises glycuronic acid. H. D.

Phosphorus content of the blood, m uscles, and urine during scurvy. A. Michaux (Compt. rend.,

1933, 196, 1341—1344).—The P content of the urine and blood of guinea-pigs decreases during scurvy; th a t of the striated muscles decreases during chronic, but not during acute, scurvy. R. S. C.

Chemotherapy of infections of Trypanosom a cotigolense. Elective action of organic poly- arsenicals. E. F o u r n e a u , J . T r e f o u e l , (M m e.) J. T r e f o u e l , D . B o v e t , and P. K c e t s c h e t (Compt. rend., 1933, 196, 1173—1175).—Toxicities towards mice and chemotherapeutic indices are recorded for a large no. of derivatives of C6H 6, Ph2, CO(NHPh),, [NHPh,CH2,]2, benzidine, and azobenzene containing two -As03H2 groups, which have a more favourable action on experimental infections of T. ccmgolense than have monoarsinic acids, bu t are inactive towards T. brucei. A. C.

Chloride content of urine of d iseased and healthy cattle w ith special reference to tuberculous cattle. M. V e s p e r (Diss., Leipzig, 1931; Bied. Zentr., 1932, 3, A, 86).—Reduced Cl' in urine of diseased cattle is not a sp. result of disease, but is due to disturbed digestive conditions. In tuberculous cows no reduction was observed. A. G. P.

Influence of aliphatic hydroxy-acids on the solubility of rare-earth sa lts of v ita l dyes. G.Ca n n e r i (Annali Chim. Appl., 1933, 23, 58—61).— The low solubility of these salts, used in the chemotherapy of tuberculosis, may be increased by addition of Na citrate. T. H. P.

B asal m etabolism of Am erican-born Chinese girls . F . G. B e n e d i c t and M . H. M e y e r (Chinese J . Physiol., 1933, 7, 45:—59).—D ata from 18 subjects indicate a basal metabolism 6—9% lower th an th a t of American girls. F . 0 . H.

Catalytic oxid ising action of body flu ids on tissu e m etabolism . L. K a r c z a g (Biochem. Z., 1933, 260, 44—46).—Ultra-filtrates (I) from human blood-serum, cerebrospinal fluid, and the aq. humor of the pig’s eye, used alone as nutrient media, increase, often very greatly, the respiration of guinea-pig kidney and mouse brain, aerobic and anaerobic glycolysis being a t the same time inhibited. The metabolism of mouse carcinoma proceeds aerobically in (I) instead of anaerobically as in Ringer’s solution, no glycolysis taking place. W. McC.

Effect of m uscular w ork on the oxidations in the body. I. K a n a i (Biochem. Z., 1933, 260, 129— 138).—In healthy rats biological oxidations (I) become more complete as a result of muscular exercise (II). When great fatigue (III) begins, (I) becomes less complete, especially in untrained rats. The N metabolism remains unchanged during (II) until i t becomes severe with subsequent (III), when increase occurs.

W. McC.M easurem ent of tissue respiration. M . D i x o n

and D. K e i l i n (Biochem. J ., 1933, 27, 86—95).—The method of Dickens and Simer (A., 1931, 1182) has been modified. A new type of flask, which necessitates the use of only one manometer and two readings for each experiment, allows the 0 2 or C 02 of respiration of a tissue or cell suspension to be determined, using as medium either phosphate buffer, HCOj'-Ringer solution (I), or serum in equilibrium


with the physiological tension of C02. W ith (I), a third reading gives the aerobic glycolysis.

F. 0 . H.Growth and reproduction on synthetic d iets.

III. F ats. G. A. H a r t w e l l (Biochem. J ., 1933, 2 7 ,146— 150).—R ats fed on a basal diet of caseinogen, potato starch, salt mixture, marmite, and cod-liver oil show better growth with addition of bacon-fat (I), lard (II), or margarine than with th a t of butter, beef or m utton suet, or olive oil. W ith (I) or (II), reproduction does not occur, whilst with any of the above synthetic diets, reproduction, growth, and condition of the fur are inferior to those of ra ts fed on kitchen scraps. F. 0 . H .

N utritive value of sperm - and finback-whale o ils. Y. S a h a s h i (Sci. Papers Inst. Phys. Chem. Res. Tokyo, 1933, 20, 245—253).—The oils have no growth-promoting effect in young rats. The cetyl and oleyl alcohols derived from them are definitely toxic, although neither they nor the pure waxes produce seborrhcea in young ra ts either by oral administration or intraperitoneal injection. A daily dose of 50—100 mg. of linoleic acid per os has a beneficial effect on the seborrhcea of ra ts supplied with whale oils. P. G. M.

Physiological actions of the ether-soluble substances of polished rice. Y. S a h a s h i (J. Agric. Chem. Soc. Japan, 1932, 8, 1093—1103).— Higher unsaturated fa tty acids (clupanodonic, hirag- onic) hindered the growth of rats. The linoleic acid of rice is necessary for normal nutrition. No difference was observed between the nutritive vals. of E t,0-ex tracted polished rice and wheat flour.

Ch . A b s .Role of the liver in cholesterol m etabolism .

A. L. M j a s s n ik o v (Klin. Woch., 1932, 11, 1910; Chem. Zentr., 1933, i, 79).—In dogs poisoned w ith P or salvarsan the blood-cholesterol rapidly rises, and then slowly falls. The liver has the power of producing as well as of excreting cholesterol.

A. A. E.Degradation of cholesterol. H. B e u m e r and

H. F a s o l d (Biochem. Z., 1933, 259, 471—474).—In infants receiving cholesterol, and in ra ts either starving or on an ordinary diet, no degradation of cholesterol could be detected. On feeding cholesterol or sitosterol to ra ts considerable destruction occurred, bu t is regarded as entirely due to intestinal bacterial action. P. W. C.

N utritive value of pentosan. III. Glycogen accum ulation in the body of rats on xylan feeding . IV. M ethods of treatm ent and the kinds of an im al for the d igestib ility of pentosan. H.I w a t a (J. Agric. Chem. Soc. Japan, 1932, 8 , 1175— 1179, 1252—1258).—III. Glycogen accumulation is slightly less when xylan is fed than when starch is fed, bu t the val. calc, on the digestible substance is practically const.

IV. When straw of rice, barley, wheat, Panicum crus-galli, L., var. frumentaceum, Hook., or coarse hay of Muscanthus sinensis, Anders., was treated with cold 0-75—1-5% NaOH for 4 hr. or 1% Ca(OH)2 for2 days, or was boiled w ith 1% Ca(OH), for 1-5—3 hr. the digestibility of the pentosan was 1-4—2-1 times

th a t of the untreated material. When rice straw was treated with 0-25% NaOH for 4 hr., or with wood-ash solution for 2 days, or was boiled with H 20 for 3 hr., no increase in digestibility was observed. Rabbits digest 78-9, ra ts 33-1, and guinea-pigs 62-9% of xylan. C h . A b s .

Glycogen changes of the organisation centrein am phibian gastrula. M. W. W o r d e m a n (Proc. K . Akad. Wetensch. Amsterdam, 1933, 36, 189—194). —A method of following the changes in the glycogen content during the development of the egg and embryo of the Mexican axolotl is described. The probability of a genetic connexion between plasma and glycogen is discussed. M. S. B.

Effect of bile acids on carbohydrate m etabolism . XX. Glycogen synthesis by bile sa lts on adm inistration of different am ino-acids. S.F uzita (Arb. med. Univ. Okayama, 1932, 3, 192— 200).—Glycogen synthesis in starving dogs is increased by adm inistration of bile salts. ¿-Alanine and Meucine increase, whilst glycine decreases, the synthesis of liver-glycogen after adm inistration of bile salts.

Ch . A b s .Factors influencing the m etabolism of glucose

ingested by fasting dogs. M. D an n and W. H. C h a m b e r s (J. Biol. Chem., 1933, 100, 493—514).— Determinations of the R.Q- after adm inistration of varying amounts of glucose to dogs fasted for about3 weeks showed th a t the inhibition of carbohydrate oxidation was complete for about 4 hr. following the ingestion. 400 g. of glucose administered over a period of 4 days did not restore normal metabolism. The recovery val. of other foods tested decreased in the order cracker meal, wheat-germ extract, yeast concentrate, and maltose, the first three being in the reverse order to th a t of their vitamin content. The effectiveness of insulin (2—6 units per kg.) was < th a t of yeast concentrate, b u t the combined effect exceeded th a t of either alone. A. L.

Cause of selective absorption of sugar from the intestine. W . W i l b r a n d t and L . L a sz t (Biochem. Z., 1933, 259, 398—417).—Galactose is most quickly and glucose, fructose, mannose, xylose, and arabinose with decreasing velocity absorbed from the ra t’s small intestine. Absorption of glucose bu t not of xylose is accelerated by P 0 4" ' and it is suggested th a t phosphorylation precedes absorption. Under the action of CH2I-C02H absorption of hexosesis, bu t of pentoses is not, inhibited. Phosphorylation of glucose in presence of intestinal mucosa extract is inhibited by CH2I*C02H but is unaffected by NaF, NaCN, and urethane. The action of CH2I'C 0 2H is a direct action on the absorption of sugar and is not brought about indirectly by increasing blood-sugar. Increased hexose phosphate content in the intestinal wall during absorption of glucose could not be detected. P. W . C.

P hysiology of the surviving m am m alian heart. VII. Consum ption of sugars by the cat’s heart. R. VON P o m 6 t h y (Biochem. Z., 1933,260, 192—200; cf. A., 1929, 467).—Results of previous workers concerning the glucose consumption (I) of the surviving heart are confirmed. Mannose, fructose, and galactose are consumed to the extent of

BIOCHEMISTRY. 631

two thirds, one fifth, and one sixth of (I), respectively, whilst lactose and maltose are not consumed.

W. McC.M etabolism of silkw orm s, II. M ethyl-

glyoxal as an interm ediate product in the carbohydrate m etabolism of B o m b ix m o r i, L. A.S m o l in (Biochem. Z., 1933, 260, 34—38; cf. A., 1932, 638).—Pulped silkworms (deprived of intestines and of contents of the digestive system), -extracts of such worms and pupae produce AcCHO from Na hexose diphosphate. W. McC.

Sexual variation in carbohydrate m etabolism . II. Acetoacetic acid in fasting rats and guinea- pigs. J . S . B u t t s and H . J . D e u e l , jun. (J. Biol. Chem., 1933, 100, 415—428).—No sexual variation in the excretion of ketonic substances (I) is observed with fasting rats. Doses of Na acetoacetate which were toxic for female ra ts had no deleterious effects on males; with a daily dose of 1-5 mg. per sq. cm. body-surface the excretion of (I) in females is > in males. The same is true for guinea-pigs. The ketosis is reduced by feeding carbohydrate. H. D.

Intervention of liver in fixation and synthesis of peptides. R. M a r t e n s (Bull. Soc. Chim. biol., 1933,15, 369—378).—Administration to a dog of 5 g. of peptone (I) per kg. body-wt. is followed after 25—30 min. by an increase in portal blood-polypeptide-N (II) from 4-57 to 5-20 mg. per 100 c.c. in the portal vein, whilst no change is observed in the peripheral veins. W ith man an increase in (II) ocuurs after 1 hr., and (II) becomes const, after 2 hr. In dogs injected with ThOa or with ligatured bile- ducts a similar increase in (II) occurs 30 min. after absorption of (I). Men suffering from hepatic lesions show the same effect 90 min. after injection of (I). The subsequent increases of (II) observed are due to the synthetic action of the liver which is unimpaired by the lesions. H. D.

Dependence of the structure of tissue-proteins on the m etabolism of the organs. I. E. G. S c h e n c k and H. W o l l s c h it t (Arch. exp. Path . Pharm., 1933, 170, 151—165).—The amounts of free and combined tryptophan (I) in various tissues (liver, kidney, muscle, heart) and body-fluids of ra ts depend on the state of the organism. Thus variations occur with differences in diet. The utilisation of orally administered (I) also depends on the condition and diet of the animal. Inclusion of protein in the diet produces formation of body-protein, and differentiation between exogenous and endogenous protein metabolism no longer holds. Plasma-proteins are probably derived from organ-proteins. F. 0 . H.

Cow’s m ilk or hum an m ilk ? W. S c h a r f n a g e l (Siiddeut. Apoth-Ztg., 1932, 72, 379; Chem. Zentr., 1933, i, 79).—The advantage of m other’s milk in the nutrition of infants is a ttribu ted to sp. protein groups and particularly to the diastase content. The saliva of new-born infants contains little diastase. A. A. E.

Creatinuria and m uscular contraction. L. H é d o n (Bull. Soc. Chim. biol., 1933,15, 407—409).

Nitrogen m etabolism after blood transfusion. W. K i (Tóhoku J . Exp. Med., 1932, 20, 123—147).

Ch . A b s .

Growth retardation by the partly oxidised sulphydryl of cysteine. F . S. H a m m e t t (Science, 1933, 77, 190—191).—A partly oxidised S derivative of cysteine retards the growth of Hydra hydranths and the embryonic development of Crepidula eggs and larvae. This establishes the postulate th a t growth by increase in cell no. is regulated by the naturally- occurring chemical equilibrium between SH and its partly oxidised derivatives. L. S. T.

Variations in the grow th-accelerating pow er of chicken em bryo juice on cultivated tissu es in v itro . J . S h im iz u (Japan. Z. Mikrobiol. Path ., 1932,26, 1174—1182).—The juice is inactive after 24 days a t 0°, 10 days a t room temp., or 48 hr. a t 37°.

Ch . A b s .Effects of various organ preparations on the

grow th of tissue in v itro . I, II. M. O m m y o ji (Japan. Z. Mikrobiol. Path ., 1932, 26, 999—1014, 1183—1194).—I. Thyroid, parathyroid, ovary, p itu itary, testes, and prostate preps, accelerate the growth of fibroblasts of chick embryo in dil., and inhibit it in conc., solutions.

II . C orp u s lu te u m , lu n g , s p le e n , k id n e y p a r e n c h y m a , a n d p a n c r e a s e x t r a c t s a c c e le r a te t h e g r o w th in d il . , b u t th e s e , e x c e p t lu n g a n d l iv e r p a r e n c h y m a , in h ib it i t in c o n c ., s o lu t io n s . Ch . A b s .

Law of m axim u m norm al nutritive value [of foodstuffs]. E . B. F o r b e s (Science, 1933, 77, 306—307). L. S. T.

D igestib ility of foodstuffs. H. M o s e r (Z. Unters. Lebensm., 1933, 65, 257—274).—Curves are given relating the p n with (1) the Hirsch buffer val.(0), and (2) the sp. digestibility (s=O/calorific val. per g.) for the digestive juices and milks of various animals, and for egg, cheese, wines, fruits, and carbohydrate foods. An attem pt is made to deduce from these curves the digestibility of the various foods in the presence of digestive j uices. Ox bile shows a more rapid change in 0 with p a than human saliva or canine gastric juice, and wheat bread a greater change in s w ith p,L than the other carbohydrate foods. Between p a 2 and 3 there is a rapid rise in 0 and s, for human milk, which is absent from cow or goat milk. J . G.

Effect of diet on egg com position. I. Partia l chem ical analyses of eggs produced by pullets on different d iets. H . W. T i t u s , T . C. B y e r l y , a n d N . R. E l l is (J. N u t r i t io n , 1933, 6, 127— 138).—T h e c o m p o s it io n o f y o lk s w a s in f lu e n c e d > t h a t o f th e w h ite s b y d ie ta r y d iffe r e n c e s . A. G. P.

M ineral and nitrogen m etabolism of hens receiving varied diets. W. S c h m id t (Arch. Tierer- nahr. Tierzucht, 1932, 7, 436—464).—Comparison of artificially adjusted physiologically-acid and -alkaline diets showed the former to favour Ca and P retention and the utilisation of ingested minerals. Max. mineral retention by laying hens was produced by addition of CaC03 to physiologically acid, or CaCl2 to alkaline, diets. The C a: P ratio of the ration had no direct influence on the ratio Ca : P retained. Low physiological acidity in the diet caused greater retention of minerals than high acidity or alkalinity.

A. G. P.


Lim e and phosphoric acid requirem ent for chicks. R. M. S h e r w o o d (Texas Agric. Exp. Sta. Bull., 1932, No. 462, 14 pp.).—D ata for chicks of various ages are recorded and discussed in comparison with other workers’ results. A. G. P.

Suitab ility of the m ineral com position of young m eadow grass and sta ll rations, especially for m ilch co w s . B . Sj o l l e m a (Landbowk. Tij dschr.,1931,43, 793; Bied. Zentr., 1932, 3, A, 106).—The Ca balance of cows was, in general, negative during winter, remaining so in the grazing season as a result of increased milk production and becoming positive only in late summer. Young grass contains a relative excess of K and N and insufficient Na for a normal ration. During stall feeding, negative Na and Cl balances occur. Mg and S supplied in grass and stall feeds are normally sufficient. Heavy manuring of grassland with N and K may produce grass of very unsuitable composition. More rational manuring increases the growth of clovers and improves the mineral composition of the herbage. A. G. P.

N utritive value of h igh and low calcium - carrying w heat. E. 0 . G r e a v e s and J . E. G r e a v e s (J. N utrition, 1933, 6, 113—125).—In ra ts receiving rations consisting of 90% wheat the % of to ta l ash, Ca and P in the bones and the Ca and P of serum was higher in all cases where high-Ca wheat was used.

A. G. P.N utritive value of various types of phosphoric

acids. K. T a k a h a s h i (J. Agric. Chem. Soc. Japan,1932, 8, 515—518).—No growth (of rats) took placew ith H 3P 0 2 in absence of H 3P 0 4; w ith the other P 0 4- acids normal growth was observed. Ch . Abs .

Influence of iodine feeding on the developm ent of ew es and lam b s and on the yield and quality of w ool. E. ViiiGHELYi (Mezogaz. K utatasok, 1931, 4, 349 ; Bied. Zentr., 1932, 3, A, 105).—Rations supplem ented with 2% of CaC03 containing 0-15% K I produced greater live-wt. increases in ewes and lambs and also raised the yield and I content of wool. The quality of the wool was not affected. The yield and I content of the ewes’ milk wrere increased. A. G. P.

Is fluorine an indispensable elem ent in the d iet?G. R. S h a r p l e s and E. V. M cCo l l u m (J. N utrition,1933, 6, 163—478).—Determ ination of F is based onits bleaching action on the yellow colour produced by treatm ent of Ti compounds w ith H 20 2. The F conten t of teeth and bones in ra ts increases (within certain limits) with age and varies with the diet. Young ra ts contain very little F. A low-F diet does not affect growth or reproduction, nor produce any change in the Ca : P ratio of bones. A. G. P.

[Pharm acology of] A n itn i V isnaga. K.S a m a a n (Quart. J . Pharm ., 1933, 6, 13—22; cf. A.,1931,885).—A study of visnagan. W. S.

E xperim ental variation of the toxicity of D ig ita lis . II. Com bination of D ig ita lis w ith purine derivatives. R. K o h n and B. C. C o s t o - p a n a g io t is (Arch. exp. Path . Pharm ., 1933, 170, 226—238; cf. th is vol., 422).—The min. lethal dose to cats of a Digitalis prep, was increased by 20—30% by simultaneous adm inistration of caffeine (I) and decreased ,20—40% by th a t of theobromine or theo

phylline (II). The action of (I) could not be eliminated or reversed by admixture with (II). The effects are probably due to changes in the circulation and in cell- permeability. F. 0 . H.

Effect of strong ultra-violet irradiation on the tox icity of pure nicotine. G. W a k e h a m and C. B. J o h n s t o n (J . Amer. Chem. Soc., 1933, 55, 1601— 1604; cf. A., 1932, 540).—Intense irradiation, even for long periods, does not destroy the toxicity. The observation (loc. cit.) th a t the partial detoxication obtained by controlled irradiation is restored by over- irradiation is confirmed. H. B.

Pharm acology of “ atebrin .” G. H e c h t (Arch, exp. Path . Pharm., 1933,1 7 0 ,328—338).—Small doses of “ atebrin ” (I) (an alkylated diaminoacridine used in malaria) produce a local cell irritation and some disturbance of the central nervous system. Larger doses paralyse the intestine and affect the higher nervous centres leading to respiratory failure and death. Elimination of (I) from the body is very slow, little being excreted in the faeces. A p art appears in the bile and is re-absorbed in the intestine. F. 0 . H .

E x cre tio n of " a te b r in " in u rin e an d faeces.C. T ropp and W. W e i s e (Arch. exp. P a th . P harm ., 1933, 170, 339—346).—“ A tebrin ” (cf. preceding abstrac t) is excreted unchanged in th e urine and faeces (of m an) in approx. equal am ounts. Following adm inistra tion , th e excretion is rap id for a sh'ort period and th en rap id ly falls to a low level, a t which it rem ains for a com paratively long period. The to ta l am ount excreted is Only a fraction of th a t injected.

F. O. H.P harm acological application of azoxy-com -

pounds. G. Ca r r a r a (Annali Chim. Appl., 1933,23, 140— 144)—Acetamidoazoxytoluene (Erba-azoform) is superior in cicatrising action to diacetamidoazo- toluene. T. H. P.

Comparative pharm acology of som e condensation products of phenols w ith aliphatic aldehydes. D.T. M a c h t and W. C. H a r d e n (J . Pharm. Exp. Ther., 1933, 47, 377—390).—The actions of compounds of the series CHR(^-C6H4-0H )2, CHR(3 : 4-C6H 3Me-OH)2, and CHR[2 : 4-CGH 3(OH)2]2 (R=M e, E t, P r, Bu, w -0 5H n , w-C6H 13, and ii-CjH^) have been investigated on Lupinus albus seedlings, Staphylococcus aureus, Carassius auralus (toxic effect), cats (blood-pressure and respiration), and rabbits (kidney function). The order of activity is peculiar for each test and for each of the three series of compounds, so th a t no positive generalisation as to the relation between chemotherapeutic effect and pharmacological action can be found. W. 0 . K.

Influence of sy m p a th e tic p o iso n s a n d narco tics on m u sc le m e tab o lism . O. R i e s s e r and K. Y a m a d a (Arch. exp. Path . Pharm ., 1933, 170, 208— 225).—Continuous intravenous injection of acetylcholine (I) into normal rabbits produces changes in the musele-glycogen (II), -phosphagen (IH), and -lactic acid (IV) closely resembling those due to adrenaline (V). T hat the effect is not due to (V) is shown by the same changes occurring when (I) is injected into ergotaminised rabbits. W ith nephrec- tomised rabbits, (I) produces a marked rise in (H), a

BIOCHEMISTRY. 633

slight rise in (III), and a fall in (IV). Atropine produces a rise in (II), (IÜ), and (IV), a result due to a process more complicated than th a t of sympathetic stimulation. Aq. MgS04 produces a rise in (II) and (III) and a marked fall in (IV). Urethane has a similar action, whilst with veronal (II) is unchanged, (III) is increased, and (IV) is decreased. The mechanism of these changes is discussed. F. 0 . H.

Action of quaternary am m onium salts on nerve. S. L. C o w a n (Nature, 1933, 131, 658).— Quaternary NH4 salts have a curare-like action in preventing transmission of excitation from nerve to muscle. They do not affect muscle or medullated nerve directly in the concn. required for paralysis (cf. this vol., 527). L. S. T.

E xcretion of m orphine by norm al and tolerant dogs. W . A. W o l f f , C. R i e g e l , and E. G. F r y (J. Pharm. Exp. Ther., 1933, 47, 391— 410).—Both in normal dogs and in dogs tolerant to morphine, about 17—20% of the morphine injected (2—200 mg.) is excreted, approx. § in the urino, and £ in the faeces. No significant difference could be detected in the rates of excretion by the two types of animals.

W. O. K.Pharm acology of cocaine. II. Fate in the

anim al body. H. A. O e l k e r s and W. R a e t z . II I . Action in the organism . H. A. O e l k e r s (Arch, exp. Path . Pharm ., 1933,170, 246—264, 265—270).—II. Cocaine (I) injected into rabbits; guinea-pigs, and dogs is excreted in the urine only to the extent of approx. 1% (cf. A., 1913, i, 1135; 1925, i, 736) and not a t all in the faeces. The level of (I) in the blood reaches a max. in 10—15 min. after subcutaneous injection and then falls so th a t only traces are detectable after 1 hr. (I) also appears rapidly in the organs, the brain having a max. val. (equal to th a t of the blood) in 15—25 min., whilst (I) is also found in the liver, kidney, and muscles within 48 hr. of injection. The decomp, of (I) in vivo appears to be chemical rather than enzymic. Polarised light does not decompose (I)_(cf. A., 1930, 111).

III . The influence of heavy dosage of (I) on m etabolism appears no t to depend to any appreciable extent on its action on enzymes. Thus (I) has practically no action in vitro on pepsin, trypsin, erepsin, cathepsin, pig’s liver-esterase, or pancreatic diastase. Potato-tyrosinase, however, is accelerated, whilst soya-bean urease, serum-lipase, and the reducing action of frog’s muscle are inhibited. Damage of the liver- and kidney-tissues occurs. F. O. H.

Determ ination of percaine in urine. K. O.M ö l l e r (Biochem. Z ., 1933, 259, 458— 464).— Pptn. reactions of percaine, the results of its electrometric titration, and methods for its determination in H 20 and urine are given. The formation of a ppt. with Reinecke’s salt which after recrystallisation from EtOH had m.p. 120° is regarded as characteristic.

P. W. C.Factors influencing the susceptib ility of albino

rats to injections of sod ium am ytal. D. H.Barron (Science, 1933, 77, 372— 373).—The sex difference in the reaction to Na am ytal is confirmed. The resistance to the drug appears to be related to the H20 metabolism and in the adult ra t the testes

seem to influence the H 20 metabolism control. Injection of Ringer’s solution into the blood reduces the effectiveness of the drug. L. S. T.

Relation between the speed of passage of local anaesthetics through lipin m em branes and their anaesthetic value. J . S i v a d j i a n (J. Pharm. Chim., [viii], 17, 361—365).—The hydrochlorides of local anaesthetics of the quinoline and piperazine series (cf. A., 1930, 1597) dissolved in aq. NaOAc have been dialysed through an oil-collodion membrane. The quantity of base which passes through is related to the local anaesthetic activity, especially in the quinoline series, bu t there is not, in general, complete parallelism. The experiments broadly confirm the lipin- solubility theory of anaesthetics. W. O. K.

M axim al lim its of alcohol consum ption.E. M. P. W id m a r k (Biochem. Z., 1933, 259, 285— 293).—Assuming th a t the lethal concn. of E tO H in blood is 0-5%, a table shows the mean calc, lethal doses for persons of both sexes of varying body-wt. and gives some indication of normal variation. The results agree fairly well with clinical observations. The max. consumption of E tO H per day in a 70-kg. man is 170 g. and of MeOH 34 g. There is no evidence to support the view th a t the max. consumption is different in people who habitually drink from th a t of people who abstain from drinking EtOH.

P. W. C.Effect of m uscular exercise on the m etab olism

of ethyl alcohol. T. M. Ca r p e n t e r (J. Nutrition, 1933, 6, 205—224).—A review. A. G. P.

Uptake of ethyl alcohol by the isolated tortoise's heart. J . R o b e r t s o n and A. J . Cl a r k (Biochem. J ., 1933, 27, 83—85).—The amounts of EtO H taken up by the isolated heart of Testudo graeca from perfusion liquids containing 0-35—3-5% of EtO H were determined. W ith these concns. no arrest of the heart occurred and both the taking up and release (by washing out) of EtO H were rapid. The results indicate th a t the uptake of EtO H does not depend on differential solubility, bu t is due to adsorption on surfaces in the heart-cells. F . O. H.

Co-existence in barley radicles of substances producing hyperglycsem ia and hypoglycsem ia.E. D o n a r d and H. L a b b £ (Compt. rend., 1933, 196, 1047—1050).-—Ferm entation of an extract of the radicles which has a hyperglycaemic action on rabbits yields an EtOH-sol. fraction which causes a hyperglycemia of 36% in doses of 0-07 g. per kg., and is identified as mannitol. The fraction insol. in 95% EtO H causes a hypoglycssmia of 37-9% in doses of 0-065 g. per kg. A second hyperglycaemia-producing substance, probably hordenine, was isolated. A. C.

Dependence of cytoplasm ic structures in the egg of the sea-urchin on the ionic balance of the environm ent. A. R. M o o r e (J. Cell. Comp. Physiol.,1932, 2, 41—51).—The hyaline layer of the egg acts as an ion-protein compound and cannot be maintained intact by Ca" in acid solutions. The structural elements of the cytoplasm are maintained by alkali or alkaline-earth cations even under acid conditions and under alkaline conditions are unimpaired in the absence of these ions. The membrane system is stable


in acid conditions in the absence of inorg. cations and is destroyed by alkalinity unless inorg. cations are present in the surrounding solution. In this and similar biological systems alkali and alkaline-earth cations act additively and Ca" is approx. 100 times as effective as Na" in this respect. A. G. P.

Intracellular hydrogen-ion concentration studies. IX. pn of the sea-urchin eg g . C. G.P a n d i t and R. Ch a m b e r s (J. Cell. Comp. Physiol.,1932, 2, 243—249).—The normal cytoplasmic p n is 6-8+0-2 and th a t of injured tissues 5-3+0-2. Development of the same p# outside the egg occurs prior to visible signs of cytolysis within the egg.

A. G. P.Perm eability of the A rbacia egg to ethylene

glycol at different tem peratures. D. R. S t e w a r t and M . H. J acobs (J . Cell. Comp. Physiol., 1932, 2, 275— 283).—D ata covering a temp, range of 5—32° are given. A. G. P.

Perm eability of hum an skin to electrolytes.A. G. R . W h t t e h o u s e and H. R a m a g e (Proc. Roy. Soc., 1933, B, 113, 42—48).—Immersion of the arm in aq. LiCl or K I is not followed by any increase in the Li or I content of the urine or blood. In tac t skin is therefore impermeable to dissolved electrolytes. The skin absorbs I from I ointment. A. C.

Increase in blood-lactic acid due to undercooling. E. G e ig e r (Arch. exp. Path. Pharm., 1933, 170, 296—302).—Exposure of rabbits to cold produces a marked increase in the blood-lactic acid, the effect being greatly diminished by splanchnicotomy. This increase, together with the hyperglyca;mia resulting from subnormal temp., is therefore due to an increased liberation of adrenaline. F. O. H.

Chrom atic inclusions in the cytoplasm of cells after gam m a radiation, and changes in the nucleolus . J . C. M o t t r a m (J. Roy. Micros. Soc.,1933, 53, 28—34).—The chromatic, cytoplasmic in clusions observed in cells following irradiation are nucleolar extrusions, supporting the view tha t chrom atin is formed in the nucleolus. H. G. R.

Detoxication of copper and zinc by com plex- form ation. F. E ichholtz and A. B ir c h -H irsch - feld (Arch. exp. Path. Pharm ., 1933,170, 271— 284). — Of 71 org. and inorg. substances capable of forming complexes with heavy metals, 35 significantly decreased the toxicity of Cu towards the isolated frog’s heart, whilst of 34 substances of this type, only 4 decreased the toxicity of Zn. F . 0 . H.

M ilk-, m ucilage-, and fat-prophylaxis in lead poisoning. F . W e y r a u c h and A. N e c k e (Z. Hyg., 1933, 114, 629—636).—In dogs receiving 100 mg. Pb (as w hite lead) per kg. live wt., simultaneous administra tio n of milk or mucilage had no effect on the resorption of Pb. Tho la tter was markedly increased by adm inistration of fats. A. G. P.

Quinones as enzym e m odels. IX . COz/N H 3 quotient in anaerobic am ino-acid deam ination.B: K is o h and S . S t u t z k e (Biochem. Z., 1933, 259,455— 457).—Whereas in the oxidative deamination of glycino and serine in presence of pyrocatechol, hydroxyquinol, adrenaline, gallic acid, or resorcinol

(this vol., 313), C02 and NH 3 are eliminated in the ratio of 1 : 1 , no decarboxylation occurs when the reaction is carried out anaerobically with dinitrobenzene or nitroanthraquinone as H acceptor.

P. W. C.M olecular w eight of new oxidation enzym e.

T. S v e d b e r g and I. B. E r ik s s o n (Naturwiss., 1933,21, 330).—Observations made by means of the ultra- centrifuge of the ra te of sedimentation and of tho sedimentation equilibrium of two specimens of W arburg’s oxidation enzyme indicate th a t, although not homogeneous in size, the particles have a mean mol. wt. of about 60,000. The purer sample gave N =2-9% , whilst tho sp. vol. in solution was 0-655, so th a t the colloidal material is probably not protein.

W. O. K.Peroxidase from fruit of T rib u lu s te rre s tr is ,

Linn. N. G h a ta k and R . V. G iri (Bull. Acad. Sci. Allahabad, 1933, 2, 171— 178).—Details of the prep, of the enzyme are given. The optimum conditions for its action aro : p a 5-3—5-5,1-5 vol.-% H 20 ,, temp. 15—20°. Above 60° the activity falls rapidly ; the enzymo is more labile a t an acid p R. P. G. M.

Chain character of catalase action. G . M . S c h w a b , B. R o s e n f e l d , and L. R u d o l p h (Ber., 1933, 66, [B], 661—664).—Tho restrictive effect of mannitol, p- and m- (I) -C6H 4(OH)2, PhCHO (II), P rsOH, CH2P1x-OH (III), and stilbene on the action of liver- catalaso on H 20 2 has been examined. The order of activity is the same as th a t observed in the photolysis of H 20 2, in which, however, the effect of (III) is more pronounced. The behaviour of (I) and (II) differs greatly from th a t observed in tho photo-polymerisation of vinyl acetate or autoxidation of S 0 3". It cannot be considered th a t the restricting agent affects an identical chain carrier in the different reactions. The courso of the chain reaction, if existent, is regarded as sp. and due to the mechanism of its causation. H . W.

T oxic action of sod ium n itrite on catalase of ox blood. 0 . T. R o t i n i and F . S n a s s e l (Ferment- forsch., 1933,13, 499—504).—Tho temp, coeffs. of the catalase (I) action of 1 % aq. blood in presence of added H 20 2 for temp, of 5—25° give a heat of activity (II) of 7220+520 g.-cal. NaNO, in concns. of < 2% has an inhibitory action, which, however, is not proportional to the concn.; concns. > 2% totally inhibit the action of (I). The vals. for (II) and for the velocity of reaction, especially for temp. < 15°, indicate that N aN 02 has a dual action. F. 0 . H.

Inactivation of am ylase by heat. A. O p a r in and S- M a n s k a j a (Biochem. Z., 1933, 260, 170—179; cf. this vol., 1S7).—The resistance (I) of m alt amylase to inactivation by heat (100°) is increased by sucrose and, to a smaller extent, by glycerol, being directly proportional to the concn. of the protective substances(II) and inversely proportional to the duration of heating. (II) increase the resistance (III) of proteins to coagulation by heat and factors {change in [H ], duration of heating, concn. of (II)} which increase or diminish (III) also increase or diminish (I) in p a r a l l e l .

. P a rt of tho activity of the amylase lost on heating in presence of high concn. of (II) is restored by treatment with peptone. W. McC.

BIOCHEMISTRY. 635

A m ylosynthease. I I I . T. Mi n a g a w a (Proc. Imp. Acad. Tokyo, 1933, 9, 97— 100).—Polished rice is powdered, macerated with 3—4 pts. H 20 , and filtered. Addition of 0-01i¥-CdCl2 ppts. amylosynthease and leaves amylase in solution. The CdCl2 ppt. is suspended in H 20 and (NH4)2S04 added to sa tu ra tion ; an active ppt. of the enzyme remains suspended. Starches, which resemble natural sol. starch, can be obtained by polymerisation of dextrin or glycogen which has been treated with HC1. Trypsin and amylosynthease are antagonistic, but can bo separated by fractional pptn. with (NH4)2S04. The optimum temp, for amylosynthease is 20—25°; it is destroyed by heating a t 50° for 10 min. P . G. M.

A m ylosynthease. II , IV—V II. T. M in a g a w a (J. Agric. Chem. Soc. Japan, 1932, 8, 508—510, 811— 814, 914—916, 1068— 1069, 1310—1312).—II. An aq. extract of the residue of brewer’s yeast after removal of amylase w ith glycerol affords on saturation with (NH4)2S04 a ppt. which gives a strong amylosynthease reaction. The enzyme is destroyed by COMe2 and EtOH.

IV. Amylosynthease was separated from pressed and dried yeast. Nishimura’s amylopectinase may be a m ixture of amylase and amylosynthease. Achroodextrin, erythrodextrin, sol. rice starch, and hcxahexosan give a bluish-violet colour with I -K I after treatm ent for 1 day with amylosynthease free from amylase.

V. 2 mols. of trihexosan were polymerised by yeast- amylosynthease a t p a 6-2.

VI. Amylosynthease can be separated from amylase by pptn. with Pb(OAc)2 and decomp, of the ppt. with C02.

VII. Yeast-amylosynthease is adsorbed by Ca or A1 phosphate, Al(OH),, kaolin, or active C, and removed by elution. Yeast extract with 24—25% (NH4)2S04 ppts. amylase; saturation of the filtrate with (NH4)2S 04 then ppts. amylosynthease.

Ch . A b s .Koji d iastase. M. I to (J. Fac. Agric. Hokkaido,

1932, 30, No. 5, 243—386).—The (non-colloidal) enzyme appears to consist of an active group, a polypeptide, a complex carbohydrate, and 5— 12% of ash. Removal of Mg and P 0 4 inactivates i t ; it is not inactivated a t 100° or when heated for a short time at 130°. Various synthetic mixtures had some hydrolysing action on starch. Ch. A b s .

Em ulsin . X I. B. H e l f e r ic h and O. L a n g (Z. physiol. Chem., 1933, 2 1 6 , 123—126; cf. this vol., 379).—3-Methyl(phenyl-fi-d-glucosidc), m.p. 148-5— 150° (corr.) [2-monoacetate, m.p. 154— 155° (eorr.); triacetate, m.p. 144—145° (corr.)], was not hydrolysed by emulsin. J . H . B.

Glyoxalase. I I . j)H-activ ity curve w ith phenylglyoxal and the effect of glutathione . J . O.G ir Sa v iGi u s (Biochem. J ., 1933, 27, 537—542).—The optimum reaction, with phenylglyoxal as substrate, is a t p u 6-4—6-5. About 0-1% of reduced glutathione is required for full activation of glyoxalase (I). Rapid inactivation of (I) after a lag period is caused by 0 2. A similar lag, with subsequent rapid inactivation, independent of On, characterises anti glyoxalase action.

H . G. R.

Enzym ic ester synthesis in em ulsions. W.F a b is c h (Biochem. Z., 1933, 2 5 9 , 420— 431).—Cetyl alcohol, C5H] 1*OH, and glycerol can be esterified with oleic, palmitic, and stearic acids in aq. emulsions in presence of Na oleate or deoxycholate by ammoniacal extracts of pig’s pancreas. In the early stages of synthesis, the time, amount of enzyme, and extent of reaction are proportional. The velocity of synthesis is always greater using deoxycholato than oleate as emulsifier. Increasing the amount of emulsifier increases tho velocity within certain limits. The activity-??., curves for the synthesis of amyl oleate are given. H 20 did not influence the esterification of cetyl and amyl alcohols, but with glycerol and oleic acid it accelerated up to 7% and then inhibited.

P. W. C.Enzym ic hydrolysis of phosphatides. II.

Lysolecithin. E. J . K in g and M. D o l a n (Biochem. J ., 1933, 2 7 , 403—409).—Lysolecithin (I) was prepared by the direct action of the venom of Bothrops atrox on egg-yolk by the method of Levene, Rolf, and Sims (A., 1924, vi, 438). Separation from lyso- kephalin was attained by dissolution of the crude product in glacial AcOH and fractional pptn. with E t20 and COMe2. 22 g. of original material yielded 16-7 g. of (I). The hsemolytic action of (I) was studied. Tho inorg. P 0 4" ' liberated by an aq. extract of rabbit intestinal mucosa (II) is a max. a t p a 7-8. In 48 hr.(I) is hydrolysed to twice as great an extent as lecithin(III) by (II) a t a slightly lower optimum p a, whilst the enzyme from a bono extract, more than twice as active as (II) with regard to glycerophosphate hydrolysis, scarcely attacks (III), but attacks (I) to a considerable extent. H . D.

Phosphatase in bovine kidneys. I— III. M . M o r i (Arb. H I Abt. anat. Inst. Univ. Kyoto, 1932, C, No. 3, 52—58, 68—72, 73—78).—I. Extraction of phosphatase from the cortical tissue is described.

II . The hydrolytic power of phosphatase obtained by autolysis of kidney tissue generally diminishes in the order : Ca sucrose phosphate, Ca salts of fructose6-mono-, diethylpyro-, a-glycero-phosphoric esters. The enzyme is inactivated by dialysis.

II I . X-Rays do not affect phosphatase.Ch . A b s .

Ortho- and pyro-phosphatase of bone and cartilage. III. Effect of arsenic and fluorine sa lts on bone-phosphatase. T. Y a m a n e (Arb. I l l Abt. anat. Inst. Univ. Kyoto, 1932, C, No. 3, 35— 45).—K 3A s 0 4 increases the effect of bone-phosphatase on fructose 6-mono-, glucose 6-mono-, and diethylpyro- phosphate, bu t inhibits th a t on sucrose phosphate. The action on E t2H P 0 4 is unaffected. N aF increases the action of phosphatase in all cases. Ch . A b s .

Phosphatase of body organs. I. Effect of m anganese sa lts on the phosphatase of the kidney, d igestive organs, and d igestive juices. I . H o r i , M . M o r i , M . M orim tjra , and S. T o m ik a w a (Arb. I l l Abt. anat. Inst. Univ. Kyoto, 1932, C, No. 3,7—29).—Fission of Ca fructose 6-monophosphate by phosphatase is retarded by Mn acetate, chloride, or n itra te ; small quantities have, however, little effect on kidney-phosphatase. W ith sucrose phosphate


the action of the enzyme is inhibited by Mn salts. R abbits’ saliva contains no phosphatase; extracts of the salivary glands have strong enzymic activity towards ortho- arid pyro-phosphoric esters. Dog’s pancreas oxtract and pancreatin contain estero- phosphatase; ex tract of rabbit’s pancreas, dog’s pancreatic juice, and rabbit’s bile are inactive. Extracts and secretions of intestinal mucosa of the rabbit are strongly phospholytic. Organ extracts and secretions of the foetus behave similarly to those of the hum an adult. The phosphatase is localised chiefly in tlio renal cortex. Ch . Ab s .

Protein-synthesising enzym e in spleen. S. G. H edin (Z. physiol. Chem., 1933,216, 203—204; cf. A., 1932,777).—Previous results are amplified. J . H. B.

Specific production of protective enzym es by m eans of serum -globulin and -album in and iodised and nitrated proteins. E. A b d e r h a l d e n and S. B u a d z e (Fermentforsch., 1933, 13, 505—543). —Parenteral adm inistration of fibrin-, eu- and pseudoglobulin (I), and of serum-albumin (II) (from oxen and horses) into dogs and rabbits produces in each case the corresponding protective proteolytic enzyme (III), which is sp. not only for the type of protein, bu t also for its origin. This is true also for iodised or nitrated(I) and (II), the original protein no t being degraded by the (III) arising from the corresponding I- or N 0 2- derivative. Pepsin and trypsin-kinase hydrolyse (I) and (II) and, less readily, their I- and N 0 2-derivatives.(II) is more readily hydrolysed by pepsin than (I),whilst the reverse is true for their I-derivatives. The application of the results to immunisation and to the characterisation of proteins of the same typebut of different origin is discussed. P . 0 . H.

N ew syntheses and enzym e studies relating to proteins. M, B e r g m a n n (Klin. Woch., 1932, 11, 1569—1572; Chem. Zentr., 1933, i, 239—240).—A lecture. A. A. E.

Activation of papain by cyanide. I. D. R. P. Mu r r a y (Biochem. J ., 1933, 27, 543—556).—The action of HCN (I) is not due to the removal of traces of toxic heavy metals (II) (cf. A., 1930, 957). The effect of (II) is a function of the substrate and p a, whereas (I) is lost on storage and varies with the method of prep. The activation by citrate is additive to (I) and oxtends the zone of p a activity in bothdirections. H . G. R.

Com plex nature of “ crystalline p ep sin .”E. W aldschmtdt-Leitz and E. K ofranyi (Natur- wiss., 1933, 21, 206—207).—The authors question the claim th a t N orthrop’s “ cryst. pepsin ” (A., 1932, 1166) is identical w ith the pure enzyme. The activity of the cryst. prep, m ay be adsorbed (94%) on canta- loupe-seed globulin, leaving a solution of the inactive protein component of the prep. The bearing of this result on the alleged protein nature of other enzymes is indicated. A. C.

Benzoic acid as preservative for foodstuffs. W.L ie s e (Chem.-Ztg., 1933, 57, 315).—BzOH has no sp. effect on the arrest of digestion of albumin by pepsin ; O'05% had no action, and 0-2% had only slightly greater inhibiting action than 0-4% NaCl solution (cf. A., 1932, 91). E. H. S.

Liver-proteinases and -polypeptidases. E.A b d e r h a l d e n and E. S ch w ab (Fermentforsch., 1933, 13, 544—562).—Preps, containing proteinases (I) and polypeptidases were obtained from liver press-juice and from autolysed liver. (I) have optima a t p n3 and 7, th a t a t 7 being probably due to peptones which are attacked only a t th a t reaction. Autolvsis of liver suspensions buffered a t p n 3-8 or 8-4 is accompanied by degradation of the tissue proteins by (I), whilst the presence of a carboxypolypeptidase (II) is shown by the hydrolysis of added sarcosyltyrosine and leucylglycyltyrosine; hydrolysis by aminopolypeptid- ases (III) or acylases (IV) does not occur. W ith autolysis in non-buffered media, (II) and (III) are active, whilst in buffered media a t p n 7 the activity of(III) and (IV) after 46 hr. is > th a t of (II). The (ii) of liver autolysates, unlike th a t of trypsin preps., hydrolyses glycyl-Z-tyrosine. W ith autolysis a t p n8-4 the action of (IV) is evident before th a t of (III). Prolonged autolysis produces an increased activity of(I) and (IV). (I) are sp. in their action on the cellproteins. Chloroacetyl-Z-alanine and -o-nitroaniline require different enzymes for their hydrolysis. Autolysis in acid media, especially a t p„ 3-8, is more prolonged than th a t in neutral or alkaline media.

F. O. H.Nature of p roteases. X II. Changes in v isco s

ity of m uscle-protein and collagen solutions during peptic d igestion. I. A . S m o r o d in c e v and A . N . A d o v a (Fermentforsch., 1933,13, 563— 572).— The viscosity (I) of muscle fibrils is unchanged by peptic digestion (II) for 24 hr., whilst th a t of collagen is increased 65— 80%. This difference can be applied to the characterisation of tissues. The optimum conditions for (II) and for max. changes in (I) are determined. F. O. H.

Catheptic proteinase. E. Ma s c h m a n n and E. H el m er t (Z. physiol. Chem., 1933, 216, 141—150).— In “ zookinase-free ” preps, from animal liver, spleen, and kidney, a p a rt of the catheptic proteinase (up to 15%) is in the fully activated condition. The rest requires ac tiva tion ; p a rt of this inactive material is activated in the minced organ by the thiol compounds present in the fresh pulp bu t absent from the extracted dried prep. F resh extract is somewhat more active than dried tissue extract. These results are not in agreement with those of Waldschmidt-Leitz and others (A., 1930, 1217). J . H. B.

Action of iodoacetic acid on the proteases of tissu e, on m alignant tum our ce lls , and on cell- free extracts . D. M ic h l in and W. R d b e l (Biochem. Z., 1933, 260, 121—128).—A t p^ 4 (but not a t ^ H 74) the action of proteases (from kidney, liver, tumours, and in extracts of healthy and diseased tissue) on the digestion of gelatin is reduced or inhibited by OOOIJV- CH2I-C02H. Probably the acid acts on the natural activator. W. McC.

Developm ent of uricase in tadpoles of Jiana tem poraria . R. T r u s z k o w s k i and H. Cz u pe r sk i (Biochem. J ., 1933, 27, 66—68).—Uricase (A., 1930, 1476) is absent from the eggs, first appears on the fifteenth day of development, and remains practically const, from the nineteenth to the forty-sixth day, when it again abruptly rises. The first period of

BIOCHEMISTRY. 637

activity is probably due to the formation of hepatic uricase, and the second to development of the mesonephros. F. 0 . H.

U rease. V. O ligodynam ic action of som e non-alkali m eta ls of the first group on urease.A. R ttchelmann (Biochem. Z., 1933, 259, 358—364). —Tables show th e effect- of additions of powdered Cu, Cu20 , CuO, and colloidal Au and Ag20 on the kinetics of the urea-urease system under varying conditions. The activity of these compounds decreases in the order Cu20 , Cu, CuO. Colloidal Au inhibits in the absence, but activates in the presence, of buffer. P. W. C.

Form ation of thiocyanate in the anim al body.K. L an g (Biochem. Z., 1933, 259, 243—256).—Form ation of thiocyanate from HCN and S or readily hydro- lysable S compounds in the animal body is catalysed by an enzyme for which the name rhodanese is suggested. Rhodanese is present in almost all organs, bu t is absent from blood and muscle. I t is sp., its p s optimum is 8-3, and it is destroyed by heating above 56°. The reaction velocity is large, bu t is decreased by bivalent cations. Experiments for the isolation and purification of the enzyme are described.

P . W. C.Effect of body-fluids on ferm entation. L.

K abczag and M. H a n a k (Biochem. Z., 1933, 260, 39—43).—The ferm entation of glucose (I) by yeast and th a t of AcC02H by B. coli (II) is not affected by blood- serum (III), which, however, diminishes the fermentation of (I) by (II) sometimes very greatly. The inhibiting agent in (III) is probably in the albumin fraction, and hence ultra-filtrates of (III) and also of cerebrospinal fluid have no effect on these fermentations. W. McC.

Effect of am ines on yeast poisoned w ith iodoacetic acid. E. F. S c h r o e d e r , G. E. W o o d w a r d , and M. E. P l a tt (J. Biol. Chem., 1933, 100, 525— 535).—Evidence is given to show th a t the reactivating action of certain amines such as ;p-C6H4(NH2)2 and tyrosine on fermentation by yeast poisoned with iodoacetate (cf. Zuckerkandl and Messiner-Klebermass, this vol., 18S) is due to the alkalinity of the reaction mixtures preventing the inhibitory action of the iodoacetate. Other factors influencing the fermentation are the destruction of iodoacetate by the amines and the stimulating or toxic effect of the la tter on the fermentation. A. L.

W ildiers’ b ios. Fractionation of b ios from yeast. W. L. Mil l e r , E. V. E astcott , and J . E. Mac o n ac h ie (J. Amer. Chem. Soc., 1933, 55, 1502— 1517).—Addition of ¿-inositol (I) to media containing aq. or aq.-EtOH extracts of yeast m ay or may not increase the yeast crop, according to the condition of the cells used for prep, of the extract. The liquid in which the cells of brewer’s yeast (II) are suspended should be removed prior to the prep, of the extract, since it m ay contain sufficient (I) to render any further addition unnecessary; this may account for the results obtained by Williams et al. (A., 1929, 1339) and Narayanan (A., 1930, 375). The bios in extracts of(II) or Fleischmann’s yeast (III) is fractionated by Lucas’ method (A., 1924, i, 1338) or by Pb(OAc)2 and aq, NH3. Crude bios I I from (III) is separated further

by treatm ent of its solution with C into bios IIA (not adsorbed) and bios IL8 (adsorbed) (recovery is by extraction with aq. NH3-COMe2). Bios I I from m alt combings and tomatoes is similarly separable. The same behaviour of Wildiers’ and Toronto yeasts in media containing one, two, or all of the three constituents renders unnecessary the assumption of the existence of a classof nutrilites differingfrom Wildiers’ bios. The effects of bios 114 and TIB are not due to T1 (cf. Richards, A., 1932, 778). Solutions of crude bios I contain some IL4 [which remains dissolved when the solutions are treated with Pb(OAc)2 and aq. N H 3 (cf. Lucas, loc. cit.)]. Various factors (agitation, aeration, p a of culture medium) affecting the yeast crops have been investigated. H. B.

Conversion of glycerophosphoric acid into pyruvic acid by yeast and lactic acid bacteria.C. N e u b e r g and M. K o bel (Biochem. Z., 1933, 260, ■241—246; cf. A., 1929,1337).—A t p B 6-6 in the presence of PhMe both yeast (I) and lactic acid bacteria(II) (B. Delbi-iicki) convert glycerophosphoric acid into AcC02H (III), ordinary hj'drolytic dephosphorylation occurring a t the same time and MeCHO being produced in small amount when (I) is used. The accumulation of (III) is less with (II) than with (I).

W. McC.Production of acids and alcohol by A sp erg illu s .

IV. Production of d-gluconic acid by A . oryzce.V. Conditions of culturing for acid productionby A . oryzw . VII. Classification of koji m oulds by selective ferm entation of sugars. K. Sa k a - g uch i (J. Agric. Chem. Soc. Japan, 1932,8,264—265;1931, 7, 748—762; 1932, 8, 531—546).—IV. A .oryzce SH No. 12 produced ¿-gluconic acid (88-31% of glucose used) and H 2C20 4 from 5% glucose solution containing 2% Ca(OH)2 in 5 days a t 32°.

V. A . oryzce SH No. 28 was grown in a solution containing glucose 100, K H 2P 0 4 0-15, K 2H P 0 4 0-15, MgS04 0-1, CaCl2 0-1 g., NaCl and FeCl3 trace, in 1 litre of H 20 . H 2C20 4 may be the secondary decomp, product of sugar. The quantity of kojic acid produced increased with the acidity of the solution, and citric acid was markedly produced a t p n 6-10. Production of gluconic acid was max. a t neutrality. H 2S20 4 was produced only a t p a >7-84. Production of citric acid occurred a t 28—37° and was absent a t < 20°. Kojic acid was markedly produced a t 15— 18°. Gluconic acid and E t20-sol. org. acids were generally produced a t the lower tem p. Peptone was preferable as source of N for the production of kojic acid, peptone, glycine, and N aN 03 for th a t of citric acid, and NH4 salts for th a t of gluconic acid.

VII. 116 species of ko)i-Aspergillus were classified in 16 groups according to their ability to ferment inulin, trehalose, raffinose, lactose, and galactose.

Ch . A b s .Production of citric acid by m oulds. III.

Japanese black m oulds. K. Sa k a g u c h i and J .Ya m a y a (J. Agric. Chem. Soc. Japan., 1932, 8, 489— 497).—Using Aspergillus awamori, Nakazawa, andA . aureus, Nak., peptone (0-4%) was the most suitable source of N. W ith N aN 03, H 2C20 4 is also formed. The optimum conc. of molasses for formation of citric acid was respectively 15° and 18° Balling, and p n 3-33


and 6-10. A t p n >7-84 H 2C20 4 is produced. 13 species of black moulds were compared. Ch. Abs .

Form ation of kojic acid by A sperg illu s oryzœ .H . K a t a g ir i and K. K it a h a r a (Mem. Coll. Agric. Kyoto, 1933, No. 26, 1—29).—The optimum p u for the production of kojic acid in any medium is 2-1 ; the max. yield is 63—66% using a 5—20% glucose solution. The mould grows slowly in 5% CO(CH2*OH)2, bu t a yield of 55% of kojic acid is obtained when a 2% solution is used. No kojic acid is produced when the source of C is COMe2, glycogen, or hexose mono- and di-phosphates. (NH4)2S04 is the best source of N. A . tamarii gives similar results. P. G. M.

Action of certain m oulds on solutions of aldoses and other saccharine m aterial. VII. Form ation of d-gluconic acid from m altose . A . A n g e l e t t i (Annali Chim. Appl., 1933, 23, 84—87 ; cf. A ., 1932, 145).—Both Pénicillium luteum purpurogenum and P. crustaceum (L.), Fries, form ¿-gluconic acid from m altose and hence presumably secrete mal tase. T. H. P.

Form ation of volatile arsenic com pounds by m oulds. F. C h a l l e n g e r (Ind. Chem., 1933, 9, 134).—Many moulds, such as Pénicillium brevicaule, produce AsMe3 from As20 3 or from org. As compounds. The gas gives two cryst. compounds with acid HgCl2 : AsMe3,2HgCl2, m.p. 264°, and AsMe3,HgCl2, m.p. 224—226°. The moulds can effect reduction of Asv to As™. P. G. M.

Action of m eta ls as co-catalysts of grow th.N . N ie l s e n and V. H a r t e l iu s (Biochem. Z., 1933, 259, 340—350).—F ilter paper does not catalyse the formation of the growth substance B (A., 1932, 661 ; this vol., 189), bu t acts as a co-catalyst of growth, substances (probably metallic) arising from the paper intensifying the feeble effect of the growth substance itself. Zn salts also act as co-catalvsts of growth.

P. W. C.Action of arom atic sulphur com pounds on

pathogenic fungi. T. H a c h iy a and J . N is h im u r a (J. Pharni. Soc. Japan, 1932, 52, 756—765).—A no. of org. S compounds (including K fi-thiolnaphthoate, N a p-pheiiylthiocarbamidobenzenesulphonate -j-5H20 , and N a 1 -phenylthiocarbamidonaphthaleneA-sulphonate + 0-5H 20) have been prepared and their action on fungi such as Tricophyton interdigitale and Achorion Schônleini has been determined. NHPh-CS-OEt, which is fungicidal to T . interdigitale in a concn. of1 : 104 and to A . Schônleini in a concn. of 1 : S000, is the only one to compare in potency with trypa- flavine ( l : 2 x l 0 4 and l : 3 2 x l 0 4, respectively). Alkali salts are less active than the free acids.

P. G. M.Effect of n itrogen source on oxygen consum p

tion by R h izo b iu m . R. H. W a l k e r and D. A . A n d e r s o n (J. Bact., 1933, 25, 53—54).—In four species examined, addition of yeast to a N-free medium considerably increased 0 2 consumption. With Rh. leguminosarum, Rh. trifolii, and Rh. phaseoli NH 4C1, NaNOs, urea, and alanine had little effect, bu t with Rh. meliloti all four N sources increased the amount of 0 2 consumed. A . G. P.

Physiology of certain n itrite-form ing bacteria.D. W. Cu t l e r and L. M. Cr u m p (Ann. Appl. Biol.,

1933, 20, 291—296).—Organisms from the Waste H 20 of a sugar-beet factory were examined. Among NH 4 salts the n itrate was the most easily oxidised. In most cases the bacteria can utilise the N 0 2 produced. A. G. P. ”

A erial-earth circuit and biological activity. I. A zotobacter chroococcm n. A. I t a n o (Proc. Imp. Acad. Tokyo, 1933, 9, 47—50).—Cultures of Azotobacter chroococcum containing two electrodes, one of which is earthed and the other connected to an antenna, growr more quickly and fix more N than those having no aerial and earth circuit. The effect of earthing alone is intermediate ; th a t of connecting to the aerial only is not appreciable. A. L.

Catalysis of the b iological fixation of nitrogen.H. B o rtels (Zentr. Bakt. Par., 1933, 87, II , 476— 477).—Stim ulation of N-fixing organisms of legumes in sand culture by Mo and V is accompanied by an induced growth of green algas in the upper layers of sand. A. G. P.

Influence of cations on bacterial sporogenesis in a liquid m edium . F . W. F a b ia n and C. S. B r y a n (J. Bact., 1933, 25, 33—34).—Cations of uni- (but not of hi-, ter-, or quadri-)valent chlorides stim ulate sporogenesis in aerobic bacteria. In the presence of univalent cations sporulation is greatest a t points of max. growth. Sporogenesis is not the result of deficiency of nutrients or accumulation of metabolic products. Sporulation was not markedly affected by the reaction of the medium within p H5-0—7-5, although an acid reaction appeared slightly the more favourable. A. G. P.

Detection of m icrobial lipase by copper soap form ation. J . A. B e r r y (J. Bact., 1933, 25, 433— 434).—F at is incorporated in an agar medium, and after solidification the surface is rinsed with CuS04 solution. S treak inoculations after incubation show lipase activity by the characteristic bluish-green lines of Cu soap. A. G. P.

Effect of m edium on production of bacterial gelatinase. R. B. H a in es (Biochem. J ., 1933, 27, 466— 474).—A linear relation exists between the change in viscosity of gelatin, (I) due to its incubation with centrifugates from various bacillary cultures, and the square root of the time of incubation, from which m ay be obtained a const., k, which gives a measure of the activity of the gelatinase (II) present. With broth cultures the most active (II) produced is that by Pseudomonas and B. pyocyanetis. The curve obtained by plotting A; against the p a of the incubated(I) has a max. a t p H S. W ith cultures obtained from synthetic media using N H 4 salts as sources of N, the production of (II) ranges from nil to its optimum val., depending on the concn. of Mg" and C a '\ The growth of cultures is best in a concn. of 0-002% MgS04 and absence of CaCl2 when no (II) is formed, whereas optimum (II) formation occurs when the culture medium contains 0-002% CaCl2 and MgS04. Mere addition of these salts to centrifugates from inactive cultures has no effect. H . D.

Effect of various substances on fat production by B . m ega th eriu m , B . m yco id e s , and B . albo- laetis. J . C. S p a r r o w (J. Bact., 1933, 25, 36—37).—

BIOCHEMISTRY. 63 »

Growth and fat production were not parallel processes. F a t formation probably results from catabolic processes, and does not represent the storage of synthesised material. A. G. P.

M etabolism of the sulphur-free purple bacteria. H. G ai'f r o n (Biochem. Z., 1933, 260, 1— 17; cf. van Niel, A., 1932, 884).—Rhodovibrio parvus (rhodobacillus) (I), which grows anaerobically in light when alone and cannot assimilate CO, readily, does so in light if the salt (II) of a fa tty acid is present. In the case of the lower fa tty acids the absorption of C0o proceeds regularly in proportion to the amount of (II) present, about 0-5 mol. per CH2 group being assimilated except a t the transitions C3-C4 and Ce-C 7. Irregularities also occur amongst the higher acids. Dicarboxylic and unsaturated acids also serve in a similar way with the expected differences. During the process the metal is eliminated as hydroxide. (I) is not damaged by drying or by treatm ent with large amounts of sulphide (which is oxidised to S 04"), but is very sensitive to acid reaction, to HCN [80% reduction of C 02 assimilation (III)], and to octyl alcohol (inhibition). (I ll) is reduced by high concn. of substrate and by N 0 3'. No metabolic products have been isolated, bu t dried (I) yields a substance (C4H 60 2)„ (cryst. osazone). (I ll) in (I) resembles th a t in plants.

W. McC.Pyocyanine and grow th potential changes of

Ps. pyo cya n eu s. G. B. R e e d and E. M. B o y d (Canad. J . Res., 1933, 8,173—179).—Measurements of growth potentials of Ps. pyocyaneus in broth and in a synthetic medium show th a t in the depths of the medium the potential becomes more negative than that of leucopyocyanine, whilst the surface layer remains more positive, as indicated by the formation of a blue layer. The synthetic medium used as a control maintained a high positive E h under both aerobic and anaerobic conditions. Similar results were obtained with a strain of Ps. pyocyaneus producing no pyocyanine, the potential in the depths of the medium being slightly less negative. The potentials observed are therefore not prim arily due to the presence of the pyocyanine, but diffusion of the pigment enables it to act as respiratory catalyst. A. A. L.

Respiratory catalysts in spores and vegetative cells of certain aerobic bacilli. H. L. A. T arr (Biochem. J ., 1933, 27, 136— 145).—Endospores (1) ofB. subtilis (two strains), B. mesentericus, and B. megatherium dehydrogenated certain hexoses and disaccharides anaerobically with methylene-blue (II) as H acceptor. Vegetative cells (III) dehydrogenated glucose (IV) more rapidly than did the (I) which they produce. The dehydrogenation by (III) was accelerated by previous heating of suspensions of (III) a t 80° for 30 min. or by aerobic incubation with (IV) for 30 min. a t 40° before addition of (II). The latter treatm ent prevented the inhibition due to 5% of ethyl- urethane (V) which normally occurred with the dehydrogenase activity of (I) and (III). Saturated aq. phenylurethane (VI) had an inhibitory effect on (I) and (III), whilst KCN partly inhibited only (III). (I) exhibited a small endogenous 0 2 uptake which was increased 10—40 times by addition of (IV). (I ll) oxidised (IV) more rapidly than their corresponding

(I). In the oxidation of (IV), freshly prepared (I) had a time lag of 50—60 min., which was considerably decreased by previous heating a t 60—90° for 30 m in .; such treatm ent had little effect on the respiratory catalysts of (I). The aerobic oxidation of (IV) by (I) and (III) was inhibited by (V) and (VI). W ith one strain of B. subtilis, the aerobic oxidation by (III) was inhibited by KCN and H 2S, whilst with (I) of the same organism, H 2S accelerated and KCN inhibited the oxidation; with the three other species, H 2S had no effect, whilst KCN inhibited the oxidation.

P . 0 . H.Oxybiotic and anoxybiotic gas m etabolism of

pathogenic bacteria. IV. Sem i-m icro-m ethod for m easuring the respiration and ferm entation of bacteria and other cells. T. W o h l f e il (Zentr.Bakt. Par., 1932, I, 125, 200—216; Chem. Zentr.,1933, i, 442—443).—Air free from C02, N2 free from0 2, or A is passed through the culture, and the effluent gas is analysed in a modified Haldane apparatus. A. A. E.

U tilisation of certain substituted sugars by bacteria. S . A. K o s e r and F . S a u n d e r s (J . Bact.,1933, 25, 32).—Substitution of OMe for OH in the sugar mol. decreases the ease of bacterial attack. Glucosamine was utilised by most glucose-splitting organism s; gluconic acid was less generally attacked. No cultures examined fermented glucose othylmer- captal. A. G. P.

Spore-form ing bacteria concerned in butyric acid decom position. W . W e r n e r (Zentr. Bakt. Par., 1933, 8 7 , II , 446—475).—Activity of various species in various nutrient media is recorded.

A. G. P.Stim ulating effect of potato extract on butyric

acid bacteria. E. L. T a tum and W. H. P e t e r s e n (J . Bact., 1933, 25, 26—27).—Increased activity of butyric acid bacteria on a maize mash medium, brought about by additions of aq. extract of potatoes, results in the complete destruction of starch and increased production of BuOH w ithout change in the proportion of other fermentation products. The stimulatory factor was absent from cereals and synthetic media. Its isolation and chemical reactions are recorded. A. G. P.

Ferm entation of acetoacetic acid and pyruvic acid by the acetone-butanol organism Cl. aceto- biitylicinn. W . H. P e t e r s o n and M. J . J o h n s o n (J . Bact., 1933, 25, 69).—Addition of acetoacetic acid to actively fermenting cultures of Cl. acelobutylicum results in its transformation into COMe2. The change is effected by actively reproducing cells or by cell suspensions, the la tter being effective when buffered to p H 5-2— 6-4 with P 0 4" '. Pyruvic acid under similar conditions yields AcOH, C0Me2, and acetyl- methylcarbinol. A. G. P .

Gluconic acid ferm entation. III. T . T a k a - h a s h i and T . A s a i (Zentr. Bakt. Par., 1933, 8 7 , II , 385— 412).—Cultural characteristics of B. Hoshigaki, var. glucuronicum I , I I , and I I I , are described and the effects of varying concns. of sugars, EtOH , AcOH, and NaCl on the activity of the organisms recorded.

A. G. P.


T rim e th y len e glycol fe rm en ta tio n . C. H.W erkman , C. W . D avis, and C. A. Tarnutzer (J. Bact., 1933, 25, 33).—Production of trimethyleno glycol by organisms of the Gitrobacter group is prevented by addition of fumaric acid (when succinic acid is formed), or of N aH S03. The latter fixes relatively large quantities of MeCHO and reduces AcOH production. Trimethylene glycol is probably not formed as a direct hydrogenation product of glycerol (Braak), but by way of an intermediate product, e.g., hydracryl-, prop-, or glycer-aldehyde. Max. yield of the glycol is J of the glycerol present. I t is suggested th a t 1 mol. of glycerol acts as a H acceptor to provide for the dehydrogenation of 2 more mols. of glycerol. E. coli does not ferment glycerol under anaerobic conditions, bu t the addition of a H acceptor (peptone, asparagine, fumaric acid, or MeCHO) initiates the fermentation.

A. G. P.B acillus sdprogenes sake , T ak a h ash i, an d th e

lac tic ac id b a c te r ia w h ich p u tre fy sak e . T.T akahashi and A. Suzuki (J. Agric. Chcm. Soc. Japan , 1932, 8 , 1064— 1068).—B. saprogenes cannot usually be cultivated on koji extract, except from a few species of koji (Aspergillus oryzee) which produce mainly EtOH. F ru it or vegetable juice promotes the growth of B. saprogenes. Ch. Ab s .

A erobic cellu lose-decom posing b a c te r ia in so il. A. K alnins (Latvij. univ. raksti, 1930, 11,I, 221—312; Bied. Zentr., 1932, 3, A, 130—131).— D ata of numerous species are recorded. In general N 0 3' and NH4 salts form the best sources of N, although certain org. compounds (e.g., peptone, NH2- acids) m ay be utilised. Cellulose, the common sugars, and inulin serve as C sources. Sugar media, bu t not cellulose media, show an increased p a w ith the growth of the organism. Cellulose decomp, produces a substance which reduces Fehling’s solution, yields glucose- phenylosazone, is formed in greater quantity when the 0 2 supply is restricted, and serves as an energy source for Azotobacter chroococcum. A. G. P.

S y n th esis of cellu lose by A cetobacter x y lim n n f ro m m an n ito l an d so rb ito l. Y. Iyhouyine (Compt. rend., 1933, 196, 1144— 1146).—C balances are recorded for 11-, 15-, and 21-day' cultures of Acetobacter xylinum containing (a) mannitol, and(b) sorbitol. In the longest cultures the yields of cellulose, sugar, and C02, in terms of the original alcohol, are 19-11, 54-95, and 17-6%, respectively, for (a), and 1-66, 88-96, and 5-96%, respectively, for(b). The products are formed by oxidative processes affording sufficient energy for the synthesis of cellulose. ‘ “ A. C.

C a lc iu m -p re c ip ita tin g b a c te r ia fro m m u d of a f re sh -w a te r lak e . F. T. W illiams and E. McCoy (J. Bact., 1933, 25, 57—58).—Aerobic and facultative organisms which ppt. CaC03 in media containing org. or inorg. Ca salts (e.g., CaS04, CaCl2, Ca lactate) are described. No relationship exists between the extent of pptn. and the final p a of the culture within the range 7-2—9-4. In media containing P 0 4" ' no P 0 4" ' occurs in the ppt. Pptn . also occurs in solid media containing mud extracts w ithout additional Ca” .

A. G. P.

A g g re ss in of G onococcus. W. Casper (Klin. Woch., 1932,11, 1996— 1997; Chem. Zentr., 1933, i, 442).—The filtrate from Gonococcus grown on serum- bouillon (pa 7-5) and the culture itself, when separately injected into a mouse, caused little toxic effect, bu t when administered together usually killed the animal. The filtrate causes toxic skin reactions, in man. A. A. E.

T ypho id to x in p u rified by ad so rp tio n w ith a lu m in iu m h y d ro x id e . I . M. Y ato (Japan. Z. Mikrobiol. Path., 1932,26,1015—1032).—The purified toxin of typhoid bacilli can produce immune bodies.

Ch . Ab s .F ilte rab le frac tio n s of tu b erc le to x in . C. N in n i

(Ann. Inst. Pasteur, 1933, 50 , 504—538).—The u ltra virus of the tubercle bacillus, which can bo obtained by filtration of a culture, will give rise to the normal acid-resisting bacillus following injection into the cervical ganglia of the guinea-pig. A granular state of the bacilli favours the formation of a biologically active filtrate. P . G. M.

C hrom ogenesis of a c id -re s is tan t bac illi. E ffect of [H’]. G. Sandor and G. R ou g ebief (Bull. Soc. Chim. biol., 1933, 15, 415—417).—Grassberger’s bacillus was grown in media containing glycerol, asparagine, and K 2H P 0 4 at different p n. In neutral or alkaline media the culture grows rapidly, but remains colourless until sufficient org. acid has been made to lower the p a. In acid media the culture is poor, bu t coloured red from the beginning. H. D.

B io log ica l effects of h ig h p re s su re s ;. ac tio n of very h ig h p re s su re s on b ac te rio p h ag es and vaccin ia v iru s . J . B asset, E. W ollman, -31. A. Machebceuf, and M. B ardach (Compt. rend., 1933, 196, 1138— 1139; cf. this vol., 313).—Staphylococcal bacteriophage is destroyed by exposure to a pressureof 2000—3000 atm . for 45 min. Phages of B. typhosusand B. subtilis are more resistant, and not completely destroyed below 7000 atm . Their resistance is increased in the presence of the corresponding bacteria. Vaccinia virus (I) is inactivated in 45 min. a t 4500 atm . The phages and (I) are much less resistant to pressure than enzymes and toxins. A. C.

R a tio n a lisa tio n , f ro m th e v iew -po in t of physica l ch e m is try , of th e b eh av io u r of b a c te r ia tow a rd s dyes w ith spec ia l re ference to sta in ing . A. E. Stearn (J. Bact., 1933, 25, 21—23).—The discussion is based on the view th a t the bacterial cell is an equilibrated system of two components, one being more acidic than the other, the whole system possessing amphoteric properties. A. G. P.

R elation betw een th e b a c te rio s ta tic ac tion of gen tian -v io le t a n d th e o x id a tio n -red u c tio n po tentia l of th e m e d iu m . M. A. I ngraham and E. B. F red (J. Bact., 1933, 25, 23—24).—Lethal action of dyes on bacteria is examined. Presence of dyes in media tends to restrict changes in oxidation-reduction potential resulting from the addition of oxidising or reducing substances. A. G. P.

A n tib ac te ria l p o w er of try p aflav in e , israv in , p an se p tin , an d m erc u ro ch ro m e . J . Do h i (Japan. J . Dermat. Urol., 1932, 32, 952—956).—Fluorescein derivatives possessed greater bactericidal power than

BIOCHEMISTRY. 641

aeridine derivatives for Slaphylococcits albus, S. citreus, Streptococcus ‘pyogenes, and Es. coli. Ch . Abs .

D ete rm in a tio n of b ac te ric id a l p ro p e rtie s of chem ical s te r i l is e rs . R . P. Myers and A. H. J ohnson (Proe. In t. Assoc. Milk Dealers, Lab. Sect.,1932, 25, 21—55).—The germicidal potency of 0C1' preps, is indicated by the ratio C l: alkalinity (as Na20). Low corrosiveness and low bactericidal potency are associated with high alkalinity.

Ch. Ab s .O ligodynam ic ac tion of m e ta ls on b ac te ria .

G. L a Cava (Ann. Igiene, 1931, 41, 612—619; Chem. Zentr., 1933, i, 442).—The action is duo to colloidal dissolution of the metals and their penetration into the bacterial protoplasm. Ag probably dissolves as colloidal Ag20 . " A. A. E.

T oxicity of fo rm aldehyde an d m erc u ric ch lo ride so lu tions to v a rio u s sizes of sc le ro tia of R izoctonia so lani. G. B. Sanford and J . W. Marritt (Phytopath., 1933, 23, 271—280).—The standard CH20 treatm ent is not effective where medium and large sclerotia are present. Solutions of HgCl2 (1 in 500) containing 1 vol.-% of HC1 were more satisfactory. A. G. P.

E nhanced le th a l effects of A '-rays on E scherichia coli in p resen ce of in o rg an ic sa lts . W. D.Claus (J. Exp. Med., 1933, 57, 335—347).—For 0 -lJ f solutions, the synergistic effect is appreciable only with salts of heavy metals. For Pb(N 03)2 or K Br the synergistic effect is appreciable only a t high concn. or absorption coeff. The no. of effective hits per bacterium per min. (a) depends on tho nature of the salt, or possibly on its penetration into the cell; a increases as X decreases. Ch . Ab s .

Physio logy of th e to n s ils . I . L . K ostyal.IV. L. K ostyal and M. P en k er t (Arch. exp. Path. Pharm., 1933, 170, 131—142, 143—150).—Subcut- aneous injection of extracts of tonsils (I) into rabbits and children produces a hypoglycemia (II) characterised by two phases. W ith intravenous injection a preliminary hyperglycemia (III) is followed by a prolonged (II) also characterised by two phases. These reactions of (I) are probably due to an indirect action on the pancreas and liver. Atropine increases(III) but does no t influence (II). (I) not oidy resemble insulin (IV) in their action, but also synergise (IV). With normal or diseased children, the higher is tho initial blood-sugar level tho greater is the (III) produced by injection of (I).

IV. Injection of (I) into rabbits and children produces changes in n of tho blood, indicating a dilution similar to th a t occurring with (IV). Neither (I) nor(IV) inhibits the blood-diluting action of the other.Atropino does not influence tho action of (I). No relationship exists between the blood-dilution and tho(II) due to (I). F. 0 . H.

M echanism of inhibition of gastric m otility by fat. Inhibitory agent from intestinal m ucosa.T. K osaka and R. K. S. Lnvr (Chinese J . Physiol., 1933, /> p—11)-—The gastric m otility of dogs w ith fistule is inhibited by the following in order of decreasing activity : a prep, (using picric acid) of the intestinal mucosa, blood after oil feeding, colonic mucosa,

intestinal plain muscle, and gastric mucosa. Leg- muscle, liver, and fasting blood do not inhibit. The secreto-inhibitory activities of these preps, are approx. parallel to their motor-inhibitory activities and hence these effects are probably due to a single substance.

F. 0 . H.F rac tio n a tio n of liv er e x tra c ts in re sp e c t of th e

an ti-an æ m ic su b stan ce . K. F elix and H. F r ü h - w ein (Z. physiol. Chem., 1933, 216, 173—180).— Liver extracts freed from protein by means of tannic acid were fractionated by pptn. with heavy metals in order to concentrate the anti-anæmic substance. I t is quantitatively pptd. from H 2S04 solution by HgS04 in presence of EtOH and E tsO. I t probably contains N but is not a peptide. J . H. B.

H æ m opo ietin , th e an ti-an æ m ic su b stan ce in h o g ’s s to m ach . I. L. K l e in and J .F . W ilk in so n (Biochem. J ., 1933, 27, 600—610).—An active extract can bo obtained from fresh stomach, tissue, ground w ith sand, by high pressure. Active fractions can then be obtained by pptn. with EtOH, the filtrate being inactive. Hæmopoietin is more unstable than, and has different properties from, the active substance in liver ; i t has a complex org. structure, is probably a protein, and enzyme-like in its nature. H. G. R.

P u rifica tio n of sec re tin . G. Âgren and O. W ilan der (Biochem. Z., 1933 , 259, 365—373).—A prep, is obtained of which 0-005 mg. per kg. is active in cats. Spectrographic examination shows th a t this prop, contains no cyclic NH 2-acids and the Millon, xanthoproteic, ninhydrin, histidine, tryptophan, cystine, and cysteine reactions are negative, whilst the diacetyl reaction is more strongly positive than for protein. I ts mol. wt. is below 1800 and it behaves as a base. P. W . C.

Effect of p a ra th y ro id h o rm o n e on th e condition of [se ru m -jca lc iu m . R. Spiegler and Stern (Klin. Woch., 1932, 11, 1580—1586; Chem. Zentr.,1933, i, 448—449).—I t is necessary to determine ultra- filterable Ca, electro-ultrafilterable Ca, and colloidal protein-Ca. Diminution of galvanic excitability after hormone treatm ent is accompanied by diminution in colloidal Ca and increase in free Ca, and vice versa. The increase in serum-total Ca after hormone trea tment is much less in man than in animals. Other hormones also increase the to tal Ca. A. A. E.

T h y m u s e x tra c t an d b lood-calcium level.H. G. Scholtz (Biochem. Z., 1933, 259, 384—386).— No definite effect of thymocrescin on the blood-Ca in rabbits could be demonstrated, the detection being rendered difficult by the large normal variation in these animals. In dogs (small normal variation) decreases were obtained, bu t these were small, and normal vais, were reattained in about 24 hr. P. W. C.

Influence of th y m u s p re p a ra tio n s in ex p e rim e n ta l h y p e rp a ra th y ro id ism . H. G. Scholtz (Z. ges. exp. Med., 1932, 85, 547—558; Chem. Zentr.,1933, i, 447).—Rise in blood-Ca in rabbits caused by parathormone is prevented or diminished if thym us extract is also injected ; décalcification of the bones is also prevented. Thymus extracts alone reduce the serum-Ca, but have no effect on the bone-Ca.

A. A. E.


Influence of th y ro x in e on tis su e o x ida tion .G. Myhrman (Klin. Woch., 1932, 11, 2139—2140; cf. th is vol., 430).—Treatm ent of animals with thyroxine during life caused no definite acceleration of methvlene-blue reduction by the liver after death, normal livers showing a large variation.

N utR. Abs .M ech an ism of ac tion of th y ro x in e . T. von

Ve r e b ^ly (Klin. Woch., 1932, 11, 1705— 1706; Chem. Zentr., 1933, i, 447).—Addition of thyroxine to suspensions of ra t’s muscle, or ra t’s or rabbit’s liver, was not accompanied by increased oxidation, the 0 2 demand being frequently dim inished; with ca t’s or rabb it’s brain a marked increase in 0 2 demand was observed. A. A. E.

F a c to rs w h ich d e te rm in e re n a l w e ig h t. X III. H ea t p ro d u c tio n of th e r a t a s v a r ie d by th y ro id a d m in is tra tio n . E . M. Mackay, F . M. Sm ith , and K . Gloss. XIV . R elative influence of am in o -, u re a -, an d p ro te in -n itro g e n in th e d ie t. E . M. MacK ay (J. Nutrition, 1933, 6, 151— 156, 157—161). —X III. In ra ts receiving thyroid preps, there is a linear relationship between renal wt. and heat requirem ent as measured by 0 2 consumption.

XIV. The effect on renal wt. of N H 2-N (glutamic acid and glycine) is the same as th a t of protein-N (caseinogen) Urea-N is less effective. A. G. P.

A d ren a l. I I I . A ctive e x tra c t of h o rm o n e of th e a d ren a l co rtex . A. Grollman and W. M. F iror (J. Biol. Chem., 1933, 100, 429—439).—A cortical hormone is prepared by extraction of the frozen tissue with C0Me2 (I), removal of (I) in vac., and repeated extraction of the aq. residue with C6H 6 (II). The(II) solution is shaken w ith saturated aq. NaHC03 to remove adrenaline and then with JY-HCl. (II) is removed in vac. a t 35—40° after adding 0-8% saline. The resulting solution is cooled and filtered. The first(I) extraction removes only 50% of the horm one; two subsequent extractions of the glandular residue give a further 50%. A cryst. specimen was obtained by evaporating the (II) solution to dryness. A method of assaying the hormone is described. H. D.

In te rn a l sec re tio n of a d re n a l co rtex . E.Schmitz and J . K uhnau (Biochem. Z., 1933, 259, 301—319).—The chemical separation from an adrenal cortex of two substances: A , which causes an increase of the plasma-phospholipin content in the normal rabbit, and B, which causes a decrease of the plasma- cholesterol, is described. The formula} C25H 40O3 and C23H3(i0 3 are assigned to A and B, respectively. Both are insol. in H 20 , no tpp td . by digitonin, give brownish- green colours with FeCl3 and brown Liebermann- B urchardt reactions with green fluorescence. Both, on acetylation by the method of Peterson and West, give vals. equiv. to one OH group. P. W. C.

A d ren a l co rtex . I . C ortical a d re n a l insufficiency an d th e ac tio n of th e co rtic a l h o rm o n e on th e n o rm a l an d ad ren a lec to m ised dog. G. A.H arrof and A. W ein st ein (J. Exp. Med., 1933, 57, 305—333).—In Addison’s disease and in adrenal insufficiency in dogs the blood-non-protein- and -urea-N, and the serum-K and -inorg. P 0 4 increase, w hilst the serum-total base decreases, owing to lack of the cortical

hormone. When normal nutrition is restored by adm inistration of the hormone, the blood-sugar is not decreased, there is no increased pigmentation, and no change in the basal respiratory metabolism ; there is increased sensitivity to insulin and thyroid extract.

Ch . Abs .C ortin an d tra u m a tic shock . N. E . F reem an

(Science, 1933, 77, 211—212).—A discussion (cf. th is vol., 320). L. S. T.

T h eo rie s of co rtico -ad ren a l function . S. W.Britton and H . Silvette (Science, 1933, 77, 368).— A discussion. L. S. T.

M etab o lism of a n im a ls on a ca rb o h y d ra te -free d ie t. V. Effect of ad ren a lin e on glycogen d is tr ib u tio n in th e r a t . A. H y n d and D. L. R otter (Biochem. J ., 1933, 27, 165— 172).—Large doses of adrenaline (I) given to ra ts fed on either a carbohydrate-rich (II) or a carbohydrate-free diet (III) produce marked changes in the blood-sugar (IV) and th e liver-glycogen (V), bu t have no definite effect on the liver-fat. During the first phase of 6 hr., (IV) increases, whilst (V) and muscle-glycogen (VI) decrease. The next phase of 20 hr. is attended by a normal or slightly low (IV) and by (V) increasing to a max. (in approx. 16 hr.) and then falling to normal levels; with(II), (VI) follows a course parallel to th a t of (V), whilst w ith (IH), the changes in (VI) are retarded. The changes occurring during the first phase are probably true effects of (I), w hilst those of the second, being of an opposite character, are secondary effects arising from a disturbed endocrine balance following adm inistration of (I). F . O. H .

E ffect of ad ren a lin e on b lood-lac tic acid .J . A. Collazo and J . P uyal (Klin. Woch., 1932, 11, 1947— 1949; Chem. Zentr., 1933, i, 446).—In rabbits, injection of 0-5 mg. of adrenaline per kg. causes a rise in blood-lactic acid. Hyperlae tacid aania and hyperglycaemia are accompanied by hyperlactaciduria. In man, injection of 1 mg. of adrenaline causes hyper- lactacidsemia (2 hr.). A. A. E.

R ela tio n betw een sleep a n d th e ad ren a lin e conte n t of th e a d ren a ls . A. G. H olmquist (Skand. Arch. Physiol., 1932, 65,18—23; Chem. Zentr., 1933,i, 75).—W ith hedgehogs caught in June the adrenals contain twice as much adrenaline during waking periods as during sleep. A. A. E.

S p ec tro p h o to m etric d e te rm in a tio n of ad ren a line in e x tra c ts of a d re n a l g lan d s . U. S. von E uler (Biochem. Z., 1933,260,18—25).—The method which is based on the reaction of Vulpian (Compt. rend., 1856, 43, 663) yields results in good agreement with those of the biological (blood-pressure) method. No standard is required, bu t a blank determination m ust be made. The hexuronie acid in the extracts, which renders Chikano’s method (A., 1929, 474) inapplicable, does not interfere. The errors are ±2% , ± 5 % , and ± 10% when the amounts determined are 0-05, 0-02, and 0-01 mg., respectively. W. McC.

A ccuracy of in su lin a ssa y on w h ite m ic e . A.M. H emmingsen (Quart. J . Pharm ., 1933, 6, 39—SO).—A statistical rationalisation of results (min. convulsivo dose) is made in order to overcome the inaccuracy

BIOCHEMISTRY. 643

arising from the biological variation in response of individual mice. W. S.

Influence of te m p e ra tu re in assay of in su lin by m ean s of convulsions in m ice. A. M. H emming - sen and H . P. Marks (Quart. J . Pharm ., 1933, 6,81—89; cf. preceding abstract).—The authors consider 29° preferable to 37° (Trevan, A., 1927, 792) since (a) the la tter temp, is more arduous for the mico and entails a higher ra te of m ortality, (6) the two methods yield similar distributions of the convulsive doses, and (c) the increased accuracy obtained a t the higher temp, is not as great as claimed by Trevan.

W. S.A n tag o n ism of in su lin an d a tro p in e . S. L ang

(Arch. exp. Path. Pharm ., 1933, 170, 292—295).— Atropine does not influence .tho hypoglycsemic action of insulin (I) in the depancreatised dog (II), whilst in the normal dog (III) a marked antagonism occurs. With both (II) and (III), (I) temporarily decreases the NH2-acid and lipin levels of tho blood. Tho action of (I) does not involve the parasympathetic nervous system. F. 0 . H.

A n ti-in su lin an d o th e r h o rm o n es of a n te r io r p itu ita ry g lan d . H. L ucke (Arch. exp. Path. Pharm., 1933,170,166— 175).—-The anterior pituitary gland produces a hormone which is not ultra-filterable and which antagonises insulin in its action on carbohydrate metabolism. I t is not identical with the thyreotropic, sexual, or gonadotropic hormone, but is possibly identical with the growth hormone.

F. 0 . H.R elation of th e p itu ita ry to ex p e rim en ta l

d iabetes. J . F . R egan and B. 0 . Barnes (Science,1933, 77, 214).—The finding th a t extirpation of the pituitary prevents severe diabetes in dogs appears to be confirmed. L. S. T.

E xcre tio n of ke ton ic su b s tan ces on a fa t d ie t as aSected b y in jection of p itu ita ry (an te rio r lobe) ex trac t an d by p reg n an cy . J . H . B urn and H. W. Ling (Quart. J . Pharm ., 1933, 6, 31—38).—Whereas normal adult female ra ts tolerate a fa t diet, ketonic substances, in these circumstances, appear in the urine of (a) young rats, (b) adult female rats injected with p itu itary extract, and (c) female ra ts during the last stages of pregnancy. W. S.

Influence of o v a rian a n d p itu ita ry h o rm o n es on calcium m e tab o lism . T. F. D ixon (Biochem. J.,1933, 27, 410—418).—Tho serum-Ca (I) of dogs is less variable than th a t of rabbits. The (I) of rats in cestrus or dioestrus (II) or 7 days after injection of extracts of ox anterior pituitary, of parathyroidectom- ised rats in (II) or injected with trihydroxycestrin, of pregnant or pseudo-pregnant rabbits, or of dogs injected with ovary or corpus luteum extracts, is not significantly abnormal. H . D.

C rystalline oestrogenic h o rm o n es . J . S. L. Browne (Canad. J . Res., 1933, 8, 180—197).—A substance, G18H 240 3 (I), m.p. 274°, believed to be a tr i hydroxycestrin related to theelol has been isolated from “ emmenin ” (A., 1931, 398). A physiological comparison with theelol and theelin is described. (I) has the same effect as theelol on the immature intact rat, but is 5— 10 times less effective on the adult

u u

ovariectomised ra t. I t is suggested th a t the presence of tho im m ature ovary increases the activity of (I) and of theelol by increasing the rate of conversion into more active oestrogenic substances. A. A. L.

F em ale sex u a l h o rm o n e . IX . C o m p ariso n of theelo l, em m en in , an d fo llicu lar h o rm o n e h y d ra te . A. B ute nan dt and J . S. L. Brow ne (Z. physiol. Chem., 1933, 216, 49—56; cf. A., 1932, 781).—Theelol and follicular hormone hydrate aro undoubtedly tho same substance ; emmenin (obtained from placenta) is probably identical, its somewhat highor physiological activity being due to impurity.

J . H . B.P o s t-m o rte m u te rin e find ings a f te r te m p o ra ry

h o rm o n a l s te rilisa tio n . M. Maino (Arch. 1st. Biochim. Ital., 1933, 5, 3—10).—Remains of fœ tal bones were found in uterine cysts in rabbits in which fœ tal resorption had been caused by administration of œstrin in late pregnancy (this vol., 194).

R. K . C.[Sex] h o rm o n e in u rin e an d m a m m a ry sec re

tio n . E. W . W in t e r (Arch. Gyn., 1932, 151, 201— 219; Chem. Zentr., 1933, i, 246).—Ovarian hormone(I) was found (Zondek) in the urine of newly-born infants up to the third, and anterior p itu itary hormone (II) up to the ninth, day post partum. No hormone was found in tho mammary gland. In pregnancy, colostrum contains (II) from the seventh month until the sixth day after delivery ; (I) is not presont. In the first stage of the climacteric the urine contains (I), and in the last stage follicular- ripening hormone. In sterility none of the hormones was found in tho urine. A. A. E.

P hysico -chem ica l p ro p e rtie s of p ro lan . A.Mogilski (Farm. Zhur., 1932, 11—12, 337—338).— The brownish albuminous powder gives biuret and gly- oxylic acid reactions, ppts. tannin, colloidal Fe(OH)3, and Pb(OAc)2, is salted out by cone. (NH4)2S04, does not coagulate when heated, and forms no ppt. with CC13-C02H, CsH 3(0H)(S03H)-C02H, or C6H2(NO2)3-0H.

Ch . A bs.S ource of th e te s tic u la r h o rm o n e . A. Lrp-

sc h ü tz (Med. Wolt, 1932, 6, 1231—1234; Chem. Zentr., 1933, i, 445).

C hanges p ro d u ced by th e te s tic u la r h o rm o n e in n o rm a l an d ca s tra te d r a ts . V. K orenchevsky , M. D enn ison , and A. K ohn-Spe y e r (Biochem. J .,1933, 27, 557—579).—In young, normal animals the physiological variations were small. Small doses give a slight decrease in wt. of the prostate and penis, whilst large doses give an increase together with an acceleration in the involution of tho thymus. Castrated rats tend to a return of the organs to normal ; an increase in wt. of the prostate, in direct proportion to the dose, and in the penis and thyroid, and an increased involution of the thymus were observed. H. G. R .

D etection of th e m ale sexual ho rm o n e by m ean s of th e fish te s t. D. Glaser and O. H aempel (Deut. med. Woch., 1932, 58, 1247—1248; Chem. Zentr.,1933, i, 445).—The test is sp. A. A. E.

K atech ins. F. Blum (Deut. med. Woch., 1932, 58, 1874—1876; Chem. Zentr., 1933, i, 444—445).—

.644 BRITISH CHEMICAL ABSTRACTS.— A.

“ Katechins ” are substances which diminish or arrest the action of horm ones; thus “ tyronorm an ” injected with thyroxine suppresses the rise in basal metabolism. Insulin is not a hormone, bu t a k a t e c h i n ” ; the corresponding hyperglycsemic hormone is also present in the pancreas and in the blood. A. A. E.

C hem ical n a tu re of th e an tix e ro p h th a lm ic v itam in -y l. H. Seel (Z. Vitaminforsch., 1933, 2,82—93).—N orth Sea and N. Atlantic fish liver-oils (chiefly Selachii and Batoidei) show considerable variation hi composition, vitamin-/! potency, and blue v a l .; the two last are not parallel. Alga: possess marked growth-promoting power, bu t little antixerophthalmic action in rats, and the existence of two factors is suggested. A cryst. Bz derivative of vitam in-4 has been obtained which is biologically active bu t gives no SbCl3 reaction until saponified. Oxidised cholesterol promotes growth, .but the SbCl3 reaction shows certain differences from th a t of vitam in-4 from other sources. R. K . C.

V itam in -/! in th e p im en to p ep p e r. L. Ascham (Science, 1933, 77, 351).—Four mg. of pepper produced a growth response in ra ts > th a t of the Sherman unit. The dried m aterial contains 200—300 mg. of carotene per kg. L. S. T.

V itam in -/! con ten t of lu cern e a s affected by ex p o su re to su n sh in e in th e c u rin g p ro cess .M. C. Smith and I. A. Briggs (J. Agric. Res., 1933, 46, 229—234).—In comparison with samples dried in a dark chamber, lucerne leaves cured in the field lost a large proportion of their vitamin-4, content (20— 33% after 2J hr. and 96% after 7 days). No loss of green colour occurred in samples exposed for a few hr.

A. G. P.A b so rp tio n sp e c tru m of v itam in -/! a t low te m

p e ra tu re s . F . P. B o w d e n , S. D . D . Morris , andC. P . S n ow (Nature, 1933, 131, 582—-583).—When vitam in-4 concentrates are cooled to liquid air temp, the max. a t 3280 A. is displaced to 3350 A. and new bands occur a t 2900, 2770, 2580, 2510, and 2430 A. When the product obtained by irradiating carotene is cooled, the band near 32S0 A. breaks up into a series a t 3780, 3570, 3410, and 3210 A. Hence the mol. produced by irradiating carotene differs from th a t associated with the 3280 A. band in vitam in-4 concentrates. L. S. T.

V itam in -/!. I . A b so rp tio n sp e c tra of ca ro - ten o id s . I I . P ro p e r tie s of h y d ro caro ten e . I I I . R ela tio n betw een h y d ro caro ten e an d b io s te ro l,K . I v a w a k a m t (J. Agric. Chem. Soc. Japan, 1932, 8,48—54, 55—63, 64—71).—I. Carotene has absorption bands between 3300 and 3400 A. and between 2630 and 2950 A . ; biosterol has a band between 3300 and 3400 A. The absorption bands of xanthophyll and lutein are indistinguishable from those of carotene; the bands of a-crocetin and capsanthin are different.

II . Hydrocarotene, obtained by reduction of carotene with Al-Hg and E tO H in CGH 14, has reactions and absorption bands resembling those of biosterol, b u t it has not the physiological action of v itam in-4 .

H I. Biosterol and Grignard reagent afford CH4; hence an OH group is present. Carotene and hydrocarotene do not react; hence hydrocarotene is not

contained in biosterol. Xanthophyll is reduced by Al-Hg a t 60—70° to hydroxanthophyll, which reacts with Grignard reagent and resembles biosterol in chemical properties and absorption spectrum, bu t has not the physiological action of v itam in-4 .

Ch . A b s .Value an d l im its of th e chem ical v ita m in r e

ac tio n of cod-liver o il. I I I . C hem ical an d b io log ical d e te rm in a tio n of v itam in -/! in cod- liv e r oil. W. B r a n d ru p (Pharm. Ztg., 1933, 78, 433; cf. A., 1932, 973).—Vogan, a vitam in-4 concentrate in vegetable oil solution, gives a blue colour comparable with a CuS04 solution in the SbCl3-CHCl3 test, whereas cod-liver oil gives a colour similar to th a t of alcoholic Victoria-blue solution. The difference in tone is ascribed to a constituent of cod-liver oil other than vitam in-4, and the reaction is suggested for the detection of cod-liver oil. E . H . S.

In fluence of b a sa l d ie t in th e d e te rm in a tio n of v ita m in -^ . K. Culhane (Biochem. J ., 1933, 27, 69—82).—Dried yeast (I) and “ light white casein ”(II) contain vitam in-4 (in insufficient quantity to maintain growth in rats) and -D. W ith ra ts on a diet containing fat, 5% of marmite is a sufficient source ofB, whilst with fat-free diets, 5% of marmite or 8% of (I) does not prevent skin lesions. Complete deficiency of 4 invariably produces xerophthalmia (III), which, however, can be prevented or its onset retarded by a diet containing (I) or (II), and which does not readily occur when there is a deprivation of both 4 and D. The rate of incidence of (III) forms a satisfactory basis for the assay of 4 . The basal diet of Drummond and W atson (A., 1922, ii, 596) is deficient in no other vitamin necessary for the ra t than 4 . F . 0 . H,

V itam in -/l-free b a sa l d ie ts . I . A. L. Bacha- rach . II . A. L. Bacharach and E. L. Sm ith (Biochem. J ., 1933, 27, 5— 16, 17—21).—I. R ats fed on a vitam in-4-free basal diet (I) exhibit anomalous rates of growth. Thus, whilst some cease growing hi 8—10 weeks, others continue to grow for several m onths; in a few cases a growth curve (n ) similar to th a t obtained with the commencement of vitam in-4 administration is given. W ith either a fat-free or fat-rich (I), the (II) and the degree of recover}’ under curative treatment appear to be independent of the type of caseinogen used as a source of protein. Curative treatm ent in no instance produces growth equal to th a t of normal animals on a stock diet. Hence (I) is deficient in some factor other than vitam in-4. The bearing of the results on the assay- of vitam in-4 is discussed.

II. The increased rate of growth due to the addition of vitam in-4 to (I) is still less than th a t due to the stock diet. W ith such diets, the liver reserves of vitam in-4 are parallel ■with the growth performance for each group. The passage of the vitamin from the mother to the embryo or suckling offspring is discussed. F. 0 . H.

L en g th of te s t p e rio d an d accu racy ob ta in ab le in a v i ta m in - / l te s t . K . H. Coward (Biochem. J ., 1933, 27,445—450).—The mean variances (I) of the increase in wt. (II) of rats due to a dose of vitam in-4 are plotted against the durations of the tests (III). In general (I) and the standard deviation of (n ) increase with (III). Equations of curves of response (IV), obtained by

f

BIOCHEMISTRY. 645

plotting the mean (II) of groups of rats against the dose of cod-liver oil given daily, are calc. From the standard deviations of the mean (II) and the slope of(IV) the degree of accuracy of the test obtained in any given (III) is calc., and is only slightly increased by prolonging (III) beyond 3 weeks. ' H. D.

D e te rm in a tio n of v itam in-y l in a co n cen tra te , “ V ogan .” T. Moll, 0 . D almer, P. von D obe- neck, G. D omagk, and F. L aquer (Arch. exp. Path. Pharm., 1933, 170, 176—207).—The vitam in-4 content of a commercial fish-liver oil prep. (I) was determined colorimetrically and biologically. A “ ra t imit ” is defined as the min. dose necessary to maintain growth of 3 g. per week in 60% of the test animals (young rats) which m ust also show freedom from xerophthalmia. (I) contained 40,000 “ ra t units ’’ per c.c. Alleviation in spayed rats of colpokeratosis affords a more rapid but less accurate test than the rate of growth. Oral administration of excessive doses of vitamin-4, to normal animals produces toxic symptoms. F. O. H.

G row th an d ce ll-reserves in v itam in in v estig ations. V II. F a ilu re of vitam in-yl a s a g ro w th - factor. W. K ollath (Arch. exp. Path. Pliarm., 1933,170, 285—291; cf. A., 1932,1173).—The failure of rats to grow on certain basal diets containing added vitamin-4 (I) is due to the lack of another factor (II) (“ IlG -factor ” ) which occurs in fresh and autoclaved yeast, germinated and ungerminated barley, crushed cereals, and bran. Histological investigation indicates th a t both (I) and (II) play a sp. part in tissue building. F. O. H.

V itam in-yl an d -D s tu d ies w ith g row ing ch icks. C om parison of cod-liver oil an d p ilch a rd oil as sources of v itam in -y l. H. S. Gu tterid ge (Sci. Agric., 1933, 13, 374^3S 1; cf. A., 1932, 433).—Pilchard oil is as good as, and may be slightly superior to, cod-liver oil as a vitam in-4 source for chicks.

A. G. P.Effects of m o d e ra te overdosage of v itam in -D

and of -A-\—J) on th e g ro w th ra te an d longevity of the w h ite m o u se . I I . T. B. R obertson, H. R- Marston, M. C. D aw barn, J . W . W alters, and J. D. O. W ilson (Austral. J . Exp. Biol., 1933, 11,49—52).—Mice given a slight overdose of vitamin-D benefit in respect of growth rates, but when a large excess of vitam in-4 was also administered the result was deleterious in respect of growth rate and of expectation of life in young animals, although the expectation of life of those animals which lived to 750 days was not altered significantly. W . 0. Re

p ro d u c tio n of v itam in -D by ir ra d ia tio n of ergostero l th ro u g h r a t ’s ep id e rm is . N. S. L ucas (Biochem. J ., 1933, 27, 132— 135).—A 0-003% solution of ergosterol (I) in EtO H was anaerobically exposed to ultra-violet light which had passed through the epidermis (II) of a day-old rat. The resulting solution showed changes in the ultra-violet absorption spectrum characteristic of vitamin-D formation, whilst biological assay indicated a potency of 500 international units per mg. of original (I). Support is thus given to the theory of intracapillary formation of vitamin-D due to penetration of (II) by ultra-violet rays. . F . O. H.

A n tirach itic p ro p e rtie s of so m e v itam in -D p re p a ra tio n s . A. van H arreveld (Arch, neer- land. Physiol., 1933, 18, 139— 144).—Ptep. “ L ” of Reerink and Van W ijk (A., 1930, 175) has approx. the same antirachitic activity as calciferol. H . G. R.

A n tirach itic value of lucerne as affected by exposu re to su n sh in e in th e cu rin g p ro cess .M. C. Smith and I. A. B riggs (J. Agric. Res., 1933,46,235—240).—Lucerne cured in darkness is deficient in yitamin-£). A synthesis of this vitam in during curing in sunshine is indicated. Material exposed for approx.24 hr. had a mild calcifying action and after 7 days was highly antirachitic. A. G. P.

E ffect of v itam in s on b lood-ca ta lase . H. J .J usatz (Klin. W och, 1932, 11, 1501—1504; Chem. Zentr., 1933, i, 453).—Adm inistration of vitamin-D to rabbits increases the blood-catalase owing to its effect on oxidative metabolism. The increase is more marked when dried yeast is also given. In hyper- vitaminosis-D the blood-catalase falls. A. A. E.

O verdosage of ir ra d ia te d e rg o ste ro l in ra b b its . C hanges in d is tr ib u tio n of p h o sp h o ru s in blood- cells an d p la sm a . G. M. G uest and J . W arkany (J. Biol. Chem., 1933, 100, 445—454).—Large doses of irradiated ergosterol produce a rise of plasma- inorg. P and erythrocyte-org.-acid-sol. P. The same effect is produced more slowly by repeated smaller doses. H. D.

A ccuracy o b ta inab le b y line te s t in v itam in -D d e te rm in a tio n s . K . H. Coward and K . M. K ey (Biochem. J ., 1933, 27, 451—465). H. D.

C om m ercia l a ssay of v itam in -D . W. A. B room (J.S.C.I., 1933, 52,105—IOSt).—Existing methods for the biological assay of vitamin-D are reviewed and a method combining the X -ray and line tes t techniques is advanced. A simple photographic procedure for the prep, of perm anent records of line te s t bones is described.

T he D -v itam in s . II . H. Sim onnet (Z. Vitamin- forsch., 1933,2,94—109; cf. this vol., 432).—Areview.

F o rm u la of v itam in -D r B. C. P. J a n se n , J . P. W iba u t , P. J . H ubers, and P. W . W iardi (Rec. trav. chim., 1933, 52, 366—370).—The prep., by slight modifications of standard methods, of samples of probably pure vitam in-J^ from rice-polishings (A., 1929, 1344) and from yeast (Chick and Roscoe, ibid., 852) is described. Analytical data for these samples together with those already published agree best with the formula C12H 180 2N4S,2HC1 for the air-dried vitamin hydrochloride which, contrary to Windaus, probably does not contain 1 mol. of H ,0 . J . W . B.

U ltra -v io le t ab so rp tio n of c ry sta llin e p re p a r a tio n s of v itam in -D -L- R. A. P eters and J . St . L. P hiltot (Proc. Roy. Soe., 1933, B, 113, 4S—56).—A highly active cryst. prep, (this vol., 99) has max. absorption a t 245—249 m(E When its acid solution is brought to j)a 13 a broad band appears a t 330— 340 nifi (I), with max. absorption a t 233 m^. (I) disappears on heating, and subsequent acidification restores absorption a t 245 mix. The cycle of changes may be repeated and is accompanied by considerable loss of activity. A. C.


R elative ex tra c tab ility of v itam ins-/* [/},] and -G [ j B 2 ] by p la in an d acidified alcohol. H. K.Stiebelin g and I. L. Alleman (J. Amer. Chem. Soc., 1933,55,1477— 1480).—About 50% of the vitamin-jBj (I) in skim-milk powder is recovered from the extracts obtained using 80% (wt.) E tO H alone or containing (0-1JLT) gallic acid, BzOH, or HC1; 35— 40% of (I) remains in the residue. Approx. 30% of the vitamin- B 2 (II) is extracted by the EtOH-gallic acid and practically none with E tO H -H C l; about 33% of (II) is left in the residue. Largelossesof (II) are encountered in all the fractionations. Acidification does not increase the extractability of either (I) or (II). H . B.

N u tritio n . X II. C om p ara tiv e v itam in -/? x values of a n im a l foodstuffs. R . H. A. P limmer, W. H. R aymond, and J . L owndes (Biochem. J ., 1933,27 , 58—65; cf. A., 1931, 988, 1464).—The following vals. (calc, for wet and dry m aterial, respectively, in comparison with yeast as 100) were obtained : egg }7olk, 7, 13; liver, 7, 23; kidney, 8, 33; heart, 8, 36; dried skimmed milk, 10,11; hard roe, 13, 62. Brain, lung, tripe, pancreas, beefsteak, soft roe, fish muscle, and mussels contained only traces. Thus in the fresh state animal foodstuffs are inferior to cereals and pulses bu t superior to fruits and vegetables, whilst when dried they are superior to cereals and pulses.

F. O. H.V ariab ility of the need of th e v itam in -B com

p lex . A. de Vries and G. J . P uister (Arch, néer- land. Physiol., 1933, 18, 71—78).— 15% of cod-liver oil in diet delays growth and causes loss of hair. This is prevented by 12% of yeast, vitam in-IL being the effective agent. H. G. R,

S tud ies on g ro w th . I . G ro w th fac to rs in liv er. I I . E ffect of v itam in s-B j an d -11» on the co n su m p tio n an d u tilisa tio n of food.” C. E.Graham and W. H. Gr iffit h (J. N utrition, 1933, 6,169—194, 195—204).—I. Liver was superior to yeast as a source of vitam in-/i2 for rats.

II . Vitamins-Z?i and -B2 stimulate the consumption and utilisation of food. " A. G. P.

V itam in -B 4 an d adenine. R . D. H ea rd , H. W. K in n er sley , J . R. O’Br ie n , R . A. P eters , and V. R eader (Nature, 1933,131, 617—618).—Vitamin-7?4 and adenine are not identical. Active crystals previously prepared (this vol., 325) consist largely of adenine, and the active residue has yet to be separated. Irradiated adenine so far has not shown vitam in-ii4 activity. L. S. T.

A n tisco rb u tic ac tion of asco rb ic acid . J .Brüggemann (Z. physiol. Chem., 1933, 216, 139— 140).—The antiscorbutic activity is confirmed.

J . H. B.H exuron ic (ascorbic) ac id a s th e an tisco rb u tic

fac to r. L. J . H arris and S. N. R ay (Biochem. J .,1933,2 7 ,580—589).— Hexuronic acid (I) from different sources and after repurification did not vary in an tiscorbutic activity (II). The content of (I) in some cases, measured by the intensity of adsorption a t 265 m;j., of30 natural sources accounts quantitatively for (H). The rate of destruction of (I) under varying conditions and its loss with the development of scurvy resembled

those of (II). (I) is synthesised concurrently with (II) by the plant on germination. H. G. R.

O ccurrence of v itam in -C in th e E riw a n g ra p e . A. J ohannissian and H. B uniatian (Bull. inst. sci. R.S.S. Arm6nie, 1931, 213—218).—All the samples gave a positive Bezssonov colour reaction, which may be employed quantitatively. Orthuzi-Djilari, Muscat, Chardji, and Chatschabasch grapes were richest in vitamin-C. Ch . Abs .

D ete rm in a tio n of v itam in -C in d ip lo id an d te tra p lo id to m ato es. K. M. K ey (Biochem. J.,1933,2 7 ,153—156).—The juice from normal tomatoes contained 22 international units of vitamin-C per c.c. No difference existed between the contents of diploid and tetraploid tomatoes of the same genetic constitution. Hence the no. of chromosomes is not the sole factor controlling the vitamin-C content.

F. 0 . H.R eduction ex p e rim en ts w ith v itam in -C an d

ca rb o h y d ra te deriva tives. II. von E uler (Natur- wiss., 1933, 21, 236).—The adrenal glands have the largest vitamin-C content of any organ; injection of adrenaline lowers this content. On warming with dil. alkali hexose solutions show an absorption band in the ultra-violet spectrum a t 260—300 m^, similar to th a t given by pure vitamin-C preps., and have similar reducing properties. P. G. M.

M icrochem ical m eth o d fo r d e te rm in in g the hexuron ic con ten t (vitam in-C ) of foodstuffs. J . W. B irch , L. J . H a rris , and S. N. R ay (Biochem. J., 1933, 27, 590—594).—The m aterial is extracted with CC13-C02H and titrated with 2 : 6-dichlorophenol- indophenol. In acid solution, other reducing substances, e.g., glutathione, do not in terfere; in the presence of cysteine a special control is necessary.

H. G. R.T itra tio n curve an d d issocia tion co n s tan ts of

v itam in -C . J . W. Birch and L. J . H arris (Biochem. J ., 1933, 27, 595—599).—Determined by a micro-method, using 0-1 c.c. of solution >a-m=4-17, P K =11-57, (if anv) = > 1 4 . The combining wt. agreed with C6H 80 6. H . G. R.

N arco tine an d v itam in -C . S. Maruyama (Sci. Papers Inst. Phys. Chem. Res. Tokyo, 1933, 20, 259— 273).—Pure methylnornarcotine (I) could not be prepared by Rygh’s method from narcotine. The % purity of specimens was calc, from the OMe content. Doses of impure specimens of (I) equiv. to 10—30 X 10^ g., with or without addition of inactivated lemon juice, failed to delay the onset of scurVy in guinea-pigs on a C-deficient diet. P. G. M.

V egetable a ss im ila tio n an d re sp ira tio n . XXI. In d u c tio n p h ases in p h o to sy n th esis an d th e ir b ea rin g on the m ech an ism of th e p ro cess . G. E. B riggs (Proc. Roy. Soc., 1933, B, 113, 1—41).—The influence of intensity of illumination and temp, on the ratio between the initial and final rates of C02 assimilation has been studied on a moss, Milium undulalum. Schemes for the mechanism of the plioto- synthetic process, which permit mathematical trea tment, are formulated. A. C.

P ro d u c ts of ph o to sy n th esis in leaves in a r tificial an d in n a tu ra l lig h t. R. H . D astur and

BIOCHEMISTRY. 647

K. M. Samant (Ann. Bot., 1933, 47, 295— 304).— Starch formation in certain leaves in artificial light was approx. one th ird of th a t in daylight, but sucrose formation was practically the same under both conditions. In diffused sunlight tho to tal carbohydrate formed was > twice th a t produced in artificial light. In non-starch-forming leaves (Allium cepa) sugar formation in diffused light was > three times th a t in artificial light. Differences in carbohydrate formation are ascribed to differences in quality rather than intensity of the light source. A. G. P.

Influence of gaseous im p u ritie s of th e a tm o sp h ere on p la n t t ra n s p ira tio n an d a m e th o d of m ea su r in g tra n s p ira tio n ra te s . A. H eilin g (Pliytopath. Z., 1933, 5, 435— 492).—Small proportions of S 0 2 in the air accelerated and larger amounts restricted the transpiration of plants. The intake of H 20 by leaves of low H 20 content from moist air is increased by the presence of low concns. of S 0 2. Relationships between S 02 concn., transpiration rates, and sensitiveness to injury are examined. Apparatus for determining transpiration rates is described.

A. G. P.D ependence of p la n t ca ta lase ac tiv ity on

n o u rish m en t an d g ro w th . M. B iletzky (Fer- mentforseh., 1933, 13, 467—498).—A high N content [as Ca(N03)2] in the soil produces a high catalase activity (I) in germinating or developed barley and peas, whilst w ith a high P [as CaH4(P 04)2] and low N and K content (I) is absent. Fertilisation with KC1 leads to a val. of (I) intermediate between those due to N and P. Other constituents of the soil, e.g., Na, Mg, and Ca, appear to influence the (I) of germinating plants. Sunlight and, to a smaller extent, lack of H 20 reduce (1), which shows a max. val. with plants kept in the dark a t low temp.

F. 0 . H.Effect of j)CO„ on th e n itro g en -fix a tio n p ro cess

of ce rta in leg u m in o u s p lan ts . P. W . W ilson and E. B. F eed (J. Bact., 1933, 25, 54).—An increase in pC02 from 0-03 to 0-1% considerably increases the growth of clover plants, nodulation, and fixation of N. Further increases in pC 02 do not produce correspondingly greater development. Nodules of C02- treated plants are greater in size and no. and more evenly distributed throughout the root system than in untreated controls. A. G. P.

Influence of v a rio u s n itro g en o u s com pounds and m an n ito l on nodule fo rm a tio n by clover.E. W. H opkins and E. B. F red (Plant Physiol.,1933, 8, 141— 155).—The effect on agar cultures of red clover of K N 03, (NH4)2S 04, urea, asparagine, yeast, and a clover-seed extract varied considerably, but in all cases the size of the nodules decreased with increasing concns. of N. Nodules were distributed mainly on the secondary roots. When mannitol was supplied in addition to N, nodules occurred principally on tho tap roots (as in untreated controls), bu t the actual size of the nodules was inversely related to the N dosage. A. G. P.

N u tritio n of E uglena . I . E uglena g ra c ilis . H. Dusi (Ann. Inst. Pasteur, 1933, 50, 550—597).—Cul- tures can be grown in a synthetic medium in which the source of N is a n itrate or an N H4 salt, the initial

Pn being 6-5—7-5. W ith (NH4),S04 and an initial p a of 7-0, acid is produced, and the final p a after 17 weeks is 4-2. Ca(N03)2 cannot be utilised, and Ca ions appear to be unnecessary for development. Of a large no. of NH a-acids utilised as a source of N, only the simple aliphatic acids, asparagine, histidine, and phenylalanine yielded good cultures. Peptone produces the best results. In the dark, media containing peptones or polypeptides as tho source of N are rendered more effective by the addition of NaOAe. Only those fa tty acids having < 7 C atoms were able to replace AcOH. Strains grown in the light do not require the addition of a fa tty acid to tho medium.

P. G. M.N itro g en m e tab o lism of su g a r-b ee t seed lings :

dependence on th e am m o n ia - a n d n itra te n u tritio n . L. S. L u b a r s k a ja (Z. Pflanz. Diing.,1933, 28, A, 340—368).—The intake of N 0 3-N by sugar-beet seedlings in daylight is less rapid th an th a t of NH3-N. The intake and utilisation of N from NH4N 0 3 resemble more closely those of (NH4)2S04 than of K N 0 3. The utilisation of absorbed NH4* is dependent on the C : N ratio of the plants and therefore on their age and growth conditions. A large proportion of the NH4" intake is transformed into more complex N compounds within 3 hr., the surplus being stored as NH3. The toxic lim it of accumulation of N H3 varies considerably with different plants and is influenced by a no. of factors. The elaboration of N 0 3-N resembles th a t of NH4'-N except th a t the surplus accumulates as N 0 3\ Assimilation rates of N are reduced in darkness, NH4‘ being more affected than N 0 3'. E tiolated seedlings cannot utilise the N taken up, and there follows some protein decomp, w ith a narrowing of the C : N ratio. The la tte r affects not only the ra te of utilisation of N, but also the actual intake of NH4‘. A. G. P.

D is trib u tio n of n itro g en in tobacco w hen th e supp lies of n itro g en an d of lig h t a re v aried d u rin g th e g ro w in g p erio d . W. S. E isen jie n g er (J. Agric. Res., 1933, 46, 255—265).—Stems of tobacco plants had higher contents of to ta l N and NH 3-N than any other plant organs, whereas leaves showed high vals. for % dry m atter and protein. Max. N 0 3' occurred in all instances in the mid-vein of the leaf. P lants grown in darkness for 11 days contained more NH3-N than those grown in light. In the tissues of plants deprived of N for 11 days there remained an ample supply of N 0 3-N. Differences in lighting affect principally the N 0 3' and a-NH2-acid contents. Large excess of N as compared w ith other nutrients produced plants of low dry m atter content but high proportions of N 0 3'. A. G. P.

C ytology, m ic ro c h em is try , an d m ic ro g rap h ics of th e tobacco p lan t. M. J. Chaze (Mem. Manuf. E ta t. Tabacs, 1930, 6, 298; Bied. Zentr., 1932, 3, A, 62).—Nicotine could not be detected in plant tissues by customary alkaloid reagents. Solution of I in Ivl yielded the characteristic ppt. only after washing the tissue in EtOH containing tartaric acid. Nicotine contents of tissues increased with vacuole formation and in general nicotine accumulated in surface tissues, e.g., near stom ata, root hairs, and epidermal cells.

6 1 8 BRITISH CHEMICAL ABSTRACTS.— A.

Nicotine is not a growth activator, bu t an excretion product of the synthesis of N compounds. A. G. P.

D evelopm ent of s tru c tu ra l co n stitu en ts in the b arley p lan t. A. G. N orman (J. Agric. Sci., 1933, 23, 216—227).—W ith advancing growth of barley plants the ash and protein constituents increase a t first, but fall steadily to m aturity. The cellulose fraction shows an initial peak followed by a stationary period. The cellulosan (or associated polysaccharide) portion of the cellulose increases with age more especially after the period when growth increments begin to decline. Lignin increases steadily .with growth until m aturity is approached, and decreases during the final 7— 15 days. The pentose content of the hemicelluloses varies considerably, bu t is lower in m ature than in young plants, although the to ta l pentose material in the plant increased with age. In the young plants, pentoses occur mainly as polyuronides and in mature plant in the cellulosans. A. G. P.

Choline m e tab o lism in p la n ts . I I . G. K le in and H. L in ser (Biochem. Z., 1933,260, 215—225; cf. A., 1932, 1179).—The variations in the free and combined (lecithin) choline contents which occur during growth in the various parts of plants (not young), and the transport of lecithin from one part of the plant to another which takes place, resemble the corresponding changes occurring in seedlings. I t is probable th a t some of the free choline is derived from the lecithin and th a t a converse process does not occur. W. McC.

R ole of a llan to ic acid in h ig h e r p la n ts . It.F osse, P. d e Graeve , and P. E. T homas (Compt. rend., 1933, 196, 1264—1267).—A number of plant seeds contain uric acid, allantoin, and allantoic acid (I), formed by successive enzyme actions. The amount of (I) increases greatly during germination of Trifolium sativum seeds in the dark a t 31°. I t is stable a t pu 7-3, but a t pu 6-8 rapidly gives carbamide and CH0-C02H. R. S. C.

F o rm atio n of s te ro ls in g e rm in a tio n . H.Beu m er (Biochem. Z., 1933, 2 5 9 ,469—470).—During germhiation and growth of peas and beans sterol formation in etiolated is > in normal plants.

P. W. C-C hanges d u rin g rip en in g in the fa t, p h o sp h a t

ide, an d p ro te in con ten ts of seeds. B. R ewald and W. R ie d e (Biochem. Z., 1933, 260, 147—152).— In the growing soya p lant great preferential developm ent of the beans (I) a t the expense of other parts (H) occurs, and whereas in (II) ripening is accompanied by large decreases in the protein (66—75%), fa t (50%), and phosphatide (III) contents all these remain unchanged in (I). In the pods the decrease in (III) is especially pronounced. The decreases are sometimes followed, in the last stages of growth, by slight in creases. The I val. of the oil of (I) is > th a t of the oil of (II), and in (I) the degree of unsaturation of theoil also increases as ripening proceeds. W. McC.

P h o sp h o ru s m e tab o lism in h ig h e r p la n ts . I . D e te rm in a tio n of py ro - an d m e ta -p h o sp h a te , p hosph ite , an d hypo p h o sp h ate in p la n t m a te r ia l.H. Me n g d e h l . II . S te rile cu ltu re s of h ig h e r p la n ts . J . W eissflog . I I I . In tak e a n d u ti lis a tio n of o rgan ic p h o sp h o ru s com pounds by

p lan ts . IV. In tak e an d u tilisa tio n of in o rg an ic p h o sp h o ru s com pounds by p lan ts . J . W eissflog and H . Mengdehl (Planta [Z. wiss. Biol.], 1933, 19, 154— 169, 170—181, 182—241, 242—271).—I. Meta- and pyro-phosphates are determined by hydrolysis to orthophosphate with iV-HCl a t 100° (cf. Lohmann, A., 1929, 208). Phosphites are oxidised by 0-01i\r-I in presence of NaOAc and hypophosphites by 0-02Ar-Br and determined as phosphate.

II . Methods and apparatus are described. Powdered S i02 gel is used as protection against infection by atm . organisms.

I I I . Various org. P compounds served as P sources for maize in sterile cultures and in acid nutrients frequently produced plant yields > from orthophosphates. According to their effects on plants three groups of P compounds are differentiated : (a) Phytin group (e.g., phytic and nucleic acids), (6) ortho-group (H3P 0 4, hexose diphosphate), and (c) esters (liexose monophosphate, glyceryl and sucrose phosphates). The % of to tal P in plants varied with the P source in the order of groups (a)<(c)<(b), b u t the to tal dry m atter yield from (a) was <£ th a t from (c). Plants receiving (a) tended to accumulate in the roots sol. org. P and insol. P. Highest proportions of orthophosphate occurred in plants receiving (b). The stability of the P compounds with respect to the phosphatase of maize was in the order, phytic acid >nucleic acid>glyceryl phosphate>hexose diphosphate.

IV. Pyro- and meta-phosphates, phosphites, andhypophosphites were all taken up by plants. The phosphates were transformed into ortho-salts before passing out of the root system. Phosphites and hypophosphites were translocated throughout the stems and leaves, bu t were not utilised by the plant. Highest P contents occurred in plants receiving orthophosphates or KPOs. Most of the to ta l P of plants is present as orthophosphate. A. G. P.

In tak e of ions by th e p la n t an d i ts re la tio n to th e re sp ira tio n of th e ro o t. A. H. K. P e t r i e (Austral. J . Exp. Biol., 1933,11, 25—34).—When the ra te of respiration of the roots of Algerian oats grown in an artificial mineral salt medium is decreased by reducing the 0 2 supply, the intake of ions by the roots is diminished and the growth of the roots, and to a smaller extent of the shoots, is retarded. These results are discussed on the basis of a general hypothesis of the mechanism of the intake of ions by plant roots from the environment. W. O.K.

S easona l ab so rp tio n of n u tr ie n t sa lts by the F ren ch p ru n e g ro w n in so lu tion cu ltu re s . H. L.Colby (Plant Physiol., 1933,8,1—34).—N 0 3' absorption was affected by S04" starvation < by the absence of any other essential nutrient. K , Mg, and P starvation heavily depressed the N 0 3' intake and in some cases a portion of the absorbed N 0 3' was eliminated from the roots late in the season. Absence of Ca entirely prevented root growth and the absorption of other nutrients in any appreciable degree. Transference of trees from Ca nutrients to Ca-free nutrients resulted in death of the root tips, the survival period depending on the am ount of Ca previously supplied. Absence of Mg restricted the P 0 4" ' intake

BIOCHEMISTRY. 649

to a much greater extent than did absence of K ' or S04". The K absorption curve closely resembled th a t of N, bu t with a slight lag in the early p art of the season. Close correlation is recorded between temp, and rates of K and P intake. A. G. P.

U tilisa tio n of ad so rb ed ions by p la n ts . H.J en n y and E. W. Cowan (Science, 1933, 77, 394— 396).—Experiments with soya-bean plants grown in systems containing only one nutrient ion, Ca, show' th a t to ta l analysis of a soil is an inadequate indication of soil fertility, since there is no diiferentiation between adsorbed and non-exchangeable lattice ions. Since the p lant can feed on the former, the significance of the soil solution appears to have been exaggerated. The solubility concept is not adequate to account for plant growth in humid regions; ionic exchange m ust be taken into account. The study of adsorbed ions in soils should lead to a better understanding of many soil-plant relationships and fertility problems.

L. S. T.Role of ca lc iu m in th e a ss im ila tio n of iro n by

p lan ts . A. G. Schestakov (Ergeb. Veg. Lab.-arb. Prianischnikov, 1930,15, 49—81; Pied. Zentr., 1933, A, 3, 229).—Small concns. of Fe salts m ay injure plant roots, unless Ca" is present in sufficient amounts to exert a protective action. Roots of young maize plants injured by Fe develop new root hairs after addition of C aS 04 to the nutrient. In jury by Fe is intensified if the supply of P 0 4,// is deficient.

A. G. P.P o ta sh [and p la n t life]. K. Schmalfuss (Z.

Pflanz. Düng., 1933, 28, A, 330—335).—The role of K in physiological and metabolic changes in plants is discussed. The influence of K on the state of dispersion of cell colloids and its consequent regulatory effect on the H 20 status and electrolyte concn. in the tissues is emphasised. A. G. P.

P hysio log ical im p o rtan ce of th e m in e ra l elem en ts in p lan ts . IV . D is trib u tio n of p o ta s s ium in th e p o ta to p lan t. W. 0 . J ames and N. L. Penston (Ann. Bot., 1933,47, 279—293).—All organs of the plant contained K , which was particularly abundant in actively growing tissues. The average amount of K per unit wt. of dry m atter is closely related to the rate of dry m atter production. No evidence was obtained th a t K accumulation precedes or induces active growth. Similarity in the distribution of K and of protein suggests th a t translocation of K occurs in the form of K salts of NH2-acids. Storage of K occurs in the upper-middle portion of the haulm, but does not contribute to any great extent to tuber formation. Distribution of H 20 in stems resembles th a t of K . A continuous circulation of K in plants is suggested, viz., movement toward leaves in the transpiration stream and from leaves by way of the phloem. A. G. P.

Influence of variety on the m ineral content of grain. P. Schrtjmre-Pierro n (Compt. rend. Soc. Biol., 1932, 111, 846—848; Proc. Internat. Soc. Soil Sei., 1933, 8, 33).—Varietal differences in ash, Mg, Ca, K , and P 20 5 contents are considerable, the widest range of differences occurring in the Mg vals.

A. G. P.

M anganese an d th e g ro w th of L em nacew .A. Saeger (Amer. J . Bot., 1933, 20, 234—245).—Mn is essential for the growth of Lemnaceoe. In nutrients containing 0-001 mg. Mn per litre normal growth occurs, but with 1 mg. per litre there is some retardation. Al, B, Cu, F, I, or Zn (0-001 mg. per litre) could not replace Mn for this purpose. Lcmnaeece can accumulate reserve supplies of Sin if supplied in appropriate amounts. A. G. P.

M anganese an d th e g ro w th of L etnna . N. A.Clark (Plant Physiol., 1933, 8, 157— 161).—Manganese is an essential nutrient for Lenina major. Normal growth occurred hi nutrients containing Mn (1 in 3 X 10°). Fe supplied as FeCl3 in similar concn. produced large plants of lighter colour. Fe citrate produced dense chlorophyll but smaller plants. The rate of reproduction increased with the proportion of Mn in the nutrient up to a max. beyond which more Mn had no effect. A. G. P.

V acuum in filtra tio n in [p lan t] n u tr itio n exp e r im e n ts . A ssim ila tio n of am m o n iu m . K.Mothes (Planta [Z. wiss. Biol.], 1933, 19, 117— 138). —A method whereby nutrient solutions m ay be introduced directly into the leaf tissues is described. Infiltration of NH4 salts of org. acids into C-deficient leaves (e.g., after exclusion of light for 3—4 days) results in the formation of amides, which is relatively rapid in the case of malic, fumaric, and succinic acids, less rapid for tartaric, pyruvic, and lactic acids, and very slight for AcOH. Asparagine is produced from NH4 malate. From pyruvic acid more N H2- than amide-N is formed. The reverse holds for lactic acid. A. 'G. P.

A n tag o n ism . I I . E ffect of p rev io u s im m e rsion of po ta to tu b e r tis su e in so lu tions of u n iv a len t, b ivalen t, an d te rv a len t ca tions on su b se q u en t ab so rp tio n of am m o n iu m ion . G. F. A sprey (Proc. Boy. Soc., 1933, B, 113 , 71—82).— Immersion of potato tissue in aq. KC1, NaCl, or LiCl increases the subsequent absorption of NH4 from aq. NH4C1, Li having a much greater effect than Na or K. CaCl2, MgCl2, and A1C13 decrease absorption. For each salt a factor, approx. const, for periods of immersion up to 24 hr., is obtained relating absorption by treated and untreated tissue. The effects described represent the sp. effect on tissue previously postulated (this vol., 436) as one factor in antagonism.

A. C.R ela tion betw een th e com position of exuded

p la n t sap an d th e soil so lu tion . W. H. P ierre andG. G. P ohlman (J. Amer. Soc. Agron., 1933, 25,144— 160).—Maizo sap contained approx. 3700 p.p.m. of to tal sohds, of which approx. one third was in the inorg. form. The total electrolyte content of the sap was in nearly all cases > th a t of the displaced soil solution. Of the total P in saps of maize, sorghum, and Sudan grass (150—450 p.p.m.) > two thirds was in the inorg. form. The concn. of P and Si in saps averaged, respectively, 500—5000 and 15—35 times th a t in soil solutions, whereas the [Ca” ] and [Cl'] were lower and the [N 03'] was very variable. A correlation between the proportion of P in saps and in the corresponding soil solutions is indicated. Variations in soil acidity of p B 4-6—6-6 affected neither


the pn of the sap, which maintained a fairly const, level (4-4— 4-8), nor its Ca", P, and Cl' contents. W ith higher ranges of p n there was an increased Si content. Poor growth of sorghum and Sudan grass on acid soils cannot be attributed to inability of the plants to accumulate Ca and P in their saps. Successive daily samples of sap contained const, amounts of total P but increasing proportions of inorg. P and Cl'. No consistent variations in Ca" and Si contents were observed. A. G. P.

N a tu re of p o ta ss iu m com pounds in p lan ts . S. L. I nosBmzev (Ergeb. Veg. Lab.-arb. Priani- schnikov, 1930, 15, 85— 101; Bied. Zentr., 1933,3, A, 225—226).—The greater part of the K of plants exists in a complex non-dialysable form. During electrodialysis 35% of the to tal K of young pea plants and 14% of th a t in m ature plants appears a t the cathode and 16-2 and 18%, respectively, a t the anode. Dialysable K is probably in an org. form. Rates of deposition of anodic and cathodic K (in respect to the to tal deposited in each case) are similar and unaffected by the nature of the membrane used.

A. G. P.D istinctive effects of th e deficiency of c e rta in

e ssen tia l e lem en ts on th e g ro w th of tobacco p lan ts in cu ltu re so lu tio n s . J . E . McMurtrey (U.S. Dept. Agric., Tech. Bull., 1933, No. 340, 42 pp.). -—Leaves of plants growing in N-deficient solutions are light green, the lower ones tending to yellow, and roots are long, little branched, and white. P starvation produces dark green leaves, and long roots which are little branched and brown as a result of accumulation of Fe on the surface. Deficiency of Iv and Mg produces more localised effects, notably typical forms of chlorosis on older leaves. Absence of Mn, Fe, S, B, and Ca affects principally the young growing tips. Chlorosis caused by lack of Fe is characterised by retention of green colour by the leaf veins and in the case of Mn by general necrotic spotting. Chlorosis induced by S starvation is shown by leaf veins remaining paler than the tissue. Roots are more abundant and whiter than in Mn or Fe chlorosis. Deficiency of Ca or B results in the death of terminal buds, the breakdown process being of a characteristic kind in each case. A. G. P.

P h o sp h o ru s con cen tra tio n of th e exuded sap of m aize as a m easu re of th e availab le p h o sp h o ru s of th e soil. G. G. P o h lm a n n and W H. P i e r r e (J. Amer. Soc. Agron., 1933, 25, 160— 171).— Under greenhouse conditions the inorg. P content of maize sap was closely correlated with the H 20-sol. P 0 4" \ the available P 0 4'" (Truog), and with the response of the plant to P fertilisers. Some increase in [P04"'] of the sap with the age of the plant was general. A. G. P.

In tra c e llu la r hydrogen-ion concen tra tion stu d ies . V III. C y top lasm an d vacuole of L im - nob iu m ro o t-h a ir cells. R. Chambers and T. Ejerr (J. Cell. Comp. Physiol., 1932, 2 , 105— 119).— Penetration of various dyes and their behaviour on ingestion is examined. The normal cytoplasmic p a was 6-9, changing, on injury, to 5-2; th a t of the vacuole was 5-2, irrespective of the reaction of the medium or of seasonal or growth changes, but

changing on death to 6-4. The wall of the root hair in living and dead cells was more permeable to NH3 at the tip than elsewhere (cf. this vol., 627). A. G. P.

H ate of p en e tra tio n of dyes in to Valonia w ith sp ec ia l re ference to so lub ility th eo rie s of p e rm e ab ility . S. C. B rooks and M. M. Brooks (J. Cell. Comp. Physiol., 1932, 2, 53—73).—Basic dyes penetrate irrespective of their degree of dissociation. Acid dyes penetrate only if their p K vals, are > a certain val. lying between 3-0 and 5-3. Sulphonic acid dyes examined did not penetrate. A. G. P.

C hem ical ve rsu s m o rp h o lo g ica l species d ifferences. S. C. Brooks (Science, 1933, 77, 221— 222).—Chemical characteristics (sap analysis) and environmental data for different reputed species of Valonia are discussed. L. S. T.

D is trib u tio n of copper in th e K a rak a tree (C orynocarpus Icevigata). N. P. P itc a i t i i ly andF. P. W orley (J. Agric. Sci., 1933, 23, 204—207).—Cu occurred in all organs of the tree and especially in leaves and the flesh of the fruit. A considerable proportion is sol. in EtOH. A. G. P.

M in era l co n stitu en ts of A rte m is ia afra.G. W . B. van der L ingen (Analyst, 1933, 58;280).—The dried leaves contained K„0 3-32, Na20 1-19, MgO0-68, CaO 1-95, P 20 5 0-79, F e¡03 0-03, Cl 0-57, protein 17-63, to tal ash 8-94, and S i02 i-05%. J . G.

C om parative com position of hom ologous vine leaves tak en fro m fru itfu l s tem s an d s tem s deprived of g ra p es . H. L a g a tu and L. M aume (Compt. rend., 1933,196, 1168—1170).—The N, K 20, CaO, and the sum of N, K 20 , and P 20 5 contents of vine leaves are less on fruit-bearing than on sterile stems, whilst the individual val. for P2Os is greater in the same sense. K vals, indicate EL debt.

A. C.A m p h ia c liyr is dracunculoides (DC.), N u tt. :

flow ering b ra n c h e s . L. E . H arris and I. Griffith (J. Amer. Pharm. Assoc., 1933, 22, 306—309).—The dried flowering tops (5-22% ash) gave 5% of material, sol. in light petroleum, having sap. val. 158-36 and I val. 38-31. The EtO H extract (13-75%) contained a glucoside. E. H . S.

P ro d u c ts of Cocos nucífera . I I . J . P. C. Chandrasena (Biochem. J ., 1933 , 27, 3—4).—The following data were obtained for the “ milk ” of the coconut before and during germination, respectively : d 1-014—1-025, 1-008—1-020; p a, 4-8—5-4, 4-8—5*9; % total solids, 4-01—7-31, 2-90—5-02; % ash of total solids, 9-94—18-99,11-37—14-30. The p a, which remains const, even during germination, approximates to the optimum for Ricinus lipase. F. O. H.

O ccurrence of ro ten o n e an d re la te d com p ounds in th e ro o ts of Craccá v irg in iana . E. P. Clark (Science, 1933, 77, 311—312).—Rotenone, de- hydrorotenone, tephrosin, and a colourless cryst. substance, C22H 240 4, m.p. 131°, have been obtained from the roots of C. virginiana. L. S. T.

R otenone in a species of S pa tho lobus, H. A. J ones (J. Amer. Chem. Soc., 1933, 55, 1737— 1738)— Rotenone is isolated in about 1% yield from the COMe2 extract of the root of S. roxburghii, Benth.

H. B.

BIOCHEMISTRY. 651

C o n stitu en t of san ton in -free w o rm seed . H.N akam ura, T. O hta, and G. H u k u ti (Proc. Imp. Acad. Tokyo, 1933, 9, 91—93).—A cryst. compound, temisin (C15H 20O3), has been obtained in 0-3—0-5% yield from a variety of Artemisia marilima by the following procedure: the drug is boiled for 5—6 hr. with milk of lime, the filtrate is acidified and extracted with CHClj, and the residue from the extract is taken up in warm 20% E tO H ; the temisin which separates is recryst. from EtOH, m.p. 228°, [a]1,? + 65-69° (Ac derivative, m.p. 86°; JBz derivative, m.p. 133°). Oxidation w ith Na2Cr20 - yields temisone, m.p. 130— 131° (oxime, m.p. 232—233° ; tetraliydro-compound, m.p. I l l — 112°); hydrogenation yields tetrahydro- temisin, m.p. 231° (sublimes), [a]|° +79-64° (Ac derivative, m.p. 83°); heating with Se a t 320—340° yields a colourless oil, b.p. 133— 138° a t 16 mm. Lpicrate, m.p. 96° (C13H 14-C6H30 7N3)]. P. G. M.

Iso la tio n of pyrocatecho l fro m p ig m en ted onion sca les an d i ts re la tio n to d isease -re sis tan ce in onions. K. P. L in k (J. Biol. Chem., 1933, 100, 379—383).—Pyrocatechol (I) was isolated from pigmented onion skins by taking up the residue from the C0Me2 extract (A., 1929, 613; 1930, 122), with H 20, pptn. with neutral Pb(OAc)2, filtering, and decomp, of the Pb compound with H 2S04. The filtrate is made alkaline with NaH C03, extracted with E t20 , conc., and extracted w ith CGH G; the latter is removed and the residue recryst. from H 20 . (I) is not obtainedfrom non-pigmented skins and is more toxic to Colletotrichum circinans than protocatechuic acid.

H . D.Effect of g eo g rap h ica l fac to rs an d th e ty p e of

fo rests on th e tu rp en tin e s fro m P in u s sy lve s tr is . V. K restin sk i, S. Malevskaya, and F. Solodki (J. Appl. Chem., Russia, 1932, 5, 950—957).—The variety of the tree, and not the local conditions, governs the typo of the product. Ch. Abs.

Aliyella dam ascena, L . G. Ottolino (Officina,1932, 5, 273—276).—Oil (32—40%) extracted from the seeds by E t20 has sap. val. 230, acids (as oleic) 41-73, ester val. 146-68, volatile fa tty acids 4-4, nonvolatile [acids] 83-62%, m.p. 10—12°, f.p. -1 6 ° to —20°. Ch . A bs.

Seeds of P soralea corylifolia , L inn . I. H. S.Jois, B. L. Manjunath , and S. V. R ao (J. IndianChem. Soc., 1933, 10, 41—46).—The light petroleum extract of the crushed seeds contained a cryst. solid, psoralen, Cu H G0 3, m.p. 162°, and an oil which on saponification gave resinous materials with the colour reactions of sterols, and palmitic, oleic, linoleic, stearic, lignoceric, linolenic, and resin acids.

H. A. P.C om position of seeds of T heve tia neriifo lia ,

Ju ss . I. N. Ghatak (Bull. Acad. Sci. Allahabad,1932, 2, 79—84).—Extraction of the air-dried kernels with light petroleum yields 68-7% of a non-drying oil. The oil-free kernels are extracted with 95% EtO H and the extract is evaporated in vac. to a syrup, which solidifies and is extracted again w ith CHC13. The residue, after evaporation of CHC13, is recryst. from dil. EtOH in needles (thevetin, m.p. 192°, C20H3o06, Mr! -66-85°). Thevetin is tasteless and non-toxic, whilst thevetoxin (C16H 24Og, m.p. 178°, [a]™ -76-1°)’,

which is isolated from the residue after CHC13 extraction, is b itter and very toxic. Thevetin is a glucoside which, on hydrolysis, yields glucose and thevetigenin, m.p. 83° (pink in conc. H 2S04 with green fluorescence); thevetoxin similarly yields glucose and tlievetoxigenin, m.p. 81°. P. G. M.

C om position of th e f ru it of T rib u lu s te rres tr is , L inn. N. Ghatak (Bull. Acad. Sci. Allahabad, 1933,2, 163—170).—5% of oil is extracted from the powdered fruit with light petroleum ; on keeping, behenic acid, m.p. 83°, separates. Saponification gives mixed fa tty acids which contain oleic acid 27, linoleic acid 57, and saturated acids (palmitic and stearic), 16%. From the residue after petroleum extraction there wras obtained an impure glucoside, a phlobaphen, and an acidic substance, m.p. 189—191°.

P. G. M.C om position of th e non-phenolic p o rtio n of

b ay oil. S. P alkin and P. A. W ells (J. Amer. Chem. Soc., 1933, 55, 1549—1556).—The constituents are myrceno, cineol, dipentene, and limonene, and small amounts of citral, oc-phellandrene, a-pinene, and an unidentified geraniol-like alcohol. Little or no methylchavicol and methyleugenol are present.

H . B.C havicol an d eugenol fro m oil of bay . S.

P alkin and P . A. W ells (J. Amer. Chem. Soc., 1933, 55, 1556— 1558).—Details are given for the separation of chavicol, m.p. 16°, and eugenol, m.p. —7-5°, from the phenolic portion of the oil. H. B.

A b so rp tio n sp e c tru m of th e unsapon ifiab le m a t te r fro m w h e a t-g e rm oil. R. A. Morton and J . R. E disbury (Nature, 1933, 131, 618).—D ata for four different samples of wheat-germ oil extracts are recorded. L. S. T.

S te ro ls of th e b a rk of L o p h o p eta lu m to x ic u m .I. H. D ie ter l e , H. L eon hardt , and K . D orner (Arch. Pharm ., 1933, 271, 264—268).—The bark (100 g.) contains lupeol (2 g.), betulin (0-7—0-8 g.) (dipropionate, m.p. 164— 165°), and a sterol, probably C2oH480 3j m.p. 279—281° (0-3 g.). R. S. C.

C aro teno ids of th e ap rico t (P runus ann en ia ca ).H. B rockmann (Z. physiol. Chem., 1933, 216, 45— 48).—Apricots contain considerable amounts of (3- carotene and traces of y-carotene and lycopene.

J . H . B.C olouring m a t te r of Ja p a n ese eg g -p lan t

(N asu). C. K uroda and M. W ada (Proc. Imp. Acad. Tokyo, 1933, 9, 51—52).—The aglucono obtained by hydrolysis of the colouring m atter of eggplant is identified as deliphinidin chlorido (I). The glucoside, in addition to the decomp, products of (I), gives ^-coumaric acid on hydrolysis and when fused w ith NaOH. A. L.

C a lib ra tio n of flo w er-co lo u r in d ica to rs . E . P.Sm ith (Protoplasma, 1933, 18, 112—125).—The colour-pu ranges of anthocyanin colours are determined and their relationships to the reaction of cell saps discussed. Colour charts are given.

A. G. P.C onversion of p ig m en ts of r e d algae in to m eso -

b iliru b in an d m eso d eh y d ro b iliru b in . R. Lem berg and G. Bader (Naturwiss., 1933, 21, 206).—

,2 BRITISH CHEMICAL ABSTRACTS.— A.

Further evidence is given for the close relation between these and the bile pigments. Scission of the chromo- proteins is effected by hot MeOH-KOH, and the phyeobilins formed are converted into mesodehydro- bibrubin (I). Phycoerythrin gives, in addition, meso- bilirubin (II). These are identified as Me, esters. The bluish-green dehydrobilirubins form the most stable stage of hydrogenation in the bile pigments.(I) is identical with mesobiliverdin, and is the first (green) phase of the Gmclin reaction for (II). Phyco- erythrobilin appears to be identical with urobilin of urine, and phycocyanobilin a dehydrogenation product or isomeride of (I). The formulation of phyeobilins as bile pigments with saturated sido-chains indicates their origin from chlorophyll or one of its precursors. A. C.

Soluble su g a rs of Lernanea nodosa, K ütz. H. Colin and J . Augier (Compt. rend., 1933,196,1042— 1043).—The principal sugar in the EtO H extract of fresh-water Lemanea is floridoside, identical with th a t obtained from Rhodymenia pahm la (A., 1930, 825). Trehaloso is found in tho EtO H mother-liquors.

A. C. _O ccurrence of polylaevans in n a tu re a n d th e ir

possib le re la tio n sh ip to p r im a rily fo rm ed su g a r . W. F lörsheim (Diss., Hamburg, 1930 ; Biod. Zentr.,1932, 3, A, 50—51).-—Polylaevans were present in Scilla maritima. The glucose content of hydrolysed polylaevans decreased with increasing mol. wts. The reducing substances produced by acid hydrolysis increased in the order mono-, di-, tetra-laevans. Sucrose is probably the first sugar formed. All plants containing polylcevans in leaves or stems accumulate this material in rhizomes. All polylaevans in admixture with sugars are fermented by yeast. A. G. P.

O ccurrence an d m ic ro c h em is try of th e am y loids in p lan t-ce ll m em b ra n es . O. H opmann (Diss., Münster, 1930; Bied. Zentr., 1932, 3, A, 50).—W ith various plant materials examined removal of amyloids by suitable solvents from cell walls loaves a framework of cellulose, and conversely the dissolution of cellulose leaves a membrane showing amyloid reactions. In certain cases lamellae prior to lignification exhibited amyloid properties. A. G. P.

T a n re t 's “ sy n a n th rin .” H. C o h n and A. C haudun (Bull.Soc. Chim. biol., 1933,15, 402—406). —ß-Methylglucoside is obtained from “ synanthrin ” (A., 1S93. i, 618) after acid hydrolysis by treatm ent w ith 70% MeOH. ■ H. D.

Pei'sica vu lgaris . I . P resence of am ygdo- n itrile -g lu co sid e . J . R a b a ts (Bull. Soe. Chim. biol., 1933, 15, 385—394).—The EtOH extracts of P. vulgaris are treated successively with invertase and emulsin, and the changes in optical rotation and reducing power observed. The formation of HCN was noticed. Amygdonitrile-glucoside (I) is obtained by extraction with boiling 85% EtO H, cooling to remove wax, distillation of EtOH, and filtration of the aq. residue to remove chlorophyll, addition of Pb(OAc)2, removal of the Pb, and concn. of the solution in vac. The residue is extracted with EtOAc and tho latter removed. (I) is recrystallised from the residue. I t is rapidly hydrolysed by emulsin. Z-Phenylglycollic acid

is produced from (I) by boiling with conc. HC1, dilution with H 20 , and extraction with E t„0.

H. D.P resen ce of su cro se in vine leav es. G. Barbera

(Annali Chim. Appl., 1933, 23, 99—104).—This is confirmed by tho change in rotation accompanying the action of invertase on the saccharine extracts of the leaves, and by determinations of the sugars.

T. H. P.N e c ta r sec re tion of th e tu lip tre e o r yellow

p o p la r. G. E. Marvin (J. Econ. Entom., 1933, 26,170—176).—The average sugar content of nectar from freshly-opened flowers was 16-7%, rising to 35-9% on the second day. The to tal nectar per flower was from 0-5 to 3-2 g. . A. G. P .

R ate a t w h ich honey bees r ip e n honey. O. W . P ark (J. Econ. Entom., 1933, 26, 188—193).—Nectar containing 45% sugar contained approx. 60% of sugar when deposited in the comb. Green honey in the comb screened from bees increased in sugar concn. from 65 to 80% in 3 days. A. G. P.

A lcohol a s a s u g a r e x tra c ta n t in p lan t-tis su e an a ly sis . A. C. H ulme (Biochem. J ., 1933, 27,116—120).—No appreciable error (by tho formation of aldehydes etc.) results from tho use of hot EtOH in the determination of sugar in plant leaves, the results so obtained being comparable with those given by aq. extraction. F . O. H .

N itro g en o u s co n stitu en ts of a v a r ie ty of R haphanus sa tivn s , “ S a k u ra jim a -d a ik o n .” Iv. Y oshimura, T. E f u j i , and T. I wata (J. Agric. Chem. Soc. Japan, 1932, 8 , 1060—1063).—From 66-09 kg., adenine (HC1) 0-6, arginine (H N 03) 1-2, choline (Au)0-6, and trigonelline (HC1) 0-1 g. were isolated.

Ch. Ab s .i-T yrosine fro m Vicia faba , L . H . Sciimalfttss,

A. H e id e r , and K . W inkelmann (Biochem. Z., 1933, 259, 465—46S).—A Pb(OAc)2 method is given for separation of tyrosine from dihydroxyphenylalanine. The green pods of Vicia faba contain Z-tyrosine and this with 3 : 4-dihydroxyphenylalanine correspond in the bean with tyramine and hydroxytyramino of broom-pods. In both cases the amount of monohydroxy-compound is small and of the dihydroxy- compound relatively large. P. W . C.

A lkalo ids fro m Leontice e tcersm an i. A. P. Orekhov and R. A .K onovalova (Khim.Farm. Prom.,1932, 10, 371—375).—Dried bulbs of L. ewersmani (alkaloids 0-4%) contain leontamine, C14H26N2 (hydrochloride; di-iodomethylate; chloroplatinate; picrate), and leontidine, m.p. 116—118°. Ch. Abs.

A lkalo ids of C hinese C orydalis anibigua, C ham , e t Sch. (Yen-hu-so). IV. C orydalis-./ an d -II. T. Q. Chou and G. H. W ang (Chinese J. Physiol., 1933, 7, 35—3S).—In addition to tho nine alkaloids previously obtained (A., 1929, 1085), corydalis-J, C30H36O5N2, m.p. 118°, [a]g +125° in EtOH (hydrochloride, m.p. 235°), and corydalis-K , m.p. 225°, [a]'if —250° in CHClj, have been isolated. The physiological properties of the two alkaloids are briefly described. F . O. H.

A lkalo ids of C hinese d ru g P e i-m u , Fritillaria rot/lei. I I . F r itim in e . T. Q. C h ou and K. K.

BIOCHEMISTRY. 653

Chen (Chinese J . Physiol., 1933, 7, 41—43).—Pei-mu of the Szechuan variety (I) appears to contain active principles different from those of the variety previously investigated (A., 1932, 1178). From the corms of (I) was isolated fritimine, C38H G20 3N2, m.p. 167°, [a]“ —50° in EtO H (hydrochloride., m.p. 230°). The alkaloid has a min. lethal dose of 40 mg. per kg. body-wt. in mice and raises the blood-sugar of rabbits. F. 0 . H.

D im in u tio n in th e am o u n t of a lka lo ids in P o lygonum a m p liib iu m ow ing to th e p ro tec tive action of w a te r . A. Sanna (Aimali Chim. Appl.,1933, 23, 51—56).—Plants growing in soil which was flooded during the first and fourth years and dry during the second and third were examined. During the dry years the plants were covered with hairs, emitted a viscous hquid over the epidermis of stem and leaves, and contained appreciable proportions of alkaloids. During the wet years they showed no hairs or hquid excretion, and only traces of alkaloids.

T. H. P.P e n e tra tio n of ch lo rid es in to th e ro o t of the

tu rn ip (B rassica ca m p es tr is ). M. V. H omes (Protoplasma, 1933, 18, 161— 193).—Relationships between the rate of penetration of Cl', the concn. of the cell sap and of the external solution, and the survival period (I) of the cells are examined. The proportion of Cl' entering the cell and (I) are influenced by the cation associated with the Cl'. Among chlorides examined the penetration of Cl was least and the toxicity greatest in the case of N H 4C1. A. G. P.

B ehav iou r of p la n t cells to w ard s h eav y -m eta l sa lts . H. K aho (Planta [Z. wiss. Biol.], 1933, 18, 664—6S2).—The toxic action towards the plasma of red cabbage cells of Zn salts was in the order B r '> C l'> N 0 3'> 0 A c '> S 0 4" ; of Cd salts, I > N 0 3'> Cl', 0 A c '> B r '> S 0 / ', and of Co salts, C N S '> B r', N 03'>C1', 0 A c '> S 0 4". Relationships are demonstrated between the toxic effects of these salts and their action on the swelling of hydrophilic gels and their diffusion rates in gelatin and agar. Heavy-metal salts on contact with the plasma surface produce a protective layer (by irreversible coagulation) which reduces the ra te of further penetration of the salt. The permeability of this layer to salts of the same metal decreases in the order of the lyotropic series C N S '>I'. . . S 04". A. G. P.

T oxic ac tion . VI. T ox icity of a lip h a tic ketones to w ard s p o ta to tu b e r . W. J . R ees (Protoplasma, 1933,17, 499—508).—The toxic action of ketones, as measured by the exosmosis of electrolytes from cut potato tubers, resembles th a t of the alcohols rather than aldehydes. The relative in crease in toxicity associated w ith each increment of CH2 to the C chain is less consistent for ketones than for alcohols. COMeBu^ is more toxic than COMeBu“.

A. G. P.Effect of e igh teen n o rm a l a lip h a tic alcohols on

grow th of L u p in u s a lbus. D. I. Macht and J . D. Meyer (Amer. J . Bot., 1933,20,145— 149).—Toxicity of the simple aliphatic alcohols increased directly with mol. wt. for the first five of the series, but not thereafter. sec.-Alcohols are in general less toxic than the corresponding primary alcohols. Mixtures of alcohols

produce in some cases antagonistic, and in others synergistic, pharmacological effects. A. G. P.

N u tritio n a l d iso rd e rs [of p lan ts ] in a lka line so ils as caused b y deficiency of ca rb o n d iox ide.J . F. B rezeale and W . T. McGeorge (Arizona Agric. Exp. Sta. Tech. Bull., 1932, No. 41, 113— 153).— Black alkali soils do not, in most cases, contain sufficient alkali to be directly toxic. Extreme deficiency of C02 is an im portant factor in their low fertility. Plants are unable to absorb P 0 4'" or N 0 3' from solutions having p n > 7 -6 approx. Optimum absorption occurs at p n 6-8— 7-0. The reaction of acid or alkaline nutrient solutions is gradually changed by growing plants towards neutrality, the change from alkalinity being more rapid than th a t from acidity. Plants absorb P 0 4" ' from phosphates a t approx. equal rates irrespective of the base present, and do so more rapidly in daylight than in darkness. The effect of variations of p„ on nutrient absorption is the same for a no. of different species of plants. P 0 4" ' absorption is slightly depressed by a high concn. of neutral salts in the nutrient. Transpiration rates of plants are not materially affected by alkalinity up to p a 9. Transpiration and ion absorption occur independently. In alkaline media plant roots elongate, although P 0 4'" and N 0 3' are not absorbed. The ameliorative action of farmyard manure on black alkali soils is largely due to the C02 evolved during its decomp. A. G. P.

B u ffe r capacity [of p la n t sa p s ] an d th e inc idence of p la n t d isease . F . W ille (Zentr. Bakt. Par., 1933, II , 8 7 ,301—331).—The period of infection of conifers with a no. of diseases is associated with low p n and low buffer capacity in the saps, low H 20 content, and rapid C 02 assimilation. Buffer capacities of saps with respect to HC1, H 2S 04, H N 0 3, H 2SiF6, and H F are recorded. The significance of the results in the protection of plants against disease is noted. A. G. P.

C hem ical com position of sp o re s of vegetab lep a ra s ite s of ce rea ls . S. Campanile (Ann. R. Staz. chim.-agrar. sperim. Roma, 1932,14, No. 286, 3— 11). —The ashes of oat-, rye-, wheat-, and maize-smut spores (Ustilago spp.) are similar in composition to those of the affected parts of the hosts, and the sp. variations hi the hosts are reproduced in the parasites. Notably high amounts of K and N arefound in the spores. R. K . C.

V aria tio n s in th e to ta l n itro g en con ten t of n o rm a l an d leaf-ro ll p o ta to es . G. Cockerham (Proc. Leeds Phil. Soc., 1933, 2, 375—382).— Pronounced differences in the diurnal variations of the to tal N content of laminae and petioles of normal and leaf-roll potatoes indicate an interference with the normal metabolism of nitrogenous substances by the presence of the sp. virus. N. M. B.

W aln u t yellow s in re la tio n to a sh co m p o sitio n , m an g an ese , iro n , an d o th e r a sh co n stitu en ts . A. R. C. H aas (Bot. Gaz., 1933, 94 , 495— 511).— In diseased trees the bark had higher Ca, Mg, Mn, inorg. P 0 4" ', and to tal ash contents, and the leaves higher Mg, Mn, Fe, and inorg. P 0 4" ' contents than did healthy trees. A. G. P.


Influence of infection on th e te m p e ra tu re of an d ca rbon dioxide evolution fro m p o ta to es . M.E glits (Phytopath. Z., 1933, 5, 341—379).—Infection of tubers .with B. phytophthorus results in a rise in temp, accompanied by increased CO, production.

A. G. P.Influence on infection by r u s t of th e im m e rs io n

of inocu lated leaves in so lu tions of m in e ra l sa lts an d o th e r su b stan ces . G. Gassner and K. H assebrauk (Phytopath. Z., 1933, 5, 323—342).— Immersion during 3—4 nights in Iv and P 0 4'" solutions retarded, and in those of N compounds (N 03',N H 4 salts, asparagine, glycine, etc.) increased, the infection. The effect of N compounds is closely related to the C supply of the plants. A. G. P.

P re p a ra tio n of palseobotan ical sec tions by th e peel m eth o d . R. Graham (Stain Tech., 1933, 8,65—68).—A plane surface of the petrifaction is etched with acid. This removes a th in layer of matrix, leaving the carbonaceous m aterial (I) standing in relief. A solution of cellulose n itrate is poured over the surface. After evaporation of the solvent, the film, containing the embedded (I), is peeled off and used as a thin section. Various grades of cellulose n itrate were tried, and the effect of various solvents and plasticisers was studied. H. W. D.

M eta l ex trac tio n a p p a ra tu s fo r phy to ch em ica l w o rk A. F. Sievers (J. Amer. Pharm. Assoc., 1933,22,182—184).—A modification of B ryant’s apparatus (A., 1929, 1161) consists of a tubular condenser and a ' jacketed receiver, and the whole apparatus is made of Sn-lined Cu. E. H. S.

M ethod an d a p p a ra tu s fo r th e s tu d y of p e rm e ab ility of g ases th ro u g h th e b i r d ’s eg g -sh e ll. A. L. R omanoff (Science, 1933, 77, 393—394).

L. S. T.D e te rm in a tio n of fluo rine [in p la n t m a te r ia ls ] .

O. B. W in ter and L. B utler (J. Assoc. Off. Agrie. Chem., 1933, 16, 105—107; cf. this vol., 242).—5—20 g. of m aterial are moistened with saturated aq. Ca(OH)2, dried, and ignited a t dull redness. If not thoroughly ashed i t is broken up, moistened with H 20 , dried, and re-ignited. The residue is mixed with a few pieces of glass or porous pot, aq. HC104 is added, and the F determined by distilling off the H 2SiF6 as described previously. J . W. S.

D e te rm in a tio n of iodine in b io log ical m a te r ia l.J . Schwaibold (Biochem. Z., 1933, 259, 453—454).— A reply to Pfeiffer (this vol., 330). P . W. C.

D e te rm in a tio n of to ta l b ase [in b io logical m a te r ia l] . S. L. W rig h t and C. L. Allison (J. Biol. Chem., 1933, 100, 1— 11).—Removal of the P 0 4 allows the use of the benzidine method for material rich in Ca and P. Preliminary titration for excess H„S04 has been eliminated and the ignition standardised. H. G. R.

C o lo rim etric m ic ro -titra tio n of b ase s in non- aqueous so lven ts. I . O. M. H e n riq u es (Bio-

chem. Z., 1933, 260, 72—104).—“ Non-aq.” solvents (e.g., a mixture of C0H c 61-6, EtO H 37-1, and H 201-3%) havo m any advantages (e.g., longer p a scale, reduced dissociation of weak electrolytes, low solubility products, no C02 error) over aq. solvents. Forty suitable indicators are listed and complete details of procedure are given (example, titra tion and determination of dissociation const, of A1C13,6H20), whilst modifications and applications to biochemical and clinical work are indicated. W. McC.

A b so rp tio n a p p a ra tu s fo r m ic ro -d e te rm in a tio n of vo latile su b s tan ces . I. M ic ro -d e te rm in a tio n of am m o n ia . E. J . Conway and A. B y r n e .I I . D e te rm in a tio n of u re a a n d a m m o n ia in body flu ids. E. J . Conway (Biochem. J ., 1933, 27, 419— 429, 430—434).—I. The test solution is placed in the outer of two chambers (I) formed by the outer wall of a circular dish and a concentric glass ring within ; the NH3 liberated by addition of saturated aq. K 2C 03 is absorbed by standard acid in the inner chamber (II), and the excess titrated . Tho influence of variation of temp., p a, the vol. of (I) and (II), and of salt addition to (I) is studied ; 99-5% absorption occurring in 60 min. a t 40° or in 100 min. a t room temp. For the titration, a modification of Tashiro’s indicator is described. Amounts of NH4 salts containing < 0-014 mg. N can be determined with a coeff. of variation of 0-5%.

II . Blood-urea is determined by placing 1 c.c. of 0-00667V-H,S04 in (II) and 0-2 c.c. of blood together with a glycerol extract of urease diluted with aq. N aH2P 0 4 in (I). The apparatus is incubated for 10 min. a t 38°. 1 c.c. of saturated aq. K 2C03 is added to (I) and the incubation repeated for 1 hr., when the excess acid is titrated . Protein-free filtrates and urine may be analysed in tho same way. The error (standard deviation) is 0-6 mg. per 100 c.c.

H. D.M icro -iodom etric d e te rm in a tio n of go ld in

a n im a l o rg a n s . S. T ukats (Biochem. Z., 1933,260, 143—146).—Org. m atter is destroyed by heating with H 2S 04 and H N 03 successively and pptn. of the Au is completed by addition of H 2C20 4. The ppt. is dissolved in aqua regia and aq. Cl,. H N 03 and Cl2 are removed, K I and starch are added, and tho solution is titra ted with 0-005V-Na2S ,0 3. 0-5— 1-5 mg. of Au can be determined with an error of 3—1-3%.

W. McC.F olin -D enis co lo rim etric m eth o d . H. F u ji-

w a r a and E. K a t a o k a (Z. physiol. Chem., 1933, 216, 133—137 ).—Aromatic amines, phenols, hydroxypheny 1 derivatives, aromatic aldehydes, naphthol, hydroxyquinoline, aliphatic hydroxy- and keto-acids, NH2OH, dimethylaminoantipyrine (but not antipyrine), indole derivatives, and most moiphine alkaloids reduce phosphotungstic and phosphomolybdic acids and K 3Fe(CN)6T-FeCl3, giving a blue colour. Of the sugars, only fructose, hydroxymethylfurfuraldehyde, and inulin give the reaction. J . H. B.

BRITISH CHEMICAL ABSTRACTS

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