Tftfi; LITHIUM Atm~u1:~1JM HYDRIDE REDTJCT!Oli ' ' . . . ' I

by

Aaron.Feldstein B~A .. ; Brooklyn College, 1944

Submitted to th$ DepartJnent pf Ohemi~try and_ the 1aouJ.ty_ot the Graduate St-l~ool of 'the Univ$rsity of Kansas in pa.rt!al t ult illln.ent of th& requirem.Qnts :ror the degree of Doctoi' of Plliloaophy.

Advisory Oolill!l.ittee;

October, 1952

R0005b 63528

I am deeply .indebted to :Oro C. A. Ve.nder Wert

tor his. g~ne:rou_s.• ;}1tJ.gge·st:tons, eneoUl!a·gament., and !ntereatwithout which this woric ooti1d not have been eomp1etad.. To my pt1.renta, :t wiah' to exp:tt&rs$ •Y gl"atitude fo.r thelri mo~a.l st1mw.as and tina~c1al help which made continuation or the WOl'k possiblee

TABLE OF OONTEMTS

I. Introduction .f) • l II. Reaotions>or Epoxides with 'Lewis Bases

'1- . ' . A, Base Catalyzed Reactions of E_pox.1des 11. " ~· • o • • 11 ••• • •••

Olassi_fiaatlo.n of Epoxide Reao.tiQnn · • • •- • • • • • •

2. J,teohania.rn. ot ];Jase Catalyzed :Reactions · • • • · • • • " • • 12

J. Direction of Ring O:penlng of Base Catalyzed Reactions o •• ·. . '! , . ,.

Theory of Direction of Ring Opening II • • Iii • • • 20

;. Transition State Theori • • •- • JS B,1, /,.oid Catalyzed Reactions ot

EpQ::ti.des • • • • • • • • • 11 ci t' • 46 1.. 'j)irec.tion of Ring Open~ng • • • 4,6

2. l\.leohaniam ot Ring Opening • • 4,8 )o Theory or Di:reotion of Ring

Opening ., • • • •• e • • • • ., .50

III. Reactions of Epoxides with Lewis A.cida A~ Mechanism of Reactions ·with Lewis

Acids • ., • fr • • • .. • • • • • • 57 B.e Reaot1ons with Lewis Acids o 60 o~ DireQtion of Ring Opening with iewia

Acids • e • o ~ o ~ ~ • o o . ~ e 65

IV. Discussion of Exp$r1.mental Results. • • • 66 A, Dire~ftion ot , R111g Opening ot

St:1.ll>a~e· -Oxid~s • • • • o 0: ·-• 66 1. 'Yiuimi:aatio.n ot Ste~i~ .Jf.aQt9r.a • 66 ·2, :tithiwtr. Aluminum. }Iyd~ide , • • • • 68

Eiperim.antal llesults. . _,

/+, ·The Subst.±tuen~ 'E:f'feo.~. • - .,

S. Direo'hion ot Ring Ope~ing • • . ' .

B. '!)eaotive.tion ot the Epo:x:ide Ring

1. Eviden·oe ot Dea~tive't_iQD. • It •

2. Theory of Deacrbivation

72

72

7) S2

82

8) 3. Reaoti.ons ot stilbe.ne 0x1ties. S/+

Co Oleava.ge ,Rea.ot1ons of $ti,lbene Oxid.es • • • • , • • ._ • " • • • • • 86

D. Direction or ~ins Open:i,ng ot Styrene Oxide with Aryl µ\hiu..m Reagents • • ii:-·. ·• ·• · • .«, • ., • • • 88 1. Di:teotion ot '!ting Opening wlt;h

Grignsrd Rea.gent$ • • •. • • -~ • 8_8

2.. Direotio.n ot Ring ()pentng ·with ,Lithium Reagents · .i- • ,. .• ., ._. '" a9

E. :Preparatiofl ot Stilbene_s

J.. :Oeh,tdratio~ ot Diaryletllanols

F, Prepa1•ation ot Sti;lbene Oxides • • •

91 91 92 9$

v.

1. Preparative Methods • 95 ·102

G. Analysis of Isom.er1¢ Reduction P:r:oduots ot Stilbene·041des;, • • 104 lo Analysis ot Redticti.o.n

Produots of p•ohlor·ostilbene O:x:id e ~ ,. o • • • •• • 104

2, Analysis of Redu.ctlo.n. P.roducta of, p-methylstilbene Oxide • • • • • • • • • • 111

Experimental Section R • •. • • • A. Thermal Analysis ot Reduation

J?roduots of p•ohlol'ostflbene Oxide • • • • • • • • .., • • • • B. O:cyoscopie Analysis of Redueti.on Products of p-methyl•

• •

atilbene Oxide o • • • • • • • 0. Synthetic P:rooedures • • ., • • ,. D. Bibliography •• ti.. . . . . ~

122

122

129 153 195

lNTROD:qOTlON:,

:fhe -che.!Ui$try o:r the u:o.srrnmetricall,1 substitu.•

ted ethylene oxd.d'.es ia• unig:u.$ in that the :re~etio.na ot ~he three-m.em.bered rings may theoretioa.lly .. yield iso•

.merio ()¢lllpou.nd~ • :whose ident.it.Y .depends on whioh ot two catpon.,.oxygen. bonds Js cleavec;L.. In. ·the i1te:rattu'.te•

:: '' .

th.e1•e are ret::6~:ded tttUnerouei at.t.em.pts to eluei.dat a the

tactot1s. ib.volv.eo. lri the deter.mi.nation. of .the direction

9..t . :t;1ng opening • ., Tl:i..is is the import:an~ ques.t1Qll both

fro.m a theo:r$tio:~1 and a E!fntheti~ apprqao.h. It is

tO\vard this end that the '3xpe:tr1m.ental wOl'k· and the ,;·,, ' . . .

theoret.i.oal aJscussions are directed • .i, ·. . ~

T.h~s thes.:ta sets forth the curentl:r aoceptefl view ot the st,er,J,.o and th.e eleotronio taotors involved

in ·the direction .of ;ri.ng opening whioh we believe to be valid.. 'l!he ,ti-eat.ment of epox1de -reactions .from th&

viewpoint of the Transition. State Theory provides a theoretioal foundation for some of the eleot:ro.o.1o theories offered. In addition, it permits the advanoe--

ment of new correlations between the nature ot the reactants and the d.irection ot ring openinso·

This thesis furthGr sets fo~th a study in the

o.b.e.m.ical reac;t~·04s of p•subatituted stilbene oxides.

New i.tttormationwhioh oonoerris the eleotronla factors, evaluated in t,lie' absenoe ot the ste:ric ef'tect:a, in.di•

oates that the' "e:tteot ot the substitu.ent on the oleavage

ot the bond between 'the o:tygen and the. oarbon atom adjacent; to the substituted phenyl .group is 1·.n the order p-CH.3)

p-a > p-01. The effect of the aubstituant on the direction ot

:ring opening ia explained 1n tar.ms of the Int e1•aotions

o.t th~ substi~uent al;ld the apoxide linkage by means ot the "Transiti:011 State Theory" and i.n terms o:r reaonanoe in th$ illitial Strate arul the. t~ansit.ion state wh1oh in-volves the ca~~on..-oarbon bond ot ~he epoxide ;iinkage.

It is hoped that the small aont:r;-1 but ions ·t'Q the

chemistry of tilt~ epoxides eI11bod1f)d in this thesis .are

ot som.e value in the devetopement of soienoe and the.

progress of ·lila.nkind.

fRE REACTIONS OF EPOX!DE$ wr.rn. LEWIS BASES

-!liE llEAO!f.l,:ON'S OF WOXIDES VII'l'H LEW'lS B1\SES

Base ·catal,.yj;ed Raaot.1ons o:t E_l)oxides ,u Ii . :..tt • . • * !' ~4•-• It ii . J J I #

Ql~s.st_t ie_~t~~~; ;o,t: E;e,c.i:i;~de Ree.o.t10n,!

A br.oad. #fury,,- ot t.ht available litera.~u.re on

the reactions of e.tnrl@$. oxides aatl 1ts substitution products has indi~ated the need. for a syste.tnati.c and log1oal classifioatio.n ot all ·Qt the reactions ot ethylene oxides in ·tar.ms ot $leot~onic theory, '!'he

ethylene oxide r 1.ng, in r·eali ty, has three reaoti ve oenters, two 4ar~on atoms of ~elatively low electron de.nsit1 and a..n oxygen atom ·ot relati'V'ely high eleotro.n

densi,ty. Acl.vantege .may be taken o:t this tact t.o

claasif y, the rea.otio.ns o;f epoxides into two m.aj o~

groups: (,A.) reae•tions with Lewis bases and (B) reactions

with. LEtwis aoid,a. 'fhe f:1ra:t of these groups, whioh oo.m.~ prise the ohan1io.ai reactions oi' epoxides \'11th Lewis bases

may be elassifi.ed int.o sS.x eu~e.gories based upon the

relative e.eid-base strengths ot the reactants and

arrangEJd in t-he order of decreasing basic character

of the attacking reagent and int.Jreasing aoidi_o

charaoter of .the epo:d.de carbon. atoms. The full

signifioa.nce of the ao1d•base relationships, henoe ot the olassif'icatio.n) will be brought out j,n the d1souss1ou

ot the taotors which intl_t1enoe the direction ot ring ·:' 1!. : • • • . ,

opening of uns~etrioally sqbstituted ethylene o:x1des ed in the appl~cation of "transition state theory••

to epoxlde :rea~tions • .Anion iattack." MEUl.1 txamples are known in which

epoxides a:re at-ta.eked by the anion ot so.me salt, as

11lustrat~d in equation I; where »• repr.esents the an.ion •.

fhe :reaotJ.on m.ay -then be completed in one ot seve:r~ itnportan~ way~·= {A) The reaction .tlUlY be completed by the

• ,: i ~ '• . .

abat;raotion ot.·a l)roton trom the solvent or hydrolyzing .media, (:B} The feactio.n may- be completed by an intra ...

mole.c,u.la:t oond$.nsat1on whioh.i;. in 't;he casf) illustrated

tor dietllyli.maionate, gives rise to a laotone (1), (O)

The ·epo,c1d1o o:x;rgen may be elim.inated to :f'or.m an

ethylene sulfi'd~ ('2,3) and (D) The reaotion may be completed ))y 'the ;Cor.mat1on. of a :f!ew, apoxide linkage (4L,

J:. I \,

-c:-c.-'o'

s I

-c -c.-' I ca o

13 Ia, ' ' C. - C. - "" 8(:) l (

0.-\

l

' \ I -~ -c..- -c. - C. -

I -c.- c.-

' s' e +

oc.M

I 9 -c-,

l

\ -c.-oS ,

\ -c- s J ... ~--

e I \ .. ,, _ ~ - a-oc.~

\

I

-c-o \

Qi\;@:!l,Si~ )>l th~ anion. ot: ,th,e betsQ..• A co.mm.only

u.aed p:rooedui'e in t·he reaction of epoxides with alcohols

(5) is ~he addition of a. small amount ot' sodium metal to the aloohoi to tor~ thQ alk:oxide, t·ollowed by

additiQn. of the .epoxide. the reaction ot the epoxide

with the anion and the uncharged m.oleoule proceeds suultaneouslt, but applll"ently, the rate ot attack ot the an.ion and 1 ts regeneration is very much faster

tlian the rate o:t attack ot the unoliarged alo.ohol.

It may be .noted. that the oonoentrat:to.n Of the attackf.ttg anion ls smaller here than 1A the case ot I. . . . . . '

~rom the· viewpoill.t of the mechanism of the reaction. the~e is litt·l'.e -di:tt·e~enoe between att~ok of •atl anion

as described in the firat category and true basic oatalysis as described above. Bence, i.n. acoordanoe with current usage, the term, "base oatalyzed reaction,. n will

-be used in. ref ere.nee to both types ot reaction.

lt. \ ' -c.-c.-..... o"

I :,:,c.t-t, -c.-c.-

1 I 08

0 (, "'• I I -c.- c.- + t\OC:.H\ ~

~e I

oc.H\ I I E) - c. - c.- + OC.H \ ~

Oat~ila1a bl tt, w~ak bas•.•"':' The reaction. ot EJpoxides with alcohols may be catalyzed by the

addition ot sm.a1i a.mou..n.ts of certain: amines su(lh as

.P1l'idine and t:Jtel'ioally hindered seoonda:ry· and tertiary

amines ( 6, 7 l as ahown in equation III~ Preswnably, th$

:f'unotio.11 ot the ami.ne is to ine:rease the nucleophilic

oharaoter of the attaok1n~ L~Nis base.

III.,

I - c.-c:.-

"-o'

\ e> 0

Nt,"i\.. \:::..1 ►

H ~ c:,C. ""i

\ I -e.-c.- +

I I 0 e

oc.M"'-1 I ~ -c::.-,-1 ' o H.

Uncutalized reaotior.1:,~;~ ... t.rhe reaot1on of an

epoxide with',,e.11 t.tnoliarged Lewis base suoli as methanol

( IVa) usua1:i.y:J.•equires . .more vigorous conditions in

the absence of' a basic o:.t' aoidio catalyst (5)~ Pri-

mary, seoondrrry, and tel'tiary amines ( g) readily l"'es.ot

with epoxides i.n the presence of alcohol or water.

Apparently, a source or protons other than the amine

is necessary for the oompletio.n of the reaction as

shown in equation (!Vb)~

IVb.

' 0 -c,-c..- + ~ '0, ~N

® ~ I I N-c.-c.- + HOli ~

\ ' oe

(!)

I c)tt

(J I I N-~-c..-l I

0 e

e ~ \ ' 1.)-c.-c.-

:.!J I I OH

(5) + OH

,O,atalla.ia bJ a .weak; ac.~4.•·• :Equation V illustr&;~es

tha meohaniQnt·::.propC?sed by Guss and Mautner ( 9) for the

reaotto.11 ot ,P'•n'it,i-ostyrene oxid& with phenol~ 1fhey .b.ad ' .·-.-: .

oonolud.ed· that ·such coo:rdination is important in the

detefm1natio.tl ot the ra.'tio of isomeric products obtained.

v,

.Q!t~l;zsis _bl, a stroJYi ... ~ol~.- The reactio.n of

epo.x1des wi'tb. ,such bases as aloohols ( 5) or a.mines

{10,11) .may be catalyzed by strong acids. The first

step, apparently, lnvol ves the tor.mat ion. of an oxoniu.m.

ion., .'?he oxonfw.n, as suggested by King, Berst, a.n.d

Hayes, (lO) is then subject to direct attack at the

carbon atom as shown in equation VO.:a, or as proposed

by ltadesch ( 12·) fol' the case of butadiene monoxide,

the oxon1um may undergo a unimola.oule.r ring opep.ing

followed by attaok ot the base on the intermediat-e

onl."bonium. ion as ·shown in equation VI'b ..

VIb C M,:c.tt • GM -C.H 1,

. , u'

,._ ~

'l!he m~~psinf sm :Of thG base oata.lY.,zed re~ctions

has been eat~blf~hed as a birn.olacula.r nucleophilic :·- I •• _.

M I lCinetiCJ e~udJ:es· .and studies o:C tho Walden inversion

' .... _.'

have aided in -the elucidatlo.n ot the meohan1sm.,-

Kinetii,1h':.. ·Hansso». (i)), Ferrero. Bet-be, and ~ l .. ,· ..... . . .

Fla.mme (11►), Pottel' and ll!al;oughl.tn (15), Sm'.lth and

Nilsson ('16) and Smith., .Mattson an4 Anderson (17)

have -~epo:rtedftha.t, th$ r.ate. ot reaction of epox1des

suoh as ethy~i~.e Q:t:1de, propyl,e.ne oxide, epiohloro,;-hjrdrin and gly~idol with a.rnm,onia and prim.art, seoondal't,

., .-· ..

and tertiary e.lllln.es is first order with respsot to Ph• attaolti.u.g reagen.~·~ Eas~ham. a.o.4 Darwent. (ll l and Eastham.,

~ . .

Darwent, and Be,aub1en (S} also reported second order rate oonstants for the roaotion of ethylene oxide with

amines e Bark•r E}lld Oro.mv,ell ( 18) ,reported, s1nt1larl1 •

that the rea.ot1o:n; of epoxy-benz1laoetophenol'le with morpb.o~

line is also a. seco.nd reaction. Banergee and sen (19 ).,

Bronsted, Kilpa~riok, and ICilpatriok (20), Porret (2i) •

Ross (22) and sen, Ba.rat, and Pal (23) ha11e demonst~ated bimolecular k1netios tor the reactions of ethylene oxide,

propylene oxide, oyolohexe.ne oxide, ep1ohlorobydrin and

glyoidol with reagents suoh as ammonium. and alkali halides• th1ocyanates and thiosultatese

talden: ·t~vertU.on.,- Walden. inversion llaa been

d;e.rnonstrated -b,y G:rlgsby ,. Hin¢, Ohanley 1 and \'lest-.

heimer (24) 1.tt)t:lle, -reaction cycl.op~tene ·oxide with

ethyl malonate ion_._ Ne,Wl\lan and va.nder?lert ·c25) found

that the reaction ot oyolohexene ox1de with. the ntal.ona.te

ion also l):ro.ceeds with Walden inve:raion. MeOasland,

Olarkei and cJa~ter (26) and Vlinstein an.d Buschan .(27)

obtained the trans ... an.t.inti•alcohol and th.us established a Wl.3.lden inversion _in t.he reaot1on of eyolohexene oxide

with a.rwnonia. 'Similarir, McOaslanci and Sttl::ith (28.) and

Fodor and ltiss; (29) proved t,hat inve,:-sion ooours in the

reaction ot cyolopentene o:x:ide with ammonia. aeisler·' .\ : '

(30) recently-established a Walden inversion in the .reaction. ot c;r.olopentene oxide ~ti oyolohexene ox14e with sodium. azide.. Nwner·ous Walden inversions have

been 1•eported ·1n. the reactions of anhydro sugars ( 31)

with amm.onia,. water, a.laoh~ls, and meroaptans. Boe'seken

and van. Loon (:32) established inversion in the alkalin& hydroi,sis ot· indene oxide. Godo-hot, Mousseron, and

Richaud (JJ) recdfded an inversion 1n the ttncatalyzed hydrolysis of cyolop.en·te.ne oxide, and swern ( 34-) estab-

lished Walden inversion 'in the alkaline hydrolysis ot 9,10-epoxystaario ac1d41 By .means of meso- and D(+) ... 2,3"J9

epoxybutane, t>iokey_, Fioket.t, and Lucas (35) proved an

in.version 1~;, -the :reaction with am.!Il.o.ni~;a In view ot the

available ev·1d-eno,~, t.hete is little doubt that the base

catalyzed ~eatfkio.ns of .epoxid.es i.n:volves a bim.oleoular

.auoleophl.lie ·atta~k- on the ri:ng carbon atoms. +t is -worth noting that Bartlett .and Ross (J6 J,

in the sodium m,et·ho:xide catalyzed· :r,eaction of methElnol

with butad1en$ monoxide, obtained ~'Videnoe in favQl!' ot a bimol~oular nuoleo~hllio attack at both ·the primary

and the seeond.a:t-y carbon at<;>m.sf! When sev-en t!m.1;3s the

no:r.mal amount of catalyst. was added, the ratio ot products :romained unchanged •. It attack on the primary position involved direct part1o1pation of the .m.etho:xida ion a.nd th~ attack on the second.at':, position did .not, a ratio of a~conda:ry alcohol. ... prittJ.ary ether to prima;:, aloob.ol~st11oondary-ether seven times greater than pre-viously observed should ha•e :resulted.

The D1~c,i?_ion ot R~llS 10penin5 The striking tact about the bas41> catalyzed reactions

of the epoxidfs is that the r~agents exhibit strong l)reter• ent1al attack at the primar,y oarbont::,11t.o.m. ot propylene

oxides, butadiene monoxides, and styr8lle oxides. As the 1"aots to be presented sUggest,. l'eact1ons o:t butad1ene

.monoxide- are J.nor·e likely to result in attack at both

the primary and the secondary carbon atoms than styrene

-Qxide, wher~a:~: m.i::x,tures in the oa.se ot :p:ro~ylatie oxides

are rarei1·repo;a;ad. ~tl+ :taw exceptions, attack oecu:s ··r· -

ma1nlr at the, J)~ima;,t oarbon atQlll i~ the .three elasses . ' ' ~- .

ot epoxid.es .,.

P,t9~l~he· •dx~~es.~ J:n the case ot th~ -»aae oata• lyz-ed r$ao;ionir of propylen~ 'Oxide, an overwhelming

n.u.nfher .of l'leports show attack at the prima.r,- carbon

a.tom.- ·Thusi ,.:ncmtt; b~ the prod.uoi; wh:Loh. oor:reaponds to

att~ok; at the aeooha.ary oarbon. .. atom has bet:in reported. in the :toll~wibg 6ases: ammonia (37, ;e) methyl.amine

()9,40) ~ ethylam:tn• (41), _1s_Qruqlwne (42), benzy-lamine

(42) ,. e.tha.tu~lami.n$s (4:l) ~ dim.ethy'lrunine (44 ,4_5), diethyl•

amine (4-5 ... 47 h: pipera~ine (48 ,49), .m.orpholiae (.50, 51) anasabine (52), b$tl'ahydroqu1.uol:l.ne (5)), deoahydroquino•

.f.

l.in~ (.54), aca-toaoeti<, eater {55.;6), oyanoacetio ester ( .57); malonio ester (1) t d1phenylaoetoni1irile ( ;1,ss,,,9}, soditun phenoie.te (61 .... 63). thiophenols (64,6.5), xn.ethyl,;

it.Y14.

ethr,l,._.allyl. uc; other aloohols (5,66,-69), l\sod1Wll

azild8 ·( 30) • aa. iitl:d.~ alu.mint\'1l lqd.r:! d;e ( 70). ~b.e

review ot epoxlde reaot.iolUI by- Winst.ein and Henderson contains additional eX.a11?,ples ot reagents which attiilck exo.lusively at the pri.tna:t1 position ot analogs of pro-pylene oxide.

O.t1J.t a t.ew·.authors .record the tormation of ·the

produot wh!.c~; 1e:orrosponds t() attack o.-t the secondal'y carbon atom ·ot,:_:propylane oxide e.n.d. its analogs. Whus; . ., .

Chitwood and_ .i*:·iu,~e { 5-) reported a t:raoe of prima17 .. /:'./>}:";_ .··

a,J.coho1-~seco.n~et:r1, ether $..n. the reaction ot p1-opylene

ox.ids wi'l~h. etllal'iol :oatalyzed by sod.iunt llydroxide.

&ver~j l3illen/~(\a.iid Knight { 69) obtained evidenoe tor' nttaok at bo·;'ll)c~:bbol1 ato.11\s, with p:11inia,:1· at;aok pre ....

·· , of, 1-,c.w.\ _ · . dominating 1.1.\ .".the re~otion"with t1llyl alct>hol.

BU.tad.ie.n'e. ;monoxide.• !ttl1nger (2) tound. that

the· reaotion tit :11u:tadiene monoxide with ammonia gave attack ma.1:nlyat- the prinla:y carbon atom, but that som.EJ ot the is•oid~r which co~,:.•esponds to attack at the

seoonde.ry oa:tt.porl. atom could b~ isolated and identified. :ea:r~let;t and- ~O$a (36}, in the reaction ot butadie.ne

'(:

.monoxide with, :•,·tmµiol, reported the 1'ot.1.11at10.11 ot secondary aloe>ll::Jt~prima,:-y :ether. whiOh corre·sponda to

ii"'•"

pl':tm.ary atts.Qk:, \1;ogethtt with smaller amoµ.nta ot the ,, .

isonier. Adani-. ti"nd: fand«rrWert. (S6) also round that a.oetoaeet1o e~ta gave a mixtu~e ot isomers.- Z~idema, <Jock, and Vf:Ui·Zyl (71) repo:rtecl a m.ixtu:r~ in the reaotio.n wi't;h cyanoao&tic este:r, but structures ha.ve· not as yet

been assigned. '11revoy and. Brown (72) and Fuchs ( 73) fou.nd that lithium aluminum hydride attacked the epoxide

ma1,eily at ·the/prim.a.ry· oa.;rlM>ll ato.nt, bn.t :fjo.il1e ot the ieomet . .

whloh. results ':tr.om. a.~taok a.t the sel)ond~r.r carbon atcua was isolated i$.dt·11ie.ntified• ·swer.n,. Billen, a.nd Knight;

(69") repo:rted :/~xclusive attack ·at th~ see.ondart ea.r~on

ato.rn ·ot 'butttc;{t,~~ nto~oxid.e in the :react-ion· :with allyl ;':1 .

·al6ol,lol, _Uef•let ()O) round tha.t· 1.11 ~!',l,~ r<¼ao~_ion or

butadien·e .to.oq~ox.t<le 'with sod.ium. .. -a~ide,. •ttaok occured

exolusivel.;v at: the seconda;t.y ea:rbo.n atom in pretei'.~iioe to pr~y att·a.ck·•.

A few oasea have bee.11 repo1-ted in which none of

the product corresponding to atta.0.k at the secqndary-

oarbon atom. was iso.l~ted or identltied,.. Thu$, 1.n

the reaction qt butadiene monoxide with, alcohols,.

catalyzed by alcoholatea, .Petrov ( 74.,,76} and Xadeseh

(12) reported only t,b.tt isolation.of seaondary a1oohola. Russfal and. Vanderwerf {l), in the reaction with malonate

ion, -obtt'11ned the product which corresponds to exclusive

attack at the p:rim.ar1 carbon atom, as did Massie (77) in the react.ion w.t~·h: m.erca.ptans.

strren~ o:d.dt•• Reeve .and Ohtisto,ttel (78) tound

that ~he metha.r+olysis ot- styrene oxide yielded the product oorrespQnding ma.inly to attack at the primaru oaiabo.n atom. Kaelin ( 79) also found some evidence tor attaok,1at the aeoo.ndary carbon in the sE1$e l'ea~tion,

Uann.1ch. Ne~:nn• and Jacobsohn (80) reported a muture in the- :t•eact:1¢.li o:t 3,4~a1m.ethO~$·tyrane oxide with second•

ary amines. :tn, the rea.otion of styrene oxide with all7l!-

alcohol, swe_rn• Billen-, and .Krlight (69) obtained a Jilixture containing .9~i1of' a product which they' identit:f.ed as 2•

allyloiy•2•phenyl.ethanol end l~ ot the isomer. Hayes

an'd Gutberle~~- 0howeyer, re•l"an the reaoti-on and oon-

cluded that the .assigned ·atruotures w~Jfe 1.uoorrect and

that ther ibase'}/oatalyzeo. reaction with a.llyl alcohol

'actually gives maiAlY prima~1 attaek., Xaelin (79)

reported that:· the met·hoxide ion attaOk$d J,J+.-diaoetOX1•

etyre:u,e o:4de,axclusively at the seobh.dary carbon ato.m. l4oEwen, Conrad,. ·and Vanderwerf (82) also reported ex-

otu·stve attack at the seoo:o.dary carbon atom with the az1de ion.,*

Severa~ l'eports ha-ve appeared in the literature in whioh the product oorresponding to. attaok at the seoo.ndt1ry carbon ot styrene oxide*~as not isolated or 1denti.tied, am.ong which are ~he f'ollowingt d:1.m.ethyl•

ami.o.e ( 8)); dlethylamine ('84) • secondary amines ( s;),

* 'l.'he possibility of isome:rization of the primary azido ... seoo.ndary '13.:loo}?;ol, it for.med, to the ~t'ioondary azido-prima:ry alcohol_ l!lay be· considered~

** Oristol and Hel.mreioh (t<\5') recently reported that the ethyl malonate ion attaoa~d exclusively at the primary oarpon atom of p-nitrosttrene oxide. ·

.rne11oa_ptru1s ( 77,86}, allylaloohol ( 69, 81} ~ ,;-ethyl

barbiturio acid (87), lithium. aliuninum hydride (72), aeetoaoetio ester {56), and .malonio ester (1,87).

qon,tradictor;r rel!ort,l!• ... Several reports have appeared in the literature which give evide.noe tor attack at the secondary carbon atom) but these have not been substantiated. 'l'hus, the work ot Emerson (88) was

den.ted by Ree.ve and Christoffel (32) Swern, Billen. and

Knight {69)· reported iihat the :t"eaotion of styrene oxide with the al-lyl ox'ide snion. gave attack mainly at th~

secondary oa.:cbon a.tom11 Doubt was cast upon. the iden.ti-ty

or the _produota isolated. by the work of liayes and

G1.1tberlet, {Slh liawol'th and Riohardson ( 89) l'epo1,'ted

that the :reaotion of sat:i-ole oxide with the aoetoaeetic ester carbon ion attacked at the eeconda.ry-oa~bon atom, but the oonolusions drawn were oontrad1oted by the subsequent vmr.k of Haworth and Atkinson ( 90) and. FU.ob.a

(73). Carpmaol ( 91) reported that he obtained 0(-~oeto.,,>6-

methylbuty:colaotone in the oondansa.tion of a.oetoaoetio ester and propylene oxide. Buohm.an and Richardson (55) end Ada!lls and Vanderwerf (,56) • however, established tbat

the aoetoaoetia ~ster anion att:acka exclusively at the primary oa:rbon atom and .not the seoonda.ry ea.rbo.u atom, a.a 1.tldioated by Oarpmael"

:Kheorz ot the Direction .of ~Ring OJ2enillg The applica:t1Qn ot m6dern eleotronio theoty,

the reinvest:J.ga.t1o.tt of epoxide reaotions in doubttul

cases, and excellent work o,n new reactions -has thrown

.new light on the question of the direction of ring opening. Not,ail of the factors involved in displaoe•

m.ent reaotiona atJ' they apply to epoxide :t'eaotiona are,

however, well understood. several of the f'~totors which

.may be oonsiii"ered are: (l)

(2)

(')

~ti (6)

(7) (~) (9.)

(10) (11)·

(12) (l)) (14,}

Energ:Lea of repulsion. bet-ween the epoxlde oaibon atoms and the attacking reagents. Bo,n.d strengths Qf the oxygen .... oarbon 'lillkages. :ease strengths of the attacking r~agents~ . Resonance in 1ihe in1t~l state. 'Rasob.a.uce -in the transitio.n state. Pola~izability of the bond between t,he substituent and epoxide carbon atom. llyperoonjugation. Polarization ot the carbon-carbon epoxide bond.· · :Sterio effects: primal."Y' oarboi1 atoms vs. secondary carbon atom. st·erlc efteots: size of substituents on the 3.9ing. steric e:tteots; size ot the attacking group. sterio i.nhi'bition ot resonance. Ste1~io effect of a. neighboring group. steric configuration of the epoxide.

Repglsion ener,stes,. "!" Ohitwood e;nd F.reure (;)

suggested that the eleotron-releasing· effect o:r th~

met-hyl group in ·propylene oxide was :responsible tor the al.m.os·t exolu$ive attack ot the .tnethoxide ion on

the pl'i.nut.ry- ca:;cbon. atom. -In the absence ot o·ther

taotors, an eleatron~releasing group should increase the eleotron density 011 the adjacent carbon a tam which

would laijva t.he primart .ciarbon .atom with a relatively { . .

low eleoti-on density. The base woUld then attack pre• ;f erentially -at ·the carbOll. Qf lower electron dens.ity be ...

oauae of the lower .re;pulsion energy, 1.e., the primary carbon ato.m.~

"" · e

13 \+ ll ,+• CH - CH" '0/

It is kn.own, however, that displa_cem.ent reactions

oceur more readily at a primary than at a seoondal'y carbon atom (·92).;, In this particular case. then, the

two factors, eleotronio and sterio, lead to the same product, and it. beooma.s· ditticult to determine the rel-

ative contributions o.t the factors whioh direct. the attack

at the prim.ar~ carbon atom..

That the repulsion energies alone are not the decisive faotor in determining the direction ot ring opening is .made olear ·1.n the case of epoxides with

eleotron withdl',awing groups. :fifleotro.n-withdrawing

groups ( 9,3) * 'su,o·h' as t.he tihloro.m.ethyl, alkox.y.m.etn,l,

vinyl, and phenyl should deorease the electron density

on the ·second~ry oarbo.tt a.tom more than the prim.arr cal'bon

atom. liai1Qe, at.tack· should oc·cur pref~rentially a.t the

.secondary atom due to tlle lower energy ·of repulsion. '?he vast .majo1fity ot report$ in the o~se ot epichloro-hydrin a.n.d the·giycid1l ethers ind10ate 11 however, that

':{

predominant attaolt ooo1U,'s at the pr1Jnar1 carbon ato.m.. This poi:Q;ts to the importance of the sterie factor.

13e , .... , s+

VIII.

Nevertheless., butadiene monoxide and styrene oxide do

give substantial yields of the product whioh corresp<>nds to attack at the secondary carbon atom.. While this has been attributed to the taot that the vinyl and the phenyl

* The assignment of au -Is { electron""withdrawin.g) etteot is based upon measurements ot the ionization oonsta.nts ot substituted e.oetio acids which appears in Inter• national Critical Tables, VI, 264. Also see ret. 94(a..).

groups ue el,eotro.n: ~itJ!dr_awi.ng .groups, it is in.con ...

siste11t with the .. fa.ct· that the olllqro.methyl and alko1:1•

.rn~thyl. epoxid·e,$ d'o .not give attack at the sEioonda.1;1

oart>on. ato~. ':Furthermore, th~ fact that butadie.ne ~on• oxide and styjien(ij o:x:id~ give- .P,roduote whi~h -oorrespa~ul

to secondary atta.Q"k ,.may, be attribtt_ted to resonance in

the trans~ td.&n 'Sta't,e and t9 pola~ization, ot the bond

between tht:l. f)econd.a:tty oa.rbon ato1n a.nd the substituent.

As noted,. observations ot the induot1v8 atteot {e.leotron-w1thdrawi11g and eleotron--releasing- eff~ots)

on the 1fepu1sion energies are.obviously obsotired bT the sterie et:1'eot in monosubstitu.ted ethyle~e oxides"

While the etfeiot ot subst11iuent on the direction o:t'

ring opening may be evaluated theoretically, experi--mental Vel!ifioa:tion .-;,,ithout elimination ot minimization

of the steric factors appears to be 1.mpo~sible 1n tlle cases oi t ed.

B,Q}l,sl strength~•- swe..rJ?-; Billen, and Knight (69)

suggested that the e:t'i'ect. o:r· the subatituents on the bond st:rengths of the ring oarbon-oJqgen bonds may be

1.m.portant in the deterJllination ot the direc·t1on or ring opening. All eleoti-on•raleas:iJlg substituent would be

expected to weaken the secondary oarbon-o:xygen bond more than the primary carbon-oxygen bond, sinoe the aaoo.nda.ry

oarbon ls relatively more nege.~ive than the primary carbon a.to.ru. Thia will facilitate attack at the

secondary oarbon atom. An eleotron ... withdrawing

substituent should facilitate attack at the p1•imary

carbon atom du·e to the greater strength o'f the secondary-

l X.

ae

" R ~c.H- c.H'L "- ··l- -

()

It m.ay be noted that bond strength considerations

and re_p1.1lsi:c>11 energy considerations lead to opposite

predictions o:f ·the direotion of ring opening.* The

relative contributions ot repulsion energies and bQ.tld strengths to the direction of ring opening will be

treated syatematioally in the discussion of the trans-

ition state theory- as applied to epoxide reaotionso

!l_a_se sy,r~ngtb.a .... Fourneau and Billeter ( 95)

reported that in the reactions ot ~-phenylgiyoidio

esters and amides with amines aniline atrlia.cked at

the O( ... oarbon atom, whereas dim.ethyls.mine attacked at

* Rem.1ok (94b) d1sousses the reversal of the substituent effect for simple baae displacement reactions.

the p •carbon a.toni. They attributed this to the

tao\,· that the ~ines differ ill base strength.. 'l:'he

etfeot ot base ··atTength on the direction of ring ,'',

opening is i.int~ma_teJ.y eonn~eted w.i.'th repulsion, enel"g1es

and bond energies. I-ts tbeoretioal foundation.a .will be

diaousserl in the tra.ns.ition state treatment of epo:x:ide

t'eaotionij where additional evidence will be presented.

, ,Resonance i;s th$ init~al ata~ .... Tam.elent Van

Zyl, a.nd Zuidema .. { 96) suggested the possibility ot

:reao.nan(je stabilization in the initial atate 01' t.he 3, '4.-dihya.:rona.phtllalene-1,2-e:poxide ro.oleoule a.st being

responsible, in part, tor d1:r:aoting the attack ot the

diethyl.m.e.lonate anion at the tl •carbon atorn.

ro " f 0

Ctl c..,Msc.o .. / '-co.,c..., tis-

As they po1n1'ed out; the resonan()E'i theor1, ·a+~h:ou.gh useful., is inad:equa~e when. ·applied ,,ithout consideration ot the steric factors, ··s.tnoe malonic eater -e.n.1011. attacks

strrene oxicle at the primary car'Ao.b. atom, whereas, reson• anoe te.vors attaok at ~he secondary carbon atom. The attack ·or the inalonate. ion on the dihyd:r.aoriaphtha,len&

oxide moleoui,:, * in whioh. the sterio factQt-s a:li& mini-

mized, is a.t the oarbon atom favored by reso1i'ano, stabilization.

:Resonance 1n the transition state.- Bat'tlett and

Ross (J6) int~odueed the concept ot ~eso.nance stabili• zation in t.he transition state to explain the tormatio.n.

ot some primary .alcohol in the reaction ot butadiene monoxide with ;me·thanol. Adams and Vanderw,r.t (.56)

applied the theory to explain the attaok ot the aceto--aoetio ester ani,on o.n the secondary carbon atom. ot butadiene monoxide. fJ.'he theor1 Jll&Y; in tact, be applied to all the base catalyzed reactions of styrene c,xide and its nuclee:rc. substitution products a.nd ot butadiee

m.onoxtde wher$ pl'oducte which correspond to attack at

* See :ref, 97,. Evide.nc.e is ctted to the etf'eot that piperidine attacka j ,4~d_ihydl'o.tiaphthalene oxide at the ~ •Qarbon atom.

E) C.Ha.:C.M-c.~'•~c.M'I. + ctt.o

'·-o'

f>'- M.1 C.'41, a c.H - c. "4 • C. H 1,

I oe

>C II,

> E> ocH,

C M1, :.c M •c.M •c M1, 'o'

9 Oc.M1 CH1.=c. "4 -c.t1-c.M1,

• /e

&cc.Ms e ~H'I - '" =c.H -c.w•

~ oe

It appa~s, then, that although the etfeot of resoh~noe at,abilizatio.n. .ma,y be observ~d in the reaotiona of butadiene- monoxides and styren.1;1 oxides despite tlle

$terio factors, the .minimization ot the ster1c taoto,;s. as 1tl the dlhy-dro.naphthalene oxide lleaotio.n, clarifies the reaonano:e etfeot even 1'U1"ther.

?,ola~i_z~ab111ty.°"'" Alexander (98) -suggested that, in

base oa..talyzed reactions Of buta.diene iao.noxide the at-tack

ot the. base\'?'~ the secondai-y carbon atom is ta.c111tated

by the polarizability of the adjacent vin:r,L group.

Th~ demand ot .the attacking base :ls an electron

deficient oen'f,er; and since the eleot1'-0n sink, in. the

tor.m of a vinyl g~oup, is on th.e secondary carbon atom,

this should be.the te:voi-ed point of attaok.

~ 111,

The theor;r m.ay, as ln the case ot !1.*esona,noe stabilization

in the tranaiti.cin state, be applied to those :reactions -:·, '

ot but.ad!ene monoxides and. styrene oxides in which

attack a.t the a.eoonde.i'y oarbon. atom oQcurs"'

Kad,esch (12) sohematically sugge$ted tha~ 1n the

;reaction of bute.di.ei.i:e m.o.no:xide wi·th methoxide ion, the

attack at, the· ,:pl;"imary carbon ato.m. is faoilita.ted by the

eleotron ... relea~e -etreot of the vinyl group whi¢h .ate.ms

from polarizat'fon b~ the double bond. cs,

o C. M:, \r

C.H,. £1_H -+CH - CH1,. . 'ul ){ I Y,

This ca.rinot be. It would appe~r that since the demand of the: ·metho:x:icie ion is for an electron

defioient eente1', only an eleotl,'on withdrawing

group may aid ch$ attack, and in this case, the attack at the secondary oar·bon atom. would O<.H'l~ pre:ferentialit as suggested by ~exande:i:-·· (98), i.rhe attact at ~.he pri•

.mary earbon a.toll'1 .ttta.Y', perhaps~ best be explaillad by

steric consideration$. . . ~- . . .

fltperoo.njuga·t1on~- Roge;t!'S C 99) su.gg~sted that the

dip9le .mo.mentr1 of. ethylene oxide and propylene oxide are

in the direotion to be expeoted i'o:r aigni:tloant oontri• buttons trom. strtiotures ot type x.

C

It ma:, be note:d that, in the transition state, hn,ei•

conjugation would favor attack at the secondary carbon ato.rn due to :resonance stabilization ..... · Si.nee it appears

that the sterio factors overshadow the electronic taototsi it is not possible .in the case of propylene. oxide to studJ'

the inductive ei'tecrts ot the methyl group or o:t.' hypei-con•

jUgat1on o~ the direotion ot r~ng ope.ni.ng... The role of

hyperoonjugation will be tr$ated m.ore extensively ill

the disou.ssion of' the experimental, ,:esults.

I.'21,ar!,~S;tion. ot th.e oarbo!!-:-oa:rbon epox.~~~ ,bo~d." ...

A nwnbe:r-·of studies have shown that ethylene oxides

l:lehave in .m.anywa:,s like the correspond1n$ ethylene

derivatives. 'l'ha ultraviolet absorption bands of

com.pounds with an epox1de linkage adjacen'b to a

dou~le bond tend to occur at wa~e lengths between,

those of' the analagous oompounda with alkyl groups

adjaee.nt to the double bond and those with conjugated

double bonds, but whose maxima are usually observed

closer ~o those in the conjugated system.a. Thia is

illustrated in 1iable I ( 99).

Table I The Absorption Maxima of Styrene Oxide

and the Corresponding Saturated and:" Unsaturated com.pounds

Xmax. .t: Ethyl benzene 2060

Styrene Oxide 2120

Sty:rene 24-55

As Rogers (99) pointed out, the eleotrons of the

~ing bonds must be more loosely held than those of

the usual single bonds and the oorreaponding orbitals

also mu.at have. a larger extension in space. It is

possible, then-, that the carbo.n-..oa:rbon bond ot the ~poxide is .more easily polarized than the Qarbon•

carbon. bond ot a straight oha.il:A alkyl group, in a Jnan.ner s1m1lal"- to an· ethylene 11:.nJr,age. We should like to· suggest; th~t 1,~~}rfr_ect of. ,a snbSJtituent s,qtra on .the

~!.,te<>.tion of :r.1ng ;012t?n,iJ1& ,of an e:go#,J~ is in ao~ !1,tl;l ita ~treqt, on th, polar:tzati~11 ,of· the onr~on ...

oarbon bortd; just as is the case wllen the two carbon a:tom.s concerned ·a1e m.u.ltiply bonded.. Eleetron with-drawing troupe such as the chloro.methyl and the alk•

ox,.methyl groups mar be expected. to aid attack of the base on the pli'ima.r1 carbon a1lon1 in. p:tiefe:renos to the

secondary oarbon.

&e

" X-eH1, .,_C.H - 'H 1,

'o'

&.e e " <:i>

C -.. V-CM1..- C.M C.H'L '-o'

The observed facts a:re that primary attack pre• dominates in; l>b.bh the ·case of an electron-withdrawing

group and an el~ot:ron ... releasing group. As p:revioual.1 pointed out, the ster1c faotor is probably .more im.por~ tant than the eleotron1o taotor which accounts for the observed di:t-eat-ion ot ring opening, ~o evaluate

properly the ~leatro.n.ic eti"eot of a substitµent on the dire()tioli of .ring openinth it becomes .neo~ass.:r1 to mlni,.mize or elim.i.n~te the steric i'aotorsw Experi--mental evidence will be prest-mted in the discussion

of the J.l•SUbstittited stilbene oxides -wh¢re t.he

sterio taeto:rs a.l'e 1ninimized.-whioh supports the con,... tention that· the ·ef.feot of a substituent on the polari• zation of the· carbon-.oa:rbo.n bo.nd ot the epoxide :pla:,s

f1 Jn.t3.jor x-ole. ill·the deter.mi.nation -of the direction ot ring opening-

Ao.a;ess1t,bilit:g: o,r ,the oa.:r.-bon ato.m~ .. - Sterio factors have only recently been considered. in the reaotions of

epoxides with Lewis baa-ea. Tam.elent van Z,l, and

Zuide.m.a (96l suggested that the aoceasibili,ty of the ring oal'.~on atqms .nu,a.y outweigh the eleotro.nio factors

in deter.mining the direotioa of ring opening. As evidenoe.., ·th~y cited the tact that, in the reaction of

styrene oxide w1 th the .rna.lon.a·te ion ( l), thE3 attack

occurred ex()lusively at the primary carbon atom in praterenoe to the carbon a4Ja.cent to the ph~nyl group,_

whereas; in the reaotit)n of 3,4-dihydt"onaph.thalene• l 1 2•oxide _(9~)', the attack occurred exolusbrol.y at the

·carbon acljaoellt to the phenyl group. In both oases t

based .o.n l"~tfd.nanee in th.o initial state and 1n the

transition ~t~t'9._; it would be expected: that attaok

oocul! mat.nly a:t the <:arbon adjacent to the phEtnyl

gtoup. The .d:i:t!fe:r-enae in t.he mode ot attaok was

attributed to th.e t·aot that the alpha ... positie>n in th&

·dihydronaphtl1ale:ne oxide is less ate:r.ioally hindered

than ·the saoond:ery·carbon ato.m in styrene oxide.

Win.stein and Bende1•aon ( 100) suggested the orde;tt of

preferential attack of a ba.se on the epoxide oa.rbo.n

atom as p:rtma:.t-Y-'> seoondary >te:r:-~_iary.

Size o:r .t.he subst1tue.nt ..... Adams and Vanderwerf

(,56) suggested that the size ot the substituent. on t.b,e

.ethylene oxide ring,. in part, de,terinined. the direou1oa ot r1.ng opening.. It wa·s found that the reaction of

st,ren_() o:d.d~ with a.oetoaoetic aster anion eave attack

at the priJlla.ry oarbon atom exclusively, but that buta ...

·diene .m.onoxid~, with_ the same anion gave a mixture of • . 1 n

1somel'~h T,hia was attributed. by them to the ·sm.a.lle:tt

size ot the vinyl group, com.pared to the phenyl group., This is tu.rt~E)r confirm.ad 'b;r the -r~equenoy with which attack at the secondary Oal'bon has been reported in

butadiene monoxide eompa.red to styrene oxide,

Sterio ta.otors: st,ze ..... o·:r the atta,oking &r,oul?•'"" Adam$ and Vanaerwer:f' (.;6} also suggested th~t the size

of the att~,cking reagent, in. part• deter.mined the direction ,.of r-ing 01>ening. The reaction ot· butad1ene

monoxide wl:th,·~ the .maio11ate e..u1on was reported by-

Russel a.n<J. Va.tidl:lrWert (1) to yield the product which

eorresponds to attaok at the primary carbon atom. ex ...

elusively, while with butad5.ene .monoxide and aoeto-

aoetio anion, a ni.ixture was obtai.o;ed, Thi~ waa

att:ributed to the fact that the acetoaoetiic eater

anion is less bulky than the m.alonate ion.

;8t,e;:ic inh.i~:\.PA9J! ,or resonanoe ..... The possibi)..ity • . ' f • • • •• '

of st~rio ;t.nhibitio.11 of reso4anqe in t~e transltio11

state may a.lao be oons.idered<) lt is posslble, :fo1•

eXe.!ilpiE'I, to assume that the a.ttaok ot the diethyl

n1alonate anion 011c the priro.e.ry carbon atom, exc1usivel1i \

is due to sterlq interterenoe with the ooplanarity

;requirelllent o,i"·:t·he reson~oe syst~.

N~i5.qbo:rl~g _grou:e, e,fte~~ ... Fu~a3t and Plat.tner

(101) end l?a.t~~i{ Rosenkrantz, and :Oje.raasi (102) '

found that 111:",t'he iithiwn alwninu.m hy~r1de reductions

ot steroid epo;+des o:r the allo a~l'ies~ where tho

hy~ogen at the 5-position is ~rans to the .methyl group at the 10..;position, the attack on 2( CC.), 3{ 0(.}@

epoxides is it the less hind,ered 2(,e )"'position which

results in the rornia.tion ot tlie 3( ~)--hydroxy ste:rold.

This is in contr:ast to the reduction. ot the 2{,G J, ) {.,.d )-epo:x:idea where the attack is at the 3( D{ ) ... position a,.nd

~·~ r~aults ;.n.1~the ferm.ation of 2(/S )•.b,Yd.10:xy steriods • ..

'l'.b.'3 e,ridenee, then, justifies the oonclusion that the sterio a:fteot of hydrogen 1n the ;-position affects

the di~ection. o'f :t'ing open1ng«i

Plattner,. Eeusser; and Feure:r (103) :reported

that :reduction of \X- a.6.d/3 -eholesterol aoetate oxides

with lithium aluminum. hytlrida led to atta.ok at the 5•

position in the ~-cholesterol acetate and at the 6-

position in the o<_.-oholesterol aoeta.te«;

,a:::r OAc. o••

?he evidence again app.ears ·to justify the conolh~ion that a ne1ghbor1ng gl"oup· - in this ease) t,he ad!~hxr

. ;--,,.-:; : ·,

group - may afteet th, diitection of ring opentng. Oonfisure.t!on.' of ,}the 'epoxide. - Fourneau and

,. Beno 1 t (106) l"e:port$d 'at ill another exe.~le ,of sterie

!;.,

ta.cto:ca 1.nfluencing the d1:rept1on or ring opening., The dlastereoisomers-pseudoephedrine, and 1-ephed ... rine-vre:re converted to the respective a.1pha•phenyl•

propylene oxides* by deaminat1on of the ohol1nea, a reaction which t:nvolves a single 1nve:tts1on. The d• epox1de obtained from l•ephed:1-ine on reaction with

\/, ''-c.(,\-t.." •f,.," -> .::: ... / O!-f NH Lf-1~ '

I~ - (." -'-" - c." \ '-=.I '-o' 1- c:.ph.e.l.v-o\e

I-;-:\_ c.~ - <-\i-c.~i + \,.: .I 0\\ Mftc.H,

.t- ep~ccO.r,\'le.

J.- e.r0 1-.,le.

~- t.H -C.N - c.. \\} \.::.I NNc.", 0 "'

cl .. 1\• c.p\..eA.v-,""'e.

* 'l'h~ $te.1teospec1ficity exhibite.d by these ep,oi(:J:c'tes was brought to our attention by R. n,1e.1er (3(?}1' ''''<'>'1'\ Alexander. an9"i:Dittm~r (106) in the.,1:a~.t:g.,patalyzed·:;;- •· 1somerizat16n or cis- and trans-2JS-:epo_xybutane, clearly proved the importance of st.ereoohemistry in the reactions o~ epox1des.

~~\\-C-11-tMl -') '0-c."-~,t\- ~II I \=,_r 'o' \::.I 6" NNC.M, ~" -c." -~",, -,

- OM :."c."\ p ~e v...floe.p"el t ,'Ae ~1.~t•,t. e.po~,ile pia•v..••p"e«l1i-1~t

~,C.\\,

methyla.rtd.ne yialded a .rnixtur~ Of l,..a_phed:?Jine and d•

ieoep.b.edrine. The raoemiq epo:rlde obtained tr0.1n. pseudo•

ephedrine on rea.otion with methylamine yield$d axolu•

aively pseudoephedrint:>r

St.e:ric hind.ranee has also been observed in the

r~a<Jtiona ot the sugat" epo.xides* Prins {104} reduced

.methyl 2, ,-anb.jtd~o-4,. 6-benzylidene-1(-D•mannopyranoeide

wit.ti lithium. .aiu.mirt'um hydride and .obtained the product

co~rea:po.tt.ding to attaok at the ;""position. Apparently-;

the .2 ... position is more sterioally hindered than the 3-pos1t1on, In contrast, methyl 2,3 .... anhydro ... 4,6~benzy-11 ...

dene- oc,. ... n.-.ailopY':ranoside on i-eduction g1ves the prodnot

which oorreaponds to ~tta.ok at the 2 .... position.

)('>C\\\,

)(X\V

ira11,aition State Th~o:t-.z

The generalized th~ory of the t:ran:sition state*

as extended by llinshelwood, Laidler• and Timm. (lOS)

.tnay be applied to the reactions of epoxides in an

et:f'o:rt to e:valua.t~ the oleqtxoni~ faotors a.tr eoti4g

the direot!o.n..or ring openins~ Oo.nside~ a typioai

displacement reaction:

A + B ·.-:- 9 --> A ··~· l3 + 0

which can ~,e broken up :t..nto four ste:ps 1:nvolvi11g four

energy 1'~etors:

Ez: E3: E4:

A.'!°.B ..!:!.co ..... > A:,:·.B C!, Q

A. ~~13 .!.!_ C . · ,,. A.~ \B. tc. C. ( tJ.1a.nsi'tdon ~tut·e)

E1 .m.ar be taken as the repµl.aion $nergy ot A for l'3 .. o, E2 as a funotio.r;t of the bond .strengtl;l. ot B - o, i 3 aa a tunotion o:r the bond strength ot A• B, and

E-4, aa a. function. ot the repulsion eriergy of A ... B tor A_. C.,

!l.it10 ass,um.ptions may now bo ro.ade 1.n, order to eva.lu,-

ate the etteat or aubst1~tien.ts on ~ea.otion i-ates; first,

* Rem.iek (94C.) ,and Water-s (107) disouss the application o:r transitic.n. stute •theory to simple three cente:rc reactions~

that ohangaa :tn l'eaotivity whiah result from: electro•

static diaplaoe.m,ents caused by substituents are due

primarily to changes 1n the energy ot activation and second~ that the additional charges o.n a given ato.rn

as a t-esult ot. the eleot:r.tonio displacements introduce

an extra. electi'oatatio ter.m. into the ene1:gy of the

bond between the g:tvel'l. atom ,a.rid its neighbor; and th1$

S11ay be oalou14ted as though it were a classioal.

coulolilbitJ t e:rm •.

liet eA *· 9.:g, and e0 represent the eftaotive

ehargea on A, ,13, and C respective.l,y i X, the inter-

atomic distances, an.d w, the :ttesonanoe oontl:':ibution ..

Then,

cu: J:a

GA eB eA eB - Wl -+ \XXV•) W1 -El :: :x:2 r,.· • ra

xq e:a e0 d-x e8e0 E2 W2 .. • w - \ ro-i) : 2 x.2 ro r1

r, {,<XVI·) \,

and E :: 'E1 + E2 ~

If a.n. H atom in the group B is substituted by l? the e:t'feotive charge on Bis ohangad. tot tsb.iz ehc..a;;o

Let this change be de»• hence it follows that

Note that the two etfectta are in the opposite direction.

In general it will be found that as a result ot introducing a aubstituent, changes in the energy of

repulsion, ~ E1 , will be far :more pronounced than

changes in the bond energy, bE2, assuming that eA, and

e0 are of the same order of .magnitude. A substituent

will., in other words, ino~eaae the energy at activation,

E. if it increases the repulai.on between the attacking

:reagf;)nt and the seat of t.he r.eaotion 1.n. the .rnoleaule

attaoked and vioe versa. Consider the case ot ethylene oxide which OO!\•

tains two reactive centers and where the group being

expelled is identical tor both centers. It follows

that the rate of attack at both carbon ato.ms in ethylene

oxide is the se.rne. Substitu.tio.n of an electron withdrawing group

gives:

Oo.llJ.pared to ethylene Q~1de, /eB ot t.he. ,8 ... a atom.

is greater tha11 '~he f 9a o:t the ~-Q atom. Since

f 8B is positive and ·eA .negative, then .!\ E, 1.s neg• ativ·e. ·Since AEa .is asaUllied to be sin.all, the ohanse in the energy of aot1 vation,. AE. -.tor attack at the

f!J •O atom is .more negative than A E tor attack at; the o<..•O a.tom.., The at·te.ck ot the grC>Up a• will take place;

prete:entie.ll,Y at the po.int of lower energy ot· act1 vatio.n,

hence. a.t: the /J ~o atom~ While the rate of attaok at

both carbon atoms is increased, ·the ratse at the /3 •O

ato.in is 1.ncr~ssd mo:re. :rp,e oo.tiolualon, then .. ¥1.. b~ drawn that t !n~ot;,Et,r a.~ re;e~~sioJ\, .. energies are .. , ori~ica·l ,_ ~nt~:ro~uctio.n 6:f! al'l ,electron wit,hdraw!ns grOUJl .int~ the

·et!!,yl~n~ ox1-_gf3 molecule.w1ll. aid the attack. or .~.h.,_Ley,1s

base. at the $~00.ndar,: carbon ato~, ,i.e. 1, thE!t ,6 ,•O ;e.to.m.. S1tnilarl31;t the· 1ntrodu~t,1<'M! of .an eleotro,n-releastns

srou;e will aid e,ttl\ok. at tho pr1.m.a.rl carbon a~om., Now oonside:r variations or R ·in the m.onosubsti•

tuted ethylene oxideso Let R• be .m.ore strongly- electron withdrawing than. _R. The ei'f eat ot changing tro.m. R to R'

. . ~

is in the same d1reot1on as changing t'ro.m H to a in

ethylene oxide s1no e the e8 on the /J -o a tom. lll U'-<

1$ m.ore positive than the 813 on the /!J -o atom 1n X>.<X\ ihe energy ot activation, theretore,is less tor attack

at the /J •C atom 1:n XX~ than in x.xin. we may oonclude,

then, the greatel' the eleotro.n • withdrawing ability

of a substitue:nt in ethylene oxide, the more likely the

attaok: at the secondary carbon a.tom, i.e~, the /1> ... c JP.>s .. ae

. ~· ,~ atom. end vice ve;isa. R'._c."-c.~,., 'Gtau ~4=-<-\.\-'-l-1 JC.)C.X\•

'o' '-D 1

In the t:reat.rnent so f a,1•, we have considered

variations in the epoxide subat.ituents assuming that A E.2~ the change in the bond energy brought about by

the substituent, 1s small compared to A E1 , the ohange

in the repulsion e.ri.e.rgies. If, however, eA were small oompal'ed to e0 then. AE2 would beoom.e the predominant,

factor. Renoe, it may 1>e stated that with the weakening

or, .removal ot any well defined charge in the attacking

reagent, the etfeot of the su.bstituent will be deter-

mined .more by its affect on the bond strength ot the bond. being broke11 in tht m.oleeule and leas by its efi':eot on the :repulsion energies.

In the oaae 'where R, a..n e1eotI'oh withdrawing

group:,. is subatituted in the ethylene oxide .m.oleoule

en:d where t.he attacking base is. A>whioh has no well

defined oharge, the rate of attaok on the ring o.arbon

atoms will now be deter.m1ned by the relative bond

strengths ot O• o<., .. c and O• f!:, .... o bonds. The effect of

an. eleotrott withdrawing group is to strengthen the

o-fa •O more than the O• 0\ .... 0 bond. We may oon,clude 1,

.!l!!en, that in- tp.e case ot an ele,otron~withctra.win& group,.,

the w,_ee.ker theattaoki~ base 2 the more likelz th;e,

att~ok at the prinµ;.~l ,carbon, ate>m& .. si~ilar.1:Z,, i;.n the

oase of an eleotl'on-reieasine; g.ttoup 1 • the . weake;r. the

e.ttack1ing base, t~e-m.ore .likely t_he attack at. th~

f!e~q,nde.r:z: . ca~b~n .. a tom.•, Ohitwocaf and Freure ( 5) reported that the un.;.

catalyzed reaotio.µ of propylene oxide with ethanol

led to a .m.ixtttre ot isom.era containing 569' of the

secondary alcohol co:rrespondirig to attaok at the

primary aa.rbori a.tom, whereast the sodium ethoxi4e

cat~lyzed reaotiori gave S3% ot the secondary aloohol and none of the primary alcohol. They attl"ibuted this

to the taot that the non-oatal.ytio reaction is less

specific in .its aourse beoa\lse the higher tem.peratu;ttes

n·eeded to gitT-e a suitable reaction rat.a lessens the

directive e:t'tect ot elec:tronio density.

An alt~rnative explanation may be offered in te1ms

of. the generalization developed by applioation of the

transition state theory; namely, that in the case of

an eleotron-l'eleasing group, i"e~, ~he methyl group,

the weaker the base" the more likely the atta.ek at tht

secondary oarbon ato.ml'f Thus, 1.n the unoatalyzed :reaction

of propylene oxide with methyl alcohol, th.a moleoule

which attacks is uncharged, whereas, in the base oata-

lyzed reaction, the attacking group is the negatively' oharged methoxide ion. Baaed on the ga.~eralization,

aom.e attaok at the secondary earbon atom might be ex~

peoted in the uncatalyzed reaction. The etfeot of the

oate.lyst is actually to ap~ed up the reaction at the

primary aapbon 'atom m.uoh .more th0.11 at the seoonda:cy

carbon atom..

Fourileau' and Billeter { 95), in the reactions ot phe.nylglycidic esters and am.ides, reported that aniline

attaoked the glyo:1.dio oo.rn_pound at the o<.-o atom; where•

as dimethylamine attaoked at the carb911 atom adjacent

to the phenyl group, They attributed this to the fact

that aniline. is a weaker base. This is in line with

the generalization that base strength may affect the

dil'eotioli ot·:ring opening.

XXX\\\•

The discuasi.on on changes 111 be.se st:t"ength, up

to this point;·1 assumed that the energy contribution,

w, of the reagents to the total energies o:t activation

is constant., ·•,fhis may be tru.e tor a given l:>e.se and

its au.ostitutlo~ p·:-oduots, i .. e_., .methyl and ethy'l

aloohol. The assumption may not be true fo~ reagents ) : .

which differ <fn function.al groups, i., e. 1 aloohols and

amines. .The ett eo;; of a change i.n functional groupi.ng

;.r;.ay be evaluated separately.

.The ~!~S~.ions o,t Epoxides wit~ L~is Ba,se! Ao:td Cat;~tyz~d Reaotiqns A{ ~P,g~des

Direp~lon ~o:r; Rins Openins

The outstanding tact in the. aoid oatalyzed ~eactio.o.s of propylene oxides, butadie.ne .monoxidea, and styrene oxides is ~hat rdxturea ot· the isom.erio

eom.pountis are. obtained whicili. usually contain a m.uch.

higher proportion ot the produot correspo.ndi.ng to

attaok at the seoond.ary oarbon ato.m than in tha aase ot th,e base catalyzed ~eaotio.ns. '!'ha effect

ot the oatalyst', then, is to increase the rate 'Of

ittaok at th~ seoondary carbon atom .much .more than

at the Pl1lmaJ:iy oarpon a.tom.

Prop_ylen~ oxidef\•·• Chitwood and li'raure ( 5 l found th.at the reaction of propylene oxide with aloo•

hol gave m.aihly att.S:ok at the primary carbon ato.tn with

some atta·ok• 1i't the seoonda~y carbon a tom. Reeve and

Sadle (66) repQrted, sim.ilarly, ·that the oxide with .methanol gave ,.malnly prima!'y with some secondary attack.

Sexton and Br~tt on ( 62) obtained a .mixtwN;; in the re•· action with -phenols a.t:J.d scheutz (6,5) ind.ioated .the same

for thiophe!lols. Petrov (67,68) al.so reported. .mixtures in the aoid catalyzed. reactions of propylene oxide with alcohols-. Sltitth {109), Fosberg and Smith (110) and

Fickett, Gar:ii.ei" 'and Lucas ( lll) obtained l!l.ixtures in

which the p:ri!!ll;~ry oarbon atom or propylene o)Cide was

attacked in prefel"ehce to the secondary ·carbon atom.

Ra.itno.ud ( 112), however, reported the attaok oocurred

ma.inly at tb.ei :Jr~oondary' atom in the same reaction.

Levene and Walti. ( 11:3) obtained .more than 50% inve1•sio11

in the acid catalyzed hydrolysis ot optioa:t.J.y aot1ve

propylene oxitl.e: whloh l.ndicates that the ~t:fi.ack occur-

red mainly at _,the seoona.ary carbon atom, Halperi,n,

Donahoe, Ictei.pherg, and Vanderwe1;:f.' (1i4) recently re•

ported simile:r,.i-esults 1n the rea.otion o:f 1,2-epoxy-

bute.ne with t.he halogen acids. Paul (115) tound that

a mixture we.s obtai,ned in the reaction of hydrochlo~io

acid. ·with ,~m.ethoxy;"".'l ,2--e:poxypentane in which primary

attack p:redo.ct.:i.nated. Butadfetiri monoxides .... Petrov (76), Kadesoh (12) 11

Bartlett .and ,-~Ross ·( 36) and. swe~n, Bill,~n ~nd Knight

(69) :r.epol:'ted that the aoid catalyzed a.dditic;,n of al·-. . . .

;·' .. . · .. ,_.·-,:,:.;· .. ; . cohols to buta~~eJie monoxide giveEJ attaok exolusiveJ..y

.'<':,.:

a.t the seo9ndat7';carbon atom. Petrov (ll6till9),

similarly( fo,tind that halogen acids adc.led to halogen

substituted. btrt~diene mo.lloxides to gi Vt!J :p:rim.al"Y aloo"'!'

hola.

;Sty:i;-,e.qe ,oxid~~o• ReE?ve a.nd Ori.stoffel {78)

found that. styrene oxide with .tllethanol gave a .mix•

ture eontainihgmostly p:r1mal.1y alcohol, i.e •• attia.Ck oocurrec:t fadstly at the seoonda1;y carbon atom..

Hayes and Gutberlet (81) reported. tha.t allyl alcohol attacked. styrene oxide at the seeondary oarbon atom..

lCing, Be:rst • and Hayes {10) round tb.a.t with pyridine

oataiyzecl by -.P'fridine salts of strong acids· a high

percentage of attaok ocourred at the secondary oa:rbon atom..., Emerson {SB} and Golum.bio and Cottle (120) found that hydrio,Uo acid added to styrene ox.id.E3 to give

exclusively the J?rim.ary alcohol.

:t~aohunism of_ Rip.g .012anins

The m:ecihanism of r i.ng opening may throw so.me

light upon the increase in secondary attack brought

abou.t by aoid catalysis. The available ld.netio data

indicate that .ihe acid catalyzed xieaotions are third

order and that the l!ate is proportional to the. oon ...

oentratio.ns or the o:id.det the acid, and the attacking base. Walden inversion usually ooours in the aoid catalyzed i-eactions, although exam.plea are known in which only p~rtial inversion ooours. AD:$' . .meohanism wll.ioh is pJ:loposed must be oonsiste.nt with the:se taets.

Kinetics .•. ~ B:ronsted ~ Kilpatrick, and Kil:pa.triok

{ 20) detel'Jn.in~d ~he· rate of reaction of glycidol with ~. ~ .. -

h..yd1'obr0:mi,o .~.Qfd a.s a· t11~rd o:r.de;- reaotion· wher~ .-do/ ·. . . ,+

·dt:k(oxide).".lJf~O) (Br) • Similarly, Smith., V(odh~,

·and Widhe '( 12,:r l ';t''ou.nd -tiia.t the· reaction ot epichloro.,. r''.'

~rdrin. wit~ fftrortg :aoicts is third ,order... Ea:at.ha11t an~

:Oa:t'\-vent (ll) -~,~:;,o:,:-ted that ·Jthylen~ o¥'ide i.n excess

pyridine ga.v-EVrt .s~'~ond order ~eaotlon whe~~.. ....do/dt = . -\;: , .

k {oxide) (·ilk}. jc~.~eaoh (12) found that the rate ot reaotion ot bu,'t;..a_-di:e.q:e :mo.tioxJ,d.e with .mE3thanol i.ri ether

catalyzed by ·'s,ui:t~tU-1¢. acs1d was· dependent u~~-n t.he

me'.th.a.nol C on'c•~ht 1-Jtion. . .. _; ..

·walden .. 'inversion .... Walden inversion has -tre .. -. ..

qUenti, been demqnatra.ted in the nQid eatalyzed re--actions of e.1Jd.1,*:i1.o epoxides. Thus, B8:i'tl:~tt {l22)

\f -~!- .

a.nd Winatein (l2f) oJ~~ained inv·e:t-sio1;1:s· in th~ :;-e.aotio.ns

or oyolohexe~'$ oxide with hyd~ochlorio and hy-drob:t".omic ··':

acids. ·w1.n.stein; Hess. and Buckles (124) and P.larke and • • I •

Owen .{125} ~e,mpn.stta,tl:3t:l an inversion 1~ the reactions of cyoloh~xen~: ,.oxide with suli'oni'o a.Qids. Winst$in and

Hende:raori (1261· oba.er.ved an inve:r:sio.n in the acid oe.ta• ' .. ' .

lyzed a.dditl,o,n' 'or an alcohol to cy-clohexen~ oxide.

:Mouss.eron and .. coworkt11rs (127-l29) deJUonstr~ted Vlald81I

inversion 'int~e acid catalyzed ·.bydrolys13s ot oycolp~n• tene; oyclohexe.tie, and oyoloheptene oxides ·a:nd theil'

derivatives.

:,t1he9::r.z· of _ Dir.eOtio'°; ot Ring ·0120.I!i:ng ~imol;ecular, r~nra 01:ening.• It ls gene:ral1y

agreed thei.t the·ti:rst ste1> in the a.aid catalyzed 'reaot,ions of' epoxides with Lewis bases 'is the a.d.dition

of a proton to the epoxide wi tll the :f.'o:tmation of an

oxoniu.nt complex~ Many reactions appear to invoive opening ot tha.oxoniwn.com.ples by attao.k of th$ base from. the real' of the epoxide earbon which results in

Wa.ld.ru,. inyersion in the·l,'ate determinit1.g step.,

R C..\-\ - c..14- R. '-o/~

"' I (£·B-t-\ ( L} R-C."' -C.\,1- R. + ~-\.\ ~ OW,. 0 c,u _ c,.u_ D \ ~@ -._ ~ '' o; ri "

If the first step is ignored, the mechanism may be

looked upon as a typical sN2 reaction which involves ,a base displicement on the oal.''Q.on:,atom of t;b.e oxonium ·,, complex -analagous t.d a.ttaok' of the base on the· uncharged

epoxide in the base catalyzed reactions.,

01S• and trans-2, 3-,.epoxybutane have ~$en, used in. I ,

several reao{).ons ·to show Walden inversion~ Thus,

Lucas and. Gould (130) and. Lucas and Garner (131)

tound an inversion. in the ieaetio.n with hydroohlorio aotdti Winste:tn, and tuoas (l:,2) and B:elmkam.p and Lucas (l:'$3) ptoved. inversion in the a,eid oataly:zed t-eaotions with alcohols~ Sim.ilal"lY·, Wilson and tuoas (134) ol:>:s!erved an inversion in the acid. cataly..-

zed hydration and alooholysis of 2 ,J,i•epoxybutane ..

The meehanism ot Walden inversion. i.t:t the reactions ot epoxide.s is disoussed. by Darzens and :Meyer (1;5).

Reuioa and, oo\vorkers (136,137) demonstrated Walden invat-sion in the addition of halogen aoids to

o1s"" and t.ra,ns-st:i.lbe4e oxide. lfuhn. and Ebel (138)

obtained 100%,fnveraion in tht, ,~lightly- acid or basic

hydr.011als of' o:i.a-epoxyeucoinio a.oid,, bu.t only a partia.l invers.ioi in the slightly aoid, h:,drolysia the t:ra.rui .... epo:x:ysuoo1nio a:oid., Pal't1al lnversidn has

also been noted., by Oldham and Robertson (139) iJl the aoid oatalyzecl hydrolysia- of a sugar and by Boeseken (140) and Boeseken and \ran Loon (141) i.n the hydrolysis of' some a.licyolia. CipOxide.

Unimoleoula:ca ring opening .... :S::adeaeb. (12) suggested that the aoid catalyzed reaction ot butad!ene mono~id,e with .methanol :ma, proceed by y1ay of a u.nirnoleoula.l' :ring opening of the oxonium complex in order to explain attack at the secondary carbon atomf>

He found ,'that the rate ot' the l.'eaotion depends upon

the me~hanoi, oonoentration,.and s,uggested tlh-it th.ta ,,· , :·;_ ~~,;

is consistent with the pro;;,os,'9d, l!ie<lhafri:sm pro\'1ided'

that k2)) lcJ"' Branch arid Calvin (142}, however, toroibl.r point

out that the dif:t'erenoe between uni ... and bimoleoule.r

prooessea does not lie in the relative rates of pre~

l:iinihary end sttcoessive reaotiona; The bim.olecul~

reaction is three oen.tered and the ra·te of :rea.otion

is propo:rt!9nal t6 the oonoent:cation ot the attacking

base~ The .r.idst generally aooepted thao:ry tor the uni ...

molecular reaction is that it is a slow ionization as ahown in s,tep Ct) followed by a ta.st reaction of the

1 • ,,

oarbon1Ul'll ion with .metl;l.~nol as 1.n step (2); 1. elt,

k; ~)k2, • The fa.ct t-h.at the. rate ot reaotion 1$ d.epend ...

en.t u:pon the .methanol oonoent::cation. oan.not be explained

away by the a.sswnption that k2 )) k3•

Nevertheless, it is probable that the l'ate determining step is the opening ot the ring and the

.mechanism. is of the 8Nl type" ·'fhe dependence of the

i'a.te· of :i.-eaotio.n upon. the .methanol oonoentration ,may be ex:pla.i.ned in terms of SWaints .PUSh ... pull termoleou-lar .ruedhanistn. (143) -wi~h third order .kinetics ... si.noe the kinetic measurements of the reaction of butadie11e

monoxide with methanol in the p:r.esanoe ot sulfuric acid were made in dry ether, a no.n ... polar solvent.

In a.oco:rdanoe with this aoheme, thel."e is formed in the transition sta·te a sol vated oxonium compJ.ea as .s:hown in step (1)" The ionization of the soi vated

oxonium ao.mplex in the iatt1 dete:r1uini.ng step to. tor.m a solvated oarbo.liium ion as $hown :i.n:ratep (2) may

satisfaotorilf explain the ,etteot. Of .m.ethanol upon the .J:;\ate,

. C-k \. :: '-M •tM - c.~ L

'() 'Et) ~"' lr ~H"

'-«~'? H c.t\\t: C-K ~ - L\-\ ,-.. Cl H

Et,

The i.nt~.mediate fo~.ma.tion ot such· a oa:r,bon1um. ion is eu._pported ·by the tact. that epoxidef! m.a.y be

iso.ma.rized. to.a.ldebydea a.:nd ketones in acid: solution and ptobab~V pioo()ee.ds thr·ough the eame intermJadiate.

Additional auj;,ppr~ eo.m.ee from the acid catalyzed a.lkyla.t1dll o:e· the benzen.e .nuc:leua, which also p:t-obablf

:proceeds by way of a oarQonium ion., since a.n 8N,2 :reaotio.tt. is always acoo.m_panied by

complete Vialde.n inverslon whereas att 5N1 reaqtion 1$

usually aooo.mpanied by partial ·wa.lden inversion, tha,e does exist direct evidenoe tor the -uni.molecular ring

opening, a~ :pr·oposed by i;ad~$oh (1.2). The beat evi-d.etioe available· oontes fi'o.m. the work of ~oesekE;ln and

his oo•workers (140,lU),. They studied the hydl'oitais ot the se\ten (';Qlnpounds listed below in both S;lkaline and acid soluti·o.rh It was tou.nd that uompoundJ ~x>cvu, x,c.,c.vu,, ,uuux.and )C..L on hydrolysis in basio and

-aoidio solution.. gave grans--glycols e:x:olusi vely♦ Oo.tn:-.,,

pounds x L, . ><. L.", and JC..Lu, on htd;!'iol.y-si·s. u alkalin~:

solution al~o. gave ti-ans•gl.yeols exc.lµsivel:t• 'J;'h~y

oonoluded that· in basic sol'Ution Walden lnveraion

occurs invariably. In aoid solut:ion.; however 1. com ....

pounds JCL\1, x a., e.nd >t 1-,,, gava. mixtu.:cea of ois- a.a.d

tre.na.;;.glycols•. They oonoluded t:hat the phenyl grpup on

th$ ethylene oxide .ring was th<a oauae. of cia ... glyool formation... The ois .... glycol :to:r.D1!:ltion may best be:, explained by a.,n SN 1, unimolecule.r, i•ing opening of the oxoniu.m com:plex at the. ca:t"bon adjacent. to the phenyl group~

~ ~ OS err-i _J --...:.../'-./• -o

XL.t X'LH )( L.lll•

Re11los an.d co--,workers (136 1 137) found that stil~ bene oxide.a, to the oontral'y, added halogen aoids 'with Walden inversion.. Thus II ois-stil bene oxide with hydro• chlorio aoid gave the threo ... halohydr:1.n and tl'.ans-stil• bene oxide gave erythro'\"halohydrin. This would tend to prove "that,_ even under ao1d oond,i tions, attack at a carbon atom adjacent to a ph~nyl group 1nay, under oerta.in oond1t.ions 1 :p.i;ooeed with ·complete Walden inversion.

In the dasa Qt. ,propylene oxide" there is prcu:>f that-

attaek at ·the s.eoortda.:cy carbon atom m:ay :proc.eed ~1

way of ail sN2 •JtJ.echanism. tsv-e.tte a.nd Walti (113) found

that ou aoid :twdrolyais of optically aetive p:ro:pylene

O;t.:lde ·more than, 50:% i.nve~sion ocouri'ed., The attack

must have bee~, a,fi the ac;1oon4ary oarbon sinee attE\ok

at the primar~ carbon a.tom would lead to r.etention ot

ounti.guration• Thia ia oonsisten t with the Y1ork of

Boeseken an.d oo .... ,voikers who i'ottnd the int:roquotion of

a m.etilyl group on .the eth.Ylena o:<:ide ~1.ng did not pre•

"feJ.l'ij the ocdu1-re.nclit of Walden i.trverslon • i.n. acid

hyd:rol;rsis.

'.REACT.ION$ QF EPOX:rtres WI'fE: LEWIS AC!DS

Ueohanil!lm' ot. Reaction The rea~tion of epox:id.$$ witf+ Lew~a .1;>ases ,has

i'eoeived eons!d~ra.ble attention: in. the ou.r.rent liter•

ature. 'fhe· f~ot!on o;r ppo:tidee- with r.ewis aoicts.; .. \', .. ~

however, ·ha.s. -~eijn. less e:x:te.nsivel,t explor$«;• The

reaotion appe,rently involves a. bimolecular .n,uoleo--

pllilio atta.ok ·of ;ti'.b.e bas1.o r~ oxygen on. ·the aoid.

o-enter of t·he ~ea~ti.n:g molecule ·to tor.tl1 an. oxonium

co.m._plex ( 144-f &ff shown. beloYft; 'J;'hta di$plao-ed 1base then

a:t·taoka the• 4tt'ibon at9m ot the oxoniwn. Qomple:ic which opens the rfiig.

I \ -C...-(.-

' o'

XL)V

+ )(

' ~ -c.-c.-0 I A

-

Kinet"ia's:.• Sjo_berg (147) deteriri:l:nad that the rate ot l'eaotio.ri. o:t epiohlorohydrin w,ith aoettl ohlorid.e

was second orde:r. ij! hls supports the postulation. ot

an Sita .rneohanis.m. :Walden -'in:vers1.on,:.. ·1n fUl'ther support; -:ot the

proposed s.1? .tn.eohaniam· is the :tact that the reaetirirl

ot· c;yolohexe.ne oxide with benzoi0: anhydride, .acyl,

halides and alkyl, ha.litles- { lli,;5 ;· .14,6,} has been shown.

to proGeed wi:~h Waldeii 1nve,.rsion~ Aeid catalysis .• - Tht:t tunc:,tion of t,he acid oil SfifJ T ~ · ·

catalyst, as io, the l'eaot:t.Qn with tawis bases,

appeal.'a to be t_hat of lowerin:g the eaatgy ot ac:µivation

but by an entirely different mechanism,, With Lewi.a

bases, the aoid. oatalyst a.eta by polarization. ot ~,b.e

cattbon!N>oxygell -bo11ds ot the, opoxide tt:1.ng* Tb,e :posit.ive

Character ot the ring ca:ttbon atoms is increased a;md

this ~e~ults in an· i:noreaae in the-rate ot reaction.

In the l'&aotlon of epoxides with Lewis acids, nowete~ 1

the tunot.1011 of the acid catalyst appears to be that

of polarization ot the bond~· of tbe a ttaclcing reagent

rathe?i than t:he epoxide itself, whi<lh the.reby ~l.nerease1

the positive 'ohal"aoter ot the acid center in the reagent as. shown below.

A->t (£) e +· C." -::ii. c..-x c-- A .+ A

I ' r I - C. -c.- + A® £.. !> -L-C.-

'o' 'o' A@

f I E) I f -c-c.- .... x-cA _.., -(_ - c.- ~ C.A 'o'@ ' r A C

A X LV

Gustus and Stevens (144,), however,, eu~gestad that

the tu.notion of the catalyst is ttthe promotion ot the deco.rnpositton ot the comple,c.."

~alo,il with, acid oatal.ized! reaotlo.ns ot Lawn, )!SE!~• ... There is t:i. .strong analogy between ~ha reactions

o:t Lewis acids and the aoid c~ta,J;yzed reactions of Lewis

bases. In the oaa~ of Lewis· aelds * the t1~st step in

the reaotion appeai"s to ,be the form.a tion of oxoniu.m

complf.!x whia·h involves the ooordtnation o:r the epoxide

oxygen a·tom and the reaoti ve carbon ee.nter of the Lewis

a.eid, whereas, In the oaae of the acid cataltzed rea.otion w.:lth Lewis bases_,,_ the first step .in the reaction appea.~s

to be the :formation dt an oxonium oo.ni_plex which invol v·es-

the c002d:1nat:t_o.il of the epoxide oxygen with a proto..ti.. '!!he ~eoond step·, in both oases, ts the attack Of a base

o.n the oa.rbon a.tiom. of the oxonium complex. From a mechanistic viewpoint thf:t reaetiona are very simila.l'•

,.\

Reaotio,nq wit,h _Lewie Acida

Aotl ~Jlitdes~ ... The :reaction ot epox:tdes with a.oyl

halides resuft'.:in the tor.matioJ.t ot a.lpha-haloeste1is

{144,145,147}14-8,,15,5). The reaction prooeeds ,readily

tJith iod!de_$. even. ·at •SO degree$ C. ;- in l~ge yield,

in tl1e abseno~ 'of catalysts. Acyl ohlotides reaet .more· slowly, but may be aatalyzed by the addition ot a drop of l!Cl.:

C) ,, (. '""· - C..\-\ ~ +- (. \( ~ c.--:t

'o' CM._ - t..H1.:C ' 0 I ~ cc, I

t-t\ \

An.gyd•r,idez ..... The reaotion· of apoxides with aoid a,nhydride~ .:procluaea .di_e2t~re (146,,150 • 156...;165) e;; Ferric

. . i' '

ohloride, zino ohloride and liCl have been used as cata.• lysts. :Sedos obtained the trana-d,i benzoate in vhe ~eaction of oyolohexene oxide with benzoic anhydride at l60 degrees ofl tor 24 hours.,

C-M a,. : c.M .. CM I

- C.ti&, I

0 I c.~o ' C..(-{ '\

0 I C. :o

I

C..t\ 3

1Uk,tl halides.t- The basioity or the epoxides is suttioient to displaoe halides f1'o.rn alkyl halides with formation of beta..i.halogenated ethers (145,146,166,167). The reaotion is usually ru.n j_n a sealed tube at 1.50 ... 250 degrees c., for one o:r two tla.ys.. The yields '.reported are lowt-

XLVII\•

AlJ2ha•halogene.t~d ~t'!.k!,~,;_ai;- Halogens are displaced on alpha-halogena·ted 'ethers in the rea.otion w:Lth epoxides

usin6 catalytio quantities or mercu:r1o chloride ..

The products ar.e unfly.trune.trical aoetals ot formal ...

d.ehyde ( l68 ,l.69:).

XL IX.

Ethers.~ Ethe;rs have been reported to undergo

the same ty;pe of reaction with epiohlorohydrin using

boron trifluoride catalysts. the reaction proceeds

readily at l.6w temperatures giving high yields ot di ethers (170-l 72).

. BF3 U.C.1,\-..•C."-u.\a.. ~ C"'MtOC...,Mr -, CLC.M.1.C.M -C.Mi

\o1 0 '91© +C.1.kro ca.Mr ~

.A_ldehy~es. a.D:d ket.qi\~s.~ '.!'he .~eaotion ot e:po:ddes

with. aldehydes ruid. k13ton~s ia a u1:1et'ul p~eparative ' '

method tor oyolio aoetala (173-lS0).

Although stannic chloride has ;been. used success""'

titully a& a catalyst, bo~on tl'ifluQ~ide ethe:rate 1s the

Jn.OSt satisf'aoto:ry of the catalysts.

LI

PhOS,Ehqrus, and ,sulfUl' .oom.J?ou.nd.s41 • The reactions

o;C epoxides with Lewie aoids are not restr.:i.oted to tb.c;se

:reagents having the poaitiv~ oente~ o:n carbon. '.Lihus,

bonds may/be 1'ormeci between the epoxide oxygen ~d sul•

tur as w~il as phosphorus.

Epoxides have been. report.ad to react with sul--

furyl ohloxcide yielding ohloroallty). esters of ohloro-

$Ulfonio a~+~s {181,182).

All>$1'IIOl'l and .'1$~;A1liua (18:;) •tu.died t.ht tea--

,PEl'ra.tu:ra~OOblp0$1 th>.n ourve tor ~ha suitu'.ll dioxide~

eth;rl1Jn~ o,r.tde syst.mn.a !he1 tou.nd a maxhu.w at ➔S d.qrc,et Ca which oor.re4po.nded to all equilaols.r

J».ixture o~ sttlfu:r dioxi:de: and •thrle.ne oxide 41 $Jid.

uswned that the co•poMd. resultetl f:.C()Jt the to:r.-t1<>n -ot a <.tovalct bon.4 between t:he epoxide oxygen and th•

. . \ fUltUl' dioxide Mleoule.

Phosphorous trlc.b.lo~ldea and t;-1b:to.ni1dea (184• 187) are also .known bo reaot with epox1de$ as show.tu

LIii

Little is. la1own a.bout the direot:ton. o:r ring opening of epo:x:1d..as wtth Lewis a<lids, Epi.chloxio ...

hy<irin has be~.h reported to g1.ve the produo.t which

cor:tteaponds to e;n•,-a.ttack on the p:rim.a.ry oar'bo.o. a.tom

of the oxoniu oo.znples w1t.\l aeyl halide (147 .l.54;1;;) • aiql llalidea (166), halQethers (168,169) and sulfu:ryl . . . . .

o,b.l.qrid.e ( 181} •· Giyo14c>l (15;-i) has .been r~ported to give a .ndxtur$ with ac;rl ·halides.. Sjoberg (147), h.owevel', repo:rted that glycidol ge.Vt;) pri.noip-.lly the p:t!oduo~ whioh {);orresponda to p~ima~r attaek~ Hunt and

Renshaw {l5l ), :rou.ud that the p,1.raa:1 carbon a.to.m. was at-

tacked in the reaction. of p;ropylene oxide with aoetyl

bt-omide. In cont1'adistinat1on, Malinovsky p.82) reported the product whi-o-h corresponds to seoo.ndary

attack was obt$.j,ned in the reaotion ct propylene ox.$.de

wit'h :sulfuryl ohior:tde. ·rt Jne.Y' be that, despite. so,me

contrary indidat!ons, the pri.tna.l-1 car'bon atom is ·att~cked prei'eren·tiall,r in this type o:t reaotipn,..

DISCUSSION OP EXPERil\EN!AL RESULTS

DISOUSSION OF EXPERDdBAL BESULTS . . . . . 1 ... ' •.. ,•• ... . -·. ·"

I>1x-e.etton o·f Ri.ns 0;2e:ning ot st11Jl!!!!. 1 .I L 5f I.. . . . . I .. I• .

· Oxide$ .· A?OWlf

¥,1:n,i!TlAzatio.n of Steric Fao·tors. It wa, pointed out it1 the discu.ssio.n, tit the

tiire()tion or ring open.:U1g ot base catalyzed reactions ot _p:copylene oxides; that the attaolc was predoxnina.ntlr at the p.r_ilna.r:t carbon. atom, with 11tti• o:r no attaok at the $eeond.a1-y carbon a\om: .indicat·ed itt the vast majority

ot -reports... The sattte is true of styrene oxide, but the ocour~enc~ o:t atta.ok at the seoondart ca::r"Qon a.tom to a small extent .. was often l'epo:rted, In the oase ot butad1ene monoxide. attack ooour:red ;pr.ed.om1.nately at the primary o~r-bon, but secondary at'.taok was aQ.rna'Wh'.at more pronounoe·d thall in the case ot styrene oxide. Attack mainly at i;he

secondary carbon, a·to111 was rareltyreported. The f}V1denoe

points tQ a. st:N.>ns ·st.erio tacrtoi· which operates to oi)-. . '" ~ .

soure the eftE,Ct· Of· electronic t.a.cto~s on tl':le direction

of ring openillS•:. The problem. is olea~ly posed- to study the elect"!"

ronio eff'eots-1 .it is neeessa'X'Y to mini.rniz~ o;, el.1.Jau;.nate ster1o hindetance as a faotor which govtr.ns the direction of ri.ng .opening. It appeus that the p•substitu.ted stil•

bene otides ware suited tor au,:,h a study• In eis ...

or trans-stilbene·o~ide, the epoxide carbon. atoms a,re sterioally. equival@t .. The 1.ntroduotion of a.

p ... sttb~tituent would not 'be exp~oted to destroy that

equivalenoe. Ordinarily• the p:i.·inoiple of vinylogy

would allor1 a predi{~::.tion that the placement of a

ph,~.nyl gx-ou;p h~rtweeh the .methyl group ·and the :ring

would .not hinder the tran~a.1asion ct the eleetronio

etfeots or the kethyl group., It ls neoess·a:rt, however, J ' '. . . . . .· to take into t:tocount whether the p-aubstltuted 1;ttil•

G\. r- e bane oxtdes·" qis.io or tre.ns-,. since it ia kn.own that a

oontiguration .may be imposed in whioh the directly

trans.m.1tted eftecte1 of the polarities o,t subst:1.tu.e.nta

is at a maximtifu ·or m:tnitn.~11 IInb.ibition of oonJugatio.n.

ef:feots is< .r.uo.r~ 1.ikel1 in the o.ia .... ; qontigu.ratiop, due to . : ,, ,_ . ;·''· -.. ' '•',

the effect of the ortho ... hy-rl~Ogen.a on the ooplana:r1ty ~ .

ot the moleotillB. .Ha.nae, it e.ppea1·s that the trans ... ;p• substituted at;ilb~e oxides .may adequately serve tc,

··- ,. '·· ·.

eluoidate ·the eleotronio e:t:reota ot the various sub•

stituents ot interest, and thus, were chosen tor study.,

p-:Methyl:fltilbene oxideJ in pa:r!tleula.r, was ay,n ...

thesized because of the olose analogy with propylene oxide. The first prediction was that the product whioh-

oorrespon<led to a.tta.Qk a.t the carbon ato.m adjacent to

the phenyl group would be obtailJ.ed predominately. ~his predioti,or1. .was based solely e>n. applloation ot the oon-cept of. repulsion ene:i."gieth the ·p ... oh.to:rostilbe.ru~

oxide was desi;red beoause i:~ was thought; on the ba$iS

ot :repulsion energies, tha~ attack would 0001m predom.• tnately at t~et carbon a.tom. adja.oen.t to the chlqrophe.n,l, group. Aotueilly, tlhe pred1~t1on.s in both. cases 41d not

eo!noide wi,t-h t'lie exp~im.e.ntal results. Aluminum. hydride was chosen as ·the base both be•

cause i'b previously had been established that its re• action$ were ot the sJ typ~ and because it was tound

to reaot r~ad.1iy with the relat;;ive-11 unrea.otive stil•· bane· oxid.eii. :Fu,,rtJier, the analysis ot the .mi:xtuie ot isoIAerio 41a:ryl: aloohC)lf!J ts tao.ilJ'..tated by the faot

that th·e individual. alcohol$ can be easily synthasi~etl. and cha:t!ae ta't' iz ed .•

·•· Lithium alttminwn h.y;ditidet ~- . ¼

studies in the direotio.ti' of ring opening have b~e..n previously re!)orted. in whioh llthi.u,m a.lwninwn. hydride

was the attacking ~eagant. Thus .• with t;Jtyrene <>xide 1

Brown (72, 10) l'epoited a 75'/o yield, ot the product

001:re·sponding to attack at. the Pl'im.ar1 carbon ato.Dl;

tvhereaa., with butt\diane monoxide* a mixture was obtained.

these au,thots· further esta'bl.J.shed the meohanism. .·ot reduction of ~;poxides a$ a bi!nolecu.J.e:i- nucleophUic ;rt$act1on _by pr,<,of ot Walden invetslon i,n the oyolo,,.

. -~ .

pent.ene oxid.e ·-~h_ct 'OY'-<lloh,xene ... o~ide serieih ·:pp1ns (104-) also obtitfued: a Walden inv$rait:on in t.he rednct'ion ., . . ,·.· .. ' , . . . ' .. ,\, ' .

ot suga:;' e:poxtaes it:o desoxysugara • ~he proof. by

Leroux and Luoas (188) t;ha.t optioa:Llf aotil"e 2,)-epo:q .. butane on redu:ct:ton with. lithium. alu.r1.d.nu.m hjrdrid_e gaye

2--butanol ot ·99_~ ·i)ptical purity- tuJ:1the:c! est'ablished the %2 chuaoter ot the .reagent. The .n_u.oleophilic oha~·-e.tlttt ot -the hydride has been established in reductio.na of halides (72,189.;191 (192:t.19)) as wallo

The .ro.eohanitam pr·Q·posed by Trevor an<l Brown {72)

as show.n below' therefore a,ppea:r~ tQ be co:r:reot. They

note that ·the a.tta:tolting g~o~p is pi'obably Al Xn •li4-"!'n;

who.re n prog:resses trom. z~o to tou:i.- as the reaction

pi'oceecis.,

LIV

~ \ -<?.--c..- '-t-1\IH-3

1 I 0 e

tithiu.m altU11inU!ll hyd:t-ide, a~parently,. a.eta in

the same manner as a. Lewis base. 'l'hus; pro_pylenQ

oxide is kno,v.n. to react w1 th the. m~thoxide ~on. ex,.

elusively at the primal'y carbon atQm. Simile.:rl.y, 11 thiu.m aiu.minum hydrid·e was ;eeported ( 70) to attac,k

propyl,ene oxide at the p:tAt.ma.ry carbon atom. In other

reactions also the hydride a,tt.a.ok:ed the p:tti:xnary carbon

atom. in prefeite.noe to a seoo.ndary or a tertiary o;arbon

a~Olil♦ Thus; '11'oster. and overend (194-) found that in i ,2-3, £>..;.dia.nbydro .tnannl tol, at tack oeourred ,~xelusi ve11 a.t the :L .... ppsitio.n. Bl'ow.n and his student.a (70,72)

tound that ·butadiijlie mcnoxide and styren.~ ox.id.fl we:re,

attao.ked ;ms.inl.;¥ .iit the p.r.iJDJA,ry carbon atoitt, 8im.1larlt1

Eli el and lr.ree.llian ( 190) repo:rted. that ~•methyl,at1l'!ette oxide 1Vf.!.S a.t~auked at the pr+ina1"1 :position. ;J:t 111ay

:b~ eonclud.ed.,. thent ~hat the lithium. alwni.t1W11 _hydrid~

red.ut)tio.llt:! of ~poxides· have·• l.itt.l,t o~· no.u._a ·Qt tb.e

oharaoteristios o't aoid c·a.taltz~d l'e~otions si.noe.

attack at the ,seo9ndar1 ~ar·bon·· ato-.m. is not observed to a.ny appreoiaple ex.tent ·e~oept wher~ Stf:iltioallf

favored as it{thtf ease ot bute.d,tene .mo.tlorlde •. .. • . 'J ·j, .· ' . . In the t-6regoing discussion of lithium. alwninu.m.:

: I. !

hydride, fairly conclusive evidence was preselfted that the reactions are ot thEi 8N2. trpeo In tll~ dis-oussion of the mechanism ot aoid catalyzed reactions ;c

it waa .mentioned th.at stilbene oxides. ey$i. under acid

conditions wli~ch :ravo:r 8i'll :reactions, react by war

of the 5r/· .mee.hanism. It appears reasonable, then,

to assume that the reactions of stilbene oxides w-ith

llthiu.m aluminum: hydride are of the bimolecular m.101eo-

philio type.

1f2.me~1me:q,tal ¼~§t.Uts. 4't .is r,ep_ortizd 111 the e::perir1l9'ntal aeqti.◊11, or

tb4s thesis t11.a.t ~.e lithium alura,il:'lttm l1Y¢ltide .~.~·. ductio:n o;f' p~met.nylatilb~.tle, c,jr4,4E? Y+~lded 59.9% of the vrod.udt Which corres'.oonds to attack s.t the

;•, ... • •"••••;,•:, ·••- l :••• •., ,•,,; :. '.,' ••,•-.;\:•_ ••••••-:••• -1,• •'." . > •• '' :• ,, •: •. • ';

c.a:rp<>n a;t;om a.ilJa.cen:t. tq tp,e: .. m'?tl:iyJ.vhe.nyl .SI'?UP ·~. 40~l-% of i,ta, ,:LJ~Pl~~tSi}t~ .. a. :r.$.,'.ti_o or +.,!10 t9 :i.oo. It ts, t~t.4~-:r tepor.t.?d; that t.h~, .~.p.a.J.,9gou$, r~~1cti9n Of

. :p-¢1++9,fQp,ti:tJJ.9p,p p;~4~ .Yt~;l.<;I.$¢1. ::>::>.1-;t Pt the Pf0;7J ,,Jiuc.t yrJ1+¢!1.,o,qr,~?$P0t1c,t~ J.p ~tta,¢1t a.t the .~o.rhon atom .AAJ~P..§ni t9,_tp.~- .!lli.Jp,:~9pli~11tl. sr9v.P an4 60~9% of its isOil~(;)~, SL· :l'."at:to q;t 0~6lrO t,g l, OQ.. As :p;reyl.9ul31y men,t,;i.qnE)<h. '{:,p,1;3p~ .r~~µ~J •. s ?-:ret 11,pt :ln e.ocp~ with pre-<il<,rt:t9n~ p~si?!g. oit. ~~p\fLl;l;l:On. e11.el"~es 9:r- by anµpgy-w,:i. t4 t4~ J"e::,o.otio~J q-f J?tOPY.+!ffn.$ ox:tltet5*: H~:q.ce* :tt b~~om¢$ ~~(}1?£.f:31.ll.'\Y ~◊ J-.n.vga.ti.G?,te n.to:re tho;roug4ly tJ:ia l?J;1$.E,\Q.4$ fQ~ .. :tJ1q ~~y:e~s,~d.. $U:r.;s:t:l:t,UJ;r1t eff eet: • . ~~ Sµ.bs;ti t.µerrt~ iftec:ts

T,h.e atilb$,ne o:Y..ido$ otte·;r:• ~ unique m~thod. fqr the ~t.µ<l,y gf th~ $1.';fegts 9.f ~. p-st.i~sti tµ?nt on a ~+4? c_4a.;tii o~r.oop.. ¥.t$;,ripw:~ lll$t,he>q;c. ;t,nvqlved. a atudy ot: t,..llg Z-$.te~ q:f :re~ct..trn1s of tJ:l.e p ... stibst:i. tuted. ?.P.4 'l:.l\~ µµ~µµ~rtA.ty;~¢4 P'?+f,~Y+ MJ.ict~e ,. b,~nzoi.q acid $s.te;r1:1, W.uid~~t h~lides, eto. Ip, tl:.f: 13Ubstitutsd. ·sti:tP$'li,$~, tl'l.~ r~"t+9 pf p,roiiµqt,$. .s~rve.s, the sa~ pµ:rppa~ $i; ~1.1.$. '-t "4~$ .. ;t'Qv,nd t..1la. t the P.""~µl:>~ti tu~n,t in<::;,:-~~?.$d ~~-<;: P~.1:!~. qt ~i;.:t,e.~·l?t_ Ol+ ~1e ap.jp~Q~;nt s1.de ,qn..~i,1. P:';l.l~Pott ~-tPi'A .... tPc ... tl1~ PW.'J:t., p~met.l,y:I.- > _;p-cy ... d;rogen... ) p.;.ahlo;rq~.. fA~ l'.ttmlet,'ioa.l :ratio 9£ t® p-methyl. t,o th~ tm,sµbs:t,ij:.uteq1 if; l~.$0 J l~OO Wld ths p.,.q1µor9- to th.e unaµl:>st4tu:ted, 1~ o. 6!~¢} l~ 00;;

i.::+'}1!:lt effect;. of,:the subet:Ltuont on th.~ l"itio ,of p~q4µ9t& ~~t.;tA~a.:-~i;.· .. ·~.:.··.1~~ .. ~~~.~-;.1;t4:t.$4:···s•t;~+Pa+1¢ oxides PC>l"NSl)()J,"J,(?,S' i;.q,, ·t.11,~··•· qrg.~,t \;f'o~~inec'.L :j.~1· :~ll~ cydpol.yses ot P!713l.).b,a ·t:1.tw~~f(:}1>~~g;y1,., 91µ¢~4,en, ~ct flµot+d.e~ :l.n

.. . . ""

aqueoua ac~t9.1~~:'.;A~ ~:1.~<;>;11.Q.JL~~cl t4e ~$9-¢~.fa;?-1+$ of ;ii~

12$ttbstitqt~c:l. h1$n,ey,;1; 1Ji+l-1.o:t".i4<?~. vr.i.·~. po:to.aal,.µrn · iodide ·. ·. -·,:,· . ' ._,., .. ', . . . • ... , '. -·:;. . . . .<

42:L c.que.qufl -~g~:tPtl,~,, J.111¢~~ ~GJ.g:t;ip1)a a,:-e -1:crl(Ywri to µ~- q£ t11e $tf''iy~e.,_ ·

The f)~ta.ct,: 9ppo s:t te ota.er hatL h~e11 det~X";~ned £or ti:11;1 $fi'e,tft, .. of p~$~~~,;;::l!t~3.fij:ta,)~~ :!µ1.e .t'ates Of r,e~, a12t.:to.~ pf p~1,1,~yl. 9b.J,,9pi,4~-s 111'@. .PO:$aasl.ur,a. iqd:tdq iii a.c~ to:n.~i p~11zY:t f4,.u9,fiu~~· rrJ. ~ apd:1.Ulll :,etb,0~4~ in ethyl :~lgol1q4:, o~n~o;t+ alllq;r.iq.q$ With ~thyl , e.i.; 90401 f ~t-lJ.YJ.. P$P,;$Q~,t$i3, .Pll. "~'.J.kalil1e hyd;ro.lyf?:1.S J .t:Ul.Q. l),~4z~d~a. on. a:q~e.J..;i.tl$ .. l?Y4f9.lyp.ia. $:i~ order, P:-phlor9.~., '> .. P"'.'!~~f?S?A::, ) :P~.mtrtl~,i.~ has l>C$ll, cdrref :I.fatted •with the :f'aot t'.l:l.at 'th;ese l;'e~cttor1a , are of th'Jt st/- 'f.,ype_'> . - . . . . . . , . . ··. . .

~-t does ·~1ot .a~$1ll .pe~~c:ip-4bi$ to ~$aunt¢• $,+:nee the effec~ .of J.p,e ~~1?$.ii~.i\~~~~$. .. i~~ 1ffjiil;,~r+~. P.Pil,,i?Q- '~•~ the sar.-!fi Q;ij .:f' o~ t,J;.t<;! ~N~- _f,Ef~9t;t.011s,, a.ncl we ·z-eve;ra~ :Co,J;· the f31/- ,:;-?~q:t,:1.g;atJ,I :t,h~t. tl1.~, r~a~t:to!lci. o.t: tho f;lti1bene: q;dµ~~- 1v:l..i:,p,) .. i tlliunt. ~lumi.11~ hyq.I"-i,de• ~l."'e al$0, ';J,N:, Evidence in fay9r o:r •a.-1 sN-=- i,11tarpreta.tion !'or the stilbem1 q:tid.e rel;l¢tions ,has p:reviGUf!J;y been. o:i.te4 whicb. l~a.",tElf3 li tt,1(;} d.ou1:rt. as to ·t.i."ie lll.eoh®iam, Direct;to.11 of Riru5 OB,e~.

Tn.e ,reve;r1;3eq. :~ffe<Jt of the p4metbyl. e.p.d tl1.e pii-· Qlllo.ro sitbstitqent 'f4$.Y' perl-iapa l:,(3 ·exple.1.iiod ·1n. terma .of the bqµq. ~tr(:jµgths Qf the: ~e.14bgn'.'."o,:yg~n baud.a ct th~ _ep<:>xid.~ 11.q.~~ qr ~?sonanQQ,. ;tnvolv-1:ns the oa.r.:7, bon~oarpon bond ot: tb.e, ~po~d.~ linkage.

-.74•·

;eo:i:ia. streJjij.5,~111«,-'; _;t11 ~p.e discµspiOn.t:\ -o:t th$ ti,.a.ns.1• tiori st;4t,e, :l'.b 1'ntn brougrrt ou_t, that the effeo~ qt a e1.1.bst:ttue11t on. tha d.!~_~tlon of r,;tng <ip~:n.1.ng; in - - -

p;J.~.e e~ talyzed r_<:?$;ct:t.o.n~ ,rne.y Vl:J;).."Y dep~ndJ.115 u.:pon the charge, El'Q.<i tn,e no:tu..~ of' tl.1e e. t ta;cking be,s (h T11us, · .. ' . -· . . . ·,., . . ' . ,· _,

-tit- d.e.C~8.S¢ l;n i;.J:le 9118+'$~. qt '°~b,ia Jl 1;tatlki:t1g pr~up in.-· creat\eS th,_(;> imi?_C:r:'t,q.p .. qi?· or l'.,Qn( a'f;,rsngt,,hs ,::rela:tiva to tf>l)11ii,i9.h ~+1$P£;iE:S _.(Qlfp}., ir j;hEf .:P,~tu-r~- of. ~iG' att;a¢k~· t1is reage:rit :t $ ~w:.:'h. '½4?-t. th~ J?~rq~n9nt, :rcpulsi.o;i.1. 1$ b,.tgh_, tJ-:t? :t~pq:t<t1;;.nc~. q:f' -1'.)qµe:t s t:reP.ttthS'. :J,":e-};at-.t~ve to ~(;?:e:>1.lJ,~~~+l. e:n,~t>eti~Jl_ ;1.~c~g.~e.$_ .{91.t,~J~.- A ~}."d. fs:otP:t;> #.i1vply~t:1 tl:i.9 po1t,<=( c;:li ;1.:ttr,t¢~$ ~n_ tll~ 'tX>&J1si, Uon :;; t~M ¢011ll1:3.1:"'00. \9 th.~, pqµg, 4ist?,rLq$.$ ,in i:,,11§ 1n1tia.1 ~taw •. A. t:r,;1ll$,~~:!PA $.t$.:c.~ J~1.,V~)J.¢l';, t,h,~ .d.Jst~"'ldG,8 qt the c~ 'bc;n,:bt.a$_ pon,ct (1"'0) Jfrttt ,c~~p9i\~.o;i:yg$:1 1:iptld,.(va.J i:t:rrp, l.?-+'6~ cqTJipai--,'.;:c:. _tq ti1.~ catiJPn,'7-o:i:;yge~J. honµ \l:'1 ) in th~ ini ti.al statr~ Hill 1ncr"€'a.£H3 the .irrrnort1;?.h◊e of the -- ,· .- "' .. ' ' : .·- --,- '' ., ; , . . - ',, ·. . .--, ' .

bc>17-d _st.raY15ths telat~.v~ i>o t;h~ repu;..pi◊n energi~s, i. e~ i 6 Ei;, .cor.w~red., t9 A!:!.\ (lMl.b}

A. E:i. = eA /¢n/fe. . -ec 1_ ~i3t r _____ ·a_ - --- -1 AE.o- = -~~ ~- ~- 1 , .. _. 1• r· 0 . l

><. >< V \\ \.

l:t, .1.~ ,Posc9::lb+~' tna.t the direct.ion of ),"iilS open~ Jrig 9.f'. tl14l,l st1,'.f..'Q~e o~~~es, ma.r, l>~- · ~ttril:)u~ect tq ths _l,1~µ.ni .aluminum hyd.p~de, .r.~~ent. _:ct .1 s oonel$i vaJ;)le the:t 9-ue. _ tp th,e _:t._a:rge .ei1 ze._ -of' th~ a.t~¢klns hyd?":tde, p~tio.ula:rly ~rt the .lat~r stages of t,.,.1-i~ reection,

··i:incl __ g.U;e t..o tn~ R~~EI-~~ Fl~ ~e Ph~eyl. 6:-0U.:PS. on: ;th~ e.po~q.e ;I.iw~e -,~t, ,.a,;QJ;.µtQµaioli o.t th~ b(?~ be7· t.w-~en, t,.11~ a.tt~~~, b$f:3~. -~ ~h~ ~ns eaJ.'"'bon e. tom o_¢~~a WAii;>A. s.i:r.E?s ;ri~f;:). tc:>. ~ ~.iSPlttQa.nt increase 1n tn~ :ratio Qf x-0 to--~~• _h~n,oe a. d.1ti;use troots;Lt~on 1ta.te~ The :t,m.pq;.,~~:p .. ci;l qt' 6 ~;, ,1.$ the.t'o'by,. ,~ncx-~a.sed; f. ~ild it )rgul4 ~ ppe(i.1.Q·~ .~1.~t, -~ ~l.~o.:'c;:,t-Qni.wi·tlid.paw:;tng e;1"0u.p $hOuld ~rtq;e;t\ ~~ a t:taP.l< 9-t tne bal3e :rela.t.l ve tcr hY.~ d;i~og$n. '3,ranch .e.rld. Oa:J.,rin (l42J>} .ha.v~ .<Ja,iil.Er.i. a.tten.7., tio,~ to- i;;h1? tatft .tua,:f.; ~- effect ,9f a ,aµl?at~tuent

. ' . .

rn:;cy be ;1n a.~¢qrd; w; ~- +. ts ~t:fe<rt on the o.o~ ·fltre11$ths t13,•~:r ~ ~e: ... N!ml..1J;l.911, ~U~li'si~s tn. $.: reaQ.ti9n. whioh invoive$ _a. <l.i.tfua$ tr.an$~ t,~qn ai~~~- lir. 1~ '$1~9 poss1,b~$ tna.t,. dur;a to ·t,be ;t:p;tere.Q.t:l9µ 9t the two phenyl g,;>c:>up;ij th~;,e: ... ;$ Jl ,1;J}1Q;,,'t~iU.l'l€i r:;>f: t11-e two c~-'boli. pprld.a (f':l.}· .:in.. tP.~; s.~u:na. Jtf:iat~ ot tlle moleoul;e'• Si:h.Q$ t,t-µ.a z~~~/~9i? W,P.µJ.µ ___ ,.,.1$.P. in~~AA:~ i:,he. 1ntpq.rtanoe of A .Es ~e:i.~t~y~ ::t,Q. A.#l:i.,.,,.-4-t ~.f.l. p~rpap$ ·Q.~t, $tWPJ.i1s ... J113 -that .;n P,'7'QlµQl-"e~:i:i+ib.E3llff. 9~4,.t tlle e~eot:ron. Wi tb.e.r~w:4¾'5. qch:t.q~1.ll~. ~µp .~~YO?'$ atte.c]i+ ~t ·t,he. flarb.on. a.to~ $'1.J~c~~t t,Q. th.~ pheµyl gX"OuP,. 51.m#.le.rl,y, a methyl g,:,oup ·siipul~ f~9il'- 'taW e:ttaok at. the c<U'.'.-bon -~torn, ad3®..~~:tr. tp -~~- ~eth;r~ph~µyl e;ro~p iin p~-r,ietJiyls°t;).J.bene ·9_~(!~,,.. i~Pl?~~~~ily:., tl,1.e e,:pe~i1I1enUll

I • • •

reauit.a ~i~e in e.ooord ~3.tb. ~he .. results pr-eo.iotei by :the tlleo_ry as o~ .. r~l.~~--,.

'fb.e -bond. strengtl1, theoi-y m~ a.ls.o lJ~ applted;. ::li.P .a new disooviq1-w ~~ re!l~nt,ly :by We. t~rs (4) • He found that 1n the rea~tion ot l~metho~--a.)-epo~-.;

the , ..

a.~taQµ: of the met~toxi,~~ o¢'c~d e~olu$lve+Y'''S:-e ~$

cat-1:)9,ri. at.o~ r,dja.e,&.r1,t' :to '.the· metho~atJvl -~roup, 1.11.1i in ti111 ptit±rt :.¢£'· E;J.;:f;:1;.P-~k ~hi:r:h ;1-ould! 'h~ pre~ . . ::, _,... '···. ' ·• .,. : . . . '

di;ot~ l:Ja.$~d, on. rew+1;11~:ri ~P.e~J.""g1~~ Since tb.¢ metl".,3f;l.. s.~o~p ls, ~;L$qtr.~ii:r:telr;1,;~iry.i ,ru.~d t.l:le: ru~tho~ethyl gr:~~ll ;1 e el.ec.tp(?;i~,,i t,l\d.~!;tw.1~'.• OC.lf-:

· .. ,· ,- it e _ _ \ 3 C..~3-3> c.H, -~ ~c..H,. OC.K3 -+ OC.1-1,..3 -i> C..l+a-fH- -Cij.-~I,~

'cf LV & ~ 3

l(i th -lt~hitt,rn e.J:u..~.!+il.il?l. :p.ydttt!,l$j! 11,ow~v~p.,. the ~t-t_a.¢1:r: Pt "t.h$· :9p;s~ !£,$ --~~ -~~ ~:~~poµ aito111 ad..Jo.~~nt. to" th~ .:n.iet~)Y:t. sr~iw:, ~t.J-t$ J'l-~c~-n~, ~ ~Jtt-t1~E? -~l."~.ns:1 tio:n ,$ ta~- '.irl. tp.(}.; ~.tt9·ti~n- 11)/fth Ji~,1,.;m al~im.µn. btd.rid;e,-, tl:l,e._ };~'.\t~~C';S~d. ~t,tf],c;n~ :t.~- to pe ~~'!J$Cteg, s,ince i.'.tle effoc:t of the oubstitu~11.ts iil to t:roa.b;)11 ti.½.e 'bo1td. bo• . n .. - ' .. .-• .. . . .. .,- -· .. =<· ·"· • . . : . . . ' . ._ . .. , tvt¢~11r ~"le pt;fs~ti .at.a~ ~2fl. the e~rbc11 atq:n $.d~acsnt· to the methyl e;r~tt:P 11!.0i"~ t~.a1'i the :c:i-~h~r ca;rbon-¢zj"gE:l:d; :bQ;~,,

The reaotion ot' p.-SJ..tl:>sti:f;.µte<l be.nzyl l;it'9m1c~e~ ' . . ' ' .

w:$. t4 _py,:-id.$.ntS' 11:1, dt;y _;t¢.etq:n~ +,,S .often <:ti teet (21(), 217) a.a- ~ examplQ o.f a ~!m?l~l'J\tlttt nr1c1'.teopnfl.~a 41spla.~:em_E;mt ~e~i+?:n i,n. whi~ll. t~ ettect .. of' t,he ,aub'stituent on. the rate of :rea.at1on is 1n accord

. • • . . . • • . . .. , • . ' • • • • .. · •,• • . . . •~ • • ; • . . . l .

wt th. i~s ef'f e~t o:o,. th~ bond. _str~ngthp :rather ti1c-in., tb,a :r-epµ,:t~ion. ,~:n .. ~r:$i~,~,t---- .,N.0:~;iy, ~P. s1v.2 :r~a.¢ti9ns,; ~~ xµt,:ro s,.vapµp_ ~e~¥,~4.\t ;t;ner.~~~~$ the r,e.te of reaQ-'.UQ_l1,. :t,u~ in, _t.pl.,~ p~,;rti.oular ~:~a~ •. t.J.le n1 tr~

' . . ~-

sroµp $l9W:$ .t'b.~ . .rJ~q::M~Rli,i. W ~ . :.Q;i t~ thl,.fJ as StW~· ,:po;i.~1:r.s ,evide~e,¢ Qf ¥~;is p9ss1~ili'f;y of. a :r~~:t-e;~l. Of tn,e, supt,;titµ~n~ 1~.,-~. _ij~tcMY Srs 2· ~e.cti◊n..,

-77-

Ca;r:bot1:::cap,boµ bond of e1:io:;9:de, linly:v~e ;tn .11:-m~thl(ls i:,ilbene;' o:;tlde ~:.:~ .. +P,; ;~l:g,l_ ln:1t1aiL state o.:e the p ...,m~ thy 1 a til p1;1ne ozj;.de rnt,~egule ~ tri,e, elE?c -~i·on7re.-l,E;aa1ng etff#C t, o.t: i:,µEJ m~thy:\ e,u1>s tiJ,µ,ent on thf.l i;;arbo21-e4:rpb,1t hc:>11,~ of .¥~$ epq;:q.de g:r;ioup ;is au,ch that. o.t,t~.c.k df the baee at the oat•bon a.tom ad.-.,'- .. •' .,··: ... , .. _. ·•·:· · .. ,.· ·-. .. '" ,·_-., -.: ', . ' ,

J1::1.c~nt to tJ::i.(;_ m'qt,,hyJ,.pb.$pY4- Gl"OUP ia f.a:~zli tatcl"

~ c.tt,- ~@. ~ ~ ,, \:.l 'o ' \::.1

xv,. qo11,si¢l.e,r nqw t):te ,poeit+v'? -900.zige o~ tl'.l.~ cru;>bon

1;.\om a4ja@.~l".L·lt. '49 .. tl-+9. m$~.,ytp+1enyl. erpup ;i.:n tr+e 'tr~ns:i. ti◊A. ate..1:.$~. :I:n.~:;t'e 9J1,,i,7;J~$ l.ittle doubt. from ·the 11'~.ewJ;oini p:f" t'$130.n~olff th~P.l"Yf :tJ.:Lat, j;,hG_ :posi1::· t.1v:e ohare;~ i~ .$~~piii!i,~d O++ .tJlJ.$ oa1··1~on atom,. wld.ch :C'e.cil1t,~tc~ .1.1tt,a9lc 9:f :im.e 1⇒i~se dt this po;+.nt.

s<=> ee CM\ ~C-" -t.~-~ ~:> ~~ /,~\-~ ~ 0\

\.:.I '0 I \,::.I \.=..f ' I \,:j 0

t ee

C-1\, 0\~~ -c"--fi1 \=.I I \.:,, 0 6>

i

..... LVI\

!lr.n.e impoi"'ta:i..'le!e ot the r¢~◊n~~1e.~ ~~u9i'>l.WP with t,h$. pos.itive ohs.re:~ on t1:i$ -cs.r~~:g, e/i .. J~1.ee~$ ~ t,h~ .mffbh;,;i.-ph~l. group is ci.µe -to 'tb,$ ~ta't.':iliziiig ,inf;l..µ~:µce pt the met,hyl grottp, ¢ . .1. the:r tJ:iP9uglt t4~- i11.du,ctiv~ et:-:. feet 1 s.a 1-:ioatula t,ecl. 1~;y s6me r•~utJ:10,rs, 0'1". t;~~ro,jsl~: iiyz:,~.n~~ 9or.i.j:ug_aJ,ioi~.• Jµ this 'bas~ ,~1ype_3?gonJ:µzs.tion m.o,;3· tt~swne 1:q.e;r_e$.sed. 1.m;pox-tµnq~ du~ t.o c9µJuse,,:1;4on_ wi tb. the epo,x;l.d~ ca.z,b.Qn:-e~t,c,)li ho:-.,4, :tt. m~ w_ell b$.

. : .

that ll$rin; l~~.~ .th.~ e~:lan.e.tion of th(;) pr~d.o:i;nina,z-~t atta~k ·o.f the: bi:.sq ~it tp.o- qg,rboµ ~~om s,c~_jt~90,rit t.o th!;' ntet~,r~h9nyl g;i•91.t1~,~

Cf P~boncc,:~'~f.b6p;. bo:qcL. o_'!: tb,Q . ~DO:i::id~ 11111-;t:,5~ . ;i,:n p}•,cnlp,r2f!i~l,r;iene; 02',1.g·a,~.-:7 .l:~• ~4e ,in:i.-i-;~a,:l. $t~tia, the ~:ef~.et i~f th,e eJ.($9't,I1(.'.ltl;.~~t.J:id,r~wi;ng J.)J?QP.~i'\t.i,~e of the

~ . . .

Qlµ .. b;r>O '£:r'OU,p ~:in ·u-ie ¢~+·':!J9~:-carbor.i. l)Ol"l;d o.f: the ~J;)Q:C"" 1de 11.tµ.t?.Eet .. ; :i,$ ~.µoh ·th?.t,. ~~ t'ti~c.l~ 9:t th~ p~.TJ~ a.tr the oarbOn. a_to)tt ad.ja.qEr11:t t,q ,:t.p.~ _phenyl g;rpµp ~s t.o ':;)~-e.~pecte.,d., .. ~e +-9~sPr.4ns, p._q, _pr~v:~ou.,oly q;e~qribed.t 1nv;,lv~~- ?-':i a.,"f'Jalog;r of t:h.¢ epox.\{if) 9.ElJ"Pt.\n~qa:rbo,11 'bond. 11~ ti1 a,11 e·t:..i11+e11io +ii1,ka.5e ~s ap.own below.~

We may now ~ort~id..et tho effect of th~ chlorine p.tcm~ on the stti.b~.liza.t.:ton flf the posit,l~te cne.r13e in the tr$-,.'1.Si tion ste,t,e.► Wli.eZ'?.as .i the me~~hyl srou}.J would stubi11,z~ tt1~ . ?R~lt,-ye charge 011 ·the o~;rhon s.t.9m o.<ijtir;ent. to J:.J.1,.e 1n:Q"tlcy-~ph~i:1yl 51"0µ1, u1ie to it~ electl."011•r$leaslng 1:i:r.-opo:i..,tiest tJ.1e c1:J.01n g1"oup cm 1;he othor .J'lci-1:;t 1-rou~(,l, 4.ee~a1)ili$e the pqiittiv~ cI-1e.rse on th~ carboq o.tci:u s.djp.qe:..1t to t11.e oi;J.ol~OJ,'il1enyl grquJ) dt.to t.o. ito :91ect~l1'."'.\d:t.h.d.rew1ng, p~•G;l)Ol"ti(:ls• Thus .~ttt;~~k o;n. t,h$ g~,t:;qon e.:t,c,rn ,adjacent to the phenyl gro11p 1roulcl b9 f~c:1.1).tv.t!=Xl :ln tl10 o.a.$e of p-,qh.loro,st:l:Lbene PXf.d.e" FµrtJ.1-9:!", :tt riY.e:J bl:;) e)cp0Ct$d tl1~t the nogRtive ch~l",Ze en th,~ o;:.i"bo11 e,tpm ?,djacent to the ahlorophen.yJ. groµ.p woul,q; 1:;g ste.b:Llized ¢1:ue to tho :rt.?sonance Eit,ruot.u:r-c wh1oll. 1nvp:lves tl1e e.xpru.1ded valence of chJ.orine t·\B:

ee> CL-~ c." -c..\-1 --0\

\:.I 'of \:.I

l (5) 130

<!:-) ,&:. =- F\'C ~ ~- '"' - \;::./ 'o, \::.i

L '"' ~e·nce, 1 t is proposed t.hat within the concept of ro ... son.a.nee inv9lving the o,Et.rbo.~-.oarbon•·bond. or;. the epo'.le-· iae a11c1 the ex:pe.n.9,ed valence of cHil.qr:l:-n$ lies the ex~, planation Of a base :9,ttaq~ p;ri3d.ominant.ly at the oa.r-bon atom adje.ce11.t to the phenyl group in p•ohl<>ro--· sti,lbene c,)tid.e.

Resonance in the Transition.state.- In the transition state of pl'opyl:~ne oxide, it appears that structures ot types I arid II:t·fi~e more important than structures of

expected.

struct~es ot type II assume greater impo~tanoe than in the former case due to an e.llylio type

substituent in

the p-.methylphenyl group in ordinary 5a2 reaotioh.s such as the base displacement reactions of ohlorids in p~meth,ylbenzyl ohlo•

ride by iodid~ in dry aoetone-,._ The methyl group slows the re-

action which may .be attributed_ to a weakening -of .the foroes of

attraction between the benzyl oarbon- atom and the ·iodide. In

the stilbene oxi~es, in oontradistinotion, the stabilization

ot the positive' charge in the transition. state, as in type II

structures, appears to be the important factor. ·1;The ef teot

of the .methyl group is to speed up the reaction. at the carbon

atom adjacent to the methylphenyl g;r.oupo Thia .may

easily be understood since i.n the transition state the

efteot of the methyl gi-oup is to stabilize tlte positive

oharge on the a.d;Jaoent oal,'bon due ~i-.ther to the induative

effect or to hjtperoonjugation. Thua in the base atta.clton p•methylstilbene oxide, the rate is taste~ at the carbon

atom adjacent to th.a .metbylphenyl group. DE.) . r,e>

G)O . ~o C..H.3*~!1--fl+~ ~ ctt3-~Cl ,,tH-;@

oe 'o

In the case of the ohloro group in p-ohloroati1hane

oxide, the ;positive charge on the carbon atom adjacent to

the ohlorophenyl group will be destabilized, thus inc.rea.sing

the importance of structures ot ty_pe'Ill in the transition

state. St:ruotur~a of typ·e. III will be further stabilized due

to the expanded valence of chlorine,.,.

The etreot ot the substituent in the sN2 reactions of

stilbene oxides ia in the same ordel" aa 8Nl reactions of

benzyl halides sinoe in t.he latter oase the ste.bi.lization

of the positive charge on the carbon atom is also the im-

portant factor in determining the :rate of' their reactione

-D~$inti1r.t1ti,on -Of' ·t.~i~ E1'ctYJ.d.~- Rtr~s-· Ev;id:ence ot n~a.e:t.;tv.atl<m~,-· Expe:t'1:.inental avl• . ,- -- .. ')\ . . .. -·· . . . .

dehi,~e ~eyo?'ted ip, t.h;ta th~si~ i~dic·at.~s tl1att the !3tl.lhei:i_e. P,>-~q.~e. ~~ _).'¢,~_§ !1:¢..~Q'.t;\ve to Jionte g.estee t..11?,n ot.r.~$.;t .. ei~s@~.a of ~po_:,~d;~s., I_!\ t~ .:r~duot:l.Q'n ot ;p~m~thyl:atJJ,b~n,~ .or;tct~.; t.:'l-i¢ e,;.:,;ai;ri3i_e J1,1ct~c!tt~s ~~t . . ' 31.~ 9.% o:t t,.~e. o~~e, d.:tc\ .n,o~ r.$~9~ ~:v~1·1 _ln the ;pr~$~c~

.. 9£ -~ l.4-re_;e ?XC(J!_StJ c.rt l,i,~~4-µ~- .~;t~,:qmn, eyci:p;3.q.~1'- Si~;:+ .+ei1~ly; in th,~ fe~lµ¢.tlon., Pf J?"":d;:hlpr,O$i:.l:J:b~:1:1;~ o~..id.e,.-that•$ .was, t'eeoverod '!;O,.;"!% .~f the <}xtae.., I~ tJ1~ ?1tte1Dpted !'l'ea._Qt;tQn. o;r. p-p .. lt~o$.ti.1l)~JW ¢t):.p._l;) w:i'th ~ac1J.µm _m<:dJ10%\o.e 1,n_ ;;$tlw""'1c_l, t1J.mo_s:t, e,'+.l 9_f· the ci~ct,e JU.'-!'$ ~"~QoJrf;tx;ed,~ !.n the' l]1d.~o}.y11;t~ 9-f P.:,Pl.t~"C ?ti+he~(J Gi;p,cti;t . .:t.rr th-a p,11 m'!~71ge qf: ijl1 $.Cid;t~ ~.t.• l,~!3-l,a i;,e,:µa:lyst, 72,, 0$. Of i;,h~ tf~a;_ ... t,;);ig mo.terieJ .. _ ~1A~ pqb◊"'f(}Z,Oq_~. Thi$ ~N' J)e compai:-$Cl. wi_-t;;h ·M1;~ 79ft yteJ.a pf ~-~•lieJ:•-,alcoht\1, pJ1t_ained J:n tlte ~~ci4 9_r:i..-t!:'.lyp9et tar.~~t.1071 q_f. 2,.J-$pO~;t1?.u.tarLe w~.tlt ms_tl,1,?,.?19i P-33) 13.® th_o,, 8.Pt ... :ri!SJ.¢1. pf: ~~.l>t~t?l'lpl. ·qbt,t;1_11ed Ji+ -~ J.i:th+u:;n o,+J.tmt-,1:J.W\1 ... PY4rJ/l$ 1~qp.u9tiQp, 9f g,:;i~• epowoutanp (l88h-

~te reme,rkable st.~1.l,ili ty t>f th~ e;t,i+bo/ne .o:d,d.e.a '.\'fO.p .uo:b_t<J .. e<:t. bY ~~'t;e, ~;~ Ji~)..:l$Jl$lab~ (lQ,5.) -~;:ld JlQmmente,<l _upqr,i t-:y R~c4 apfl Q~1:i'f:)~U. __ {;l.Q?"".'.l;)~) ~ Th~ oYJ.dea 1·re1"f) :round. to ·bf;l l."'i$~iatm:1.t to the a.otion of . ··•-•. .. . . .• • • . ·:· ··,· •• ,, .,., ,.. . • .. 1·' • .

Fep,lings '.SQl:i.tt,i9tt.$ ari411oni~.qa'.L ~;'P.V$+"' ni:tratei t;t.l~◊­

b,ol+a te~ri? q,hl9r+.~·~• )?.o't~~~.twn P~r.n1$lie;~~t~. ~""id. Qh~o.~c e.¢id R::Q.4,s:t.~0'1t~"' RElaci. e.r4 Ct?Jnpb,~ll .. ().S,9) ;f ourtd. t..l:ta.t l-;tra.ns,...sti.lbene o:dde d1,d not react .. . .. . . ...• . ·••' :, , .. · '", ... ·.•. . .- . . '

wi 1:.4 J .. ;mol£!; <:>r eyd.?;lt;>(}hl,~tiQ .. a~~~- tn ¢.1µ.or,0.fo~nt $e>ltt-· t;to~. 'l!riey ... l,~,'.tP..~" ~~:POltteq .(l§-1$) th.a:~. p, p '·-ii)rt_ethoq.;r,-

;~~S:~d::~!.tt~~ :ti~~::ri:s 1n t1101npq~. sh9rt~c1.:_JlQ ~nA~ncy t,o isQ!llen~, .o,ti;pe>;J..ymer .... _,-z~ .in ,aop,t,.(;l~t w~tli.J;,o~q_at.;t.tre;t~ sultµr~; a.~~d ()Ver ~ :P~ri~: 9.t ~ix .... hoµr.~ .•.. ,.,. ~~$e~~.!1 ei'1t:l. El_Ej~n. ;(:l.$)9J .C0.!4d ;!J,q:'G .-9Qt~ ~~---5+1,tt.ol 1~ ~$ ~().1e,t c~:tie.lf2ied ~<!rplys+$ . . Pt $ti;l..):)~µe .... ~~ii:i.~.~ $te'-:qmetz (aoo) found t~~t P"'.'\~~t...119lX1lllt1l:l)E,i~s q#'3.~ ... 4~t;I." not r,e~ot · vtth ~oili~. g~t!, a.4'1-~_t:>µFJ_ ~'Jiqiµwn ~dr<>.xi4G, £3.0tt-.d.e J,n Jiqµtcl er~Pn1$.i ~oP.1.wn ... 4bl9¢de in ii.t1u1d :•on1a,_ ~mo~:um b1-dro:d.de .1.n ~ bo;mb ~t 100:\ll :t, amntQni:utrt chlo-" .;ria.~ i~ .. ~9~wtt .J:v~~P~4~ .e/t, .l.90..~ .At~mpt~ to-.rer-• ciµQtt.~~-~.P9~4~ .. ),.l~e lfi~ pia~tnum 9?ti~~ ~-.Pl4:rPS$.P. ~i 49.i~~~./#$1, .. iA.,. ~!!. ,EJ.P4~iua_ -~gwa undel;' c;t.i:rreretl'.t. -~9~3;~p~a.: ~~q s~:v~ n9 re13.0,t49n•!r- s1m3:,.-).A;~;;.y ,,,, :~+~:11-µ.lli; J$9PP9PP.~4~,:f P,t;Lf)d.. to_ f~<:lt1Qe- the

·1

~Q~P~W'4t .Ji~ ~PPr.te,q., .l:µ~_s:> ~ii P~~-t;irpsti1w~~-9.~.4¢t -~~t~t~cl. ~e-.:~4.:t.ttP~ ~t ~mon+a •Ulld.e~ various conditions --,·.,., .... '·., ......... , . ··,··-•·•··

Jgaott or tt,eeqt1:g:g:Jiion oJ;:_. iJMl !e-oox;t94 __ ,:!ine; •. ~---~~El.d ~ .. o.~p~_el+.. (';l.9~-~:J.:98J w~lr,) vf/Jr, ~q~ conQerne4 w:1 th. tll~- +.~Q~. e>t ~@.cttMr1ty cJ.ett1on~t;r.ate,g by the st1l-b~1)$ 9JP.4~-~~ .~ey f~lt, that.; ''the_ ezt,ra.or.d1.~apy ata..-bi;l.i_ty.: 9_f 'l;~e~s w~i:i 4.ef.1.11$4 ,9cyf3tt1;ll$.n.f _ox1d~a is in keeping wi.th :th~ v.1~ws. 9t ~o~pe an4 Il.lSOld. (201) on. the ~t:rect ot -~ubatt tu~nts in rel.~eving t,J.1e e.tra.1n

. . . " i$~:r~qt, 1:q. ~m~ll .ri:µe;a,,. I'f;, ~a, pQaa1ble, s.l!30 ,, that the la.Qk; c,f .~a~t1:v1 ty

may J.:>a ..... oP.r~~l-~.t~4 .... !r1.\1;l_ thfl :r'-ns unfla. t~a.t1on p:rop1;>r•· t~esf!,. -~'1+6-., ... tJ;l,$f§! ~--b~ a. .hist.,. ~egra~ pf 'reQ9n;anoe s.t~biii~-~'.t~9~ .!n ... th.~ .sr_qun.4 J?t~t~ (3.Ild. i11 th~ ~a.n~11, .... :

~ol.l. ~~te ;4tte tq $1:.m.ct~;ttµ."'$.lf,t ,~t. ~ll;s ~YP~ '~b.own :be1Qw wb,ioh pes\tl~~ J.~ a. ~~re.nst.,!,1enJ.:ng ff)f .~e o~;rb9n'!'>o#sen 'p()ll4S ''.

/-\ H Hr=\e ® ~ -:= C 'rfC -= -"\;d :

L~ t'I ~s· $xpla.na.t;i.on i.s e;~osous ,in SO)Ill9 ;r,,esp~et$ :t,o that offered.. ·f,o:r the d.ea.ctivat.icin_ Qf the d.C>ttbl~ bond . . . . .•. . . !' . ' ··, ····· .•.•. ····•,, ;·' '.. , ' :•· . .

!rt ~e ):'$$.Ci:iicpn o.:f ~t1.l't-'~rJ;EJ 1t1. ~- 1)ro.m1n~ a1;1 a result Pt .J$.SQ~$.,

Anoth~:r pos$1bi.e ~terp:ret~t~on. or th~ lack .ot ~es.at-.:tvi ty .J~ _tb,Ert sts,:r:;,~- -b4na_:r,~e.$;; dtt~ tQ ~~ ph~ny:,, gJ;'gµpa .. ?).ovrs. .'.tA<=l t~W of ·:.:re8.cet~qn, The po~$.~bi:t.,i ty_ m~y ~ ¢3.;,e.~Jf~ l:>y i;,h,t':) comparlson of yields o~ ~~-<sttoµ :r~tes. ... tP t,il:!,e r?~ottona o:t ~tt:J.pen~ oxid,e .~Tld ot ;~tf:Y.C.49~~-~-+ .~tlj.yl~A~ .9~de~ ~s _phase e>f. tn~: PJ'91J.~~l!l.J-~ .no,r ~~-:r. tAY¢~t.1g~~iot;a, (2:0?}.,

;. ijeggti~f! of ,st1+,b$n~, o;&\d~~•.::: .. ,~~- ~~y p.otr ,be 1n-fex-r~ tt>om. the above·· that the· atilbene ond~s at'$ ,. .. , ...... ·: ... .. . ..... ., -.. •·, .. ,,, .. , .. , .. , ·,:•-•·:- . . .. .. . . .

~qmp:I..~t.~iy .d~v91~1 .. J>t &(tttvJ ~Y:• ~U.$J f-iU.ti,. F.reek and _f1µX'Phy ,(gp:;J 91'.>~~1:n~,. ~~o~l~~.~t, y,~~;L<t.s. Qf -~(ii .a..rnino.'."' alcohols j.n th~ ~action.a ot' ois- and tran.s-atilbene .· . -· .. · -~. -~ ... ' .. . ' .• ,,. :,. ' . ·. , ''. .-, ~.. .. . . ·-.. .. . . . - _;. ... ' . . . ·- . . . - . . . :·

9.xi_<1¢ ,1i t1-?, .. ~Q~1.a .. ~n .4i~~- a..~ ;J..20.~ fc:,~ lb hours. SiJD,1:La.:r-ly, th~ re)p9r-t~ the r~action~ 9t the ea.me ~P9xld,$.l:l w,~:t.~ ,-~~ p;r;-$:ri.1,rµ-y :~10- second.aey a.n4net:J a. t J'~flu~ ~e~p.,rature Q.t' t.it ~5q0 , but 1zt lowef yields.

··,.: . .

Lµtz and t.~rp~ (~04) x:-e=Po.~ted the reaot.io:ns of P,P'-4..i.ClA.~.:rqetilJ:>~n~ Q~d.-~ ~1tll ~onicJ.,. P,%'µD.aey

and. se~o11.d.a.ry ~,t:t,.~s ~$~ a.p;p:rQ~maf;~l;y t,he s~e OP.«JJ.,tt~P.~, Ree.~, -~- -~-P~,e.U (~9<5) :l,"epo;rt~ th$

.. ~aqtion. Pt l.r-tt84~1':f~•~lbene o~~d~ w1tJ.'). ~bs.oluta ethen...-Q_i IJlel'alY OJJ. $t~:~ns 1;'9,~ 15 4.a,ya at ~pqih tempt?:ratui'('+ ~~~:r.i, .. (a.QS."ep7), 9.ptii.n~ ~ht:) p~odJ1cte e~Q?.~c;~~ in the reactions ot c.1s'~ and ~a.ns~atiloone oxi.'tt~'a. with . . . · ... , .. . . , ·.. .. ·. ,.:, ... , ... , ,. . . ,· .. , ... '

Grigna.rd ;,ea.gen.~~- ~1rtepea.il and Levy {2P.8•~i~> tound t.,'11.at, th~ .P'.:Dleth.yl.~ a.nr(,Prm,t.h~xy~t+ib~nij o$1cle.s o,ou.1.d 'fl$ ia.omertzed. t.9. A+.el~hy4~f4 and, k~itj:Q~S'••witb. -l1ea.t. ~ ~~id Q~t~J..ysti.i::i~-- .... ~µ+oJJ ·•AA4. qQ~WQ~lre~s (i.3.~• l'7,. ~-+1) were $ble to .1$¢~~te ·tn~ prqduqt,s· ot, the., r~c,.ot~ons .. <;>t ¢.;fl-,, $.nd. t,l"an,r;t-~t4llbe¥i, opA,~it w; th .tl'.le h~1Qg~A ... ?..Q+4t\.-. +.t .:}.;~ .. -P~tJ~f~+,$. ~;l,S~l ttj t:$1~~~• th~ ~.t1..J.l:l¢>:µ' P,~c1eEt ~~; .. t-A~ .~Q.~_~1.3pQ~~:U~, ~tf~.Qf3.).'l~s with Gtisn.a.l;'d._ ~age,~$·$. (296-.t2Q7) 1\ tJ;:J_.q'UJ'.e~•:-.r~ ltQNSe (214-).,,

w~~l_l ailq. !{(,.ya,<:)~ ,(~15.) -~~UC~ p~$thytstilbene p;di;le wit,~ p,\_q~9.; ,t~. _tµ.oQ.~Qi e9iution, ~:t .-.,35-40° .and 6'btainect. pjm,$.~eylphero'i'b.$n.~1:J- ~'~1'.tnol.,~ 19X.9+v.s1.'V'ely •. : ~s 113 in ~o.n,,:r£!.f;l.i, ... 'f.Q ... ~fJ. .. ~;t.ure .9~t.~~4 e>ri 11\:~,\I.W\-~• e;1.lµ~nim.t .. ro:4;r1qe r_edµq~ion l1h~~~- t,b,e;.-.:~~.qm~r we.£3 t4e. .pJ::-e<ior.n:!.na,µt .. p~au.ot _ _.... ..Fl'.'Otti ·the viewpoi111~ ot the _me4~a.:ni,1:1rp.J:,f ,n~ re~0,1.r.19P:,S <rt epo:r.ides w~ th .Lewis baE!es, (?:nly th,~ __ lj._t,iu.~ ~ium1:p.um by(,1~1de r~action 1a _qi,' ~ono.~vn aip.oQ .a.@Pl-.~:. evi4t?P,c~ lA a.v:aila.pl$ that,. ~ ts :t:'8.~c.t:!:.9P..B -~~- o:t tb~. :'$.N~ 'ttYP<?, .

-86-

.Q.leavage Reactions of stilbene Oxid.es . . . .. . . ' :

It·was reported in the ex.peri.mental seotion that o.n alkalinehydroi,rsis of p•n1trostilbene oxide, 'benzal"' dehyde was isolated. and ident1:ried. In the attempted synthesis of p ... ohlorostilbene oxide by the Bergmann-

. ' ':

Hervey .method (.218), p-.ohloroben~yl chloride we$•, treated ;· ·_;: .l

with benzaidelcy'de in m!!tthanol solution in the presence of potassium carbonate. p-OhlP:t!Obenzaldehyde was isol.ated and identified. Bergmann and Hervey (218) isolated the methyl ether of p•nitrobenzyl•alcohol from the attempted aondensatio.n ot p•~it:robenzaldehyde with benzyl chloride; A possi.ble explanation may be

given iii tt\lrma or electron theory;

G N 02. --©-ctt-..B +-

t Bl+

'1.'he oleEtvage 1.'ea.otions may be ~sed to dete}'mine

.the et:rect of a aubstituent on the relative rates ot • attack o:e the base at the epo:x:ide eal'bon ato.ms,.. . . .

caution, howe:ver.,. must be used 1n dra:w1.ng oonqlusions

fro.m the examples. oited a1nee . .no a.tte.mpt was made to

deter.mine a.11 the products and theit relative percentages.

,D1~¢ti on .. oo:~ -~ ;oneP-7:m ·:9t .,&1tr~e1:v~·- -o.~fJ . w~:t+~ !~1. L1'tll1WA~·B¢t,a~n;ta.

;.~ t~'l~ p~p~~a.UO:tt *-·t ,P-t:~-t-1"..f.l~~n~y;t.p~~l· c~~-· W,~~+,: 4.~ft;i«wtr Jf~-~', '~;P$:r:t~ti.~~4. ft~e ·t<, ·eg~;;:11..,..g· ·of t.J:l.$ .Pt.Iil~t\:W1~$1~:4 ~~t,sittrJJ:, p~ldd~,: T.l;l~f' w~~k :qf ortlirt.<fi~~-- p~~s+.,f:lB; ... ~ J•~e.:~~ .. ,1~+Ql sues~;~t~ ~- ~~tJ$i·~· :b.t;L.it:; ,.pt _9b~l..PA00 ... t~~!-Pt9¢~¢.t., t.P.P.m 't4~l ~~q~o.~ Qt .$.tY~~~~ <1~4,.,. Jti~.,.Pi~-~~-l-+AA~n.sl. -i;i. th1:gin.,},

·i~;1,--a.eit1on ·C?_t r~·:.:•~a~~na wtijl. !~Wum• Jt~.~e;efi~~.:~ ~~-.,~1f4:1'.-:toi.1Et• r.;,t' ·~_t,yr~~e. q~4~. w.t:th i.1t1~.wn ~s.senta,

•Z:(:;;!~9;:1~~::::=~:; ~~~::. thµs/,. ·9~:$.t,Ql, Dpµgl~~Jt Md., J>!~~l.t.,. :{JiSl) f:'ou11d: f;h,~t st:rr~ile -9.P.A~ wi t1:l .P~~+ ii..~~~- ~~Y~: ~t·ta.c~ ai ~~--PJ?i~a.X'Y' ~a;rp9:i;i -~tp,m,: ~;®ti t;b+ $ :ta. d,µe ~Q ·-&~e f ~C:t. th.Si.~ .. at.t?-}J.~ ~t .. ~--_,pt~~ 4~zjpo11 .. ~::tpm· i.s lfr,~~ .. :~.llC!Ell:'~d. ihs.?1;, ~tli..flC_lt at ~- -~&O.Ollg;~/ ¢.P-r.~-~tl. ~t,9ni_ t;t=t. a.~n'l l>,y t.b.$ ::W,p).~~ Q.f O.lil-~Q~~t,. ,{i$9}.; .. ;vth~.-- .fc,)Unci, t~t, :Phl~l :ii f.J:-4,-µpt_ A\i~gJt~~- ,Jtt.,:tiP,~ ... 'i?C ;.:r,.~~1.?.~A-: .. ~tQtn,; +.~ .. ,if'."'.11,illyt, -4r()tia~lli'.tr~~~~~~l,~77:,P~.r4~.~;J(.. -~ ~ .:ri~~b91+. -,tont .~11

"p.4~~i-,,y:4~ng.J?~:tAAt~n:$,7.1,.,;J~,~#tPQ~.14~,. i$. l~t3_;~,J!rtetr'-"'. t)~+;t.Y -~µd.~~84. t,p.a..'11_ ,~µ~ C~\?9~ $. 1;,olli .~4j tJ.?~.P/tr W · tb;a ph.enj<t., .s:1,·•pµp _.:t~ ,s1.;".en~ ~~4.~t,. ~ . -~-~--t~. ·of the ;reaot..1,0~ ot ~.t,1.~nt .P.~4f) wi.~. pf;it~"tJ;if:l,.pg~n,l. i~~-· J,h,i_\.lm,,, -{:t.~- r~PPP'tii~~l -+P.,. ~e. ~~rtlli$~t~ ~~;~tir>n,. C<>tt, t~t'ln, tll~ w~_:r1,t Q;t:' q~~E!tol ~- r.tQ"""Wq~ke~~;:f .. i111a~e. ia ~ posaibllity t~,e ~ ~;aa/lt a.mount c,~ ~~e.: i~Q;t!le~._,~,1 )l~ve 'Q(:le:p. pro~~e~ .. b,¢.a.u,s.e· -tl:1.~ .mal:t:J;ng_~-poi~t. Q:t the product, .$.V~n. .. a.ft~Jf Ql~i,i+lt.t!.oJ:>.; lfa,e1 not ~l).arp~. Nd

·.1Sj)lll~f, h9t!~V~~· ·ttQ'il.+4 ·~e :t.s(?l~tsq. ,ql? ~~fJntiti.~. 'J.11ie .. :Proa.u~t. ~~trti.~#~4 w~11 t<i~nti_ri~ ,~:fl: :pmmE3.th;r-1'be:n.~ ~y~1,1,,ey,l. te.r:'!>~no:t.~. ,$. ;~~- ill~lti.nstP?iJ;tt w1 t..'1 -an -~µtq.enti~ ~~l$., ~Y~~_s1~¢4 .,;Xl: tlie r~aqt~o~ -9~ P-"'• .m.~th¥i'.b.a~l ~~_$p.µ;m ___ l?~rr.4Ae -w:t:t.lt b~AzQil,tiaiva~~

~i~gtion of Ans. ot?ttt~ne; ~i~itg ct-1ttm~ttP:S!1n:tr~•;,-The l.it111~m ~l ~ee.gl9:nt WE!,:i3 o:t,.o_ae,n fn.etQAA of #le p~me.~lphe,11Y"l mi'l,gn~Eilurn ~mi~~ be.c.,~uise Pf the ca.ta.• 1ytl.Q 1¢.l;~enqe ot,· t'l;e .m~e~~ i_q11 'ff.h.iQh dj.peote th" a.t~(tK 9f. tJ.t~ ~71 sroup '~(). t}te .$~QOX,.cim e.~:r'bon. ai;O.lll· ot· .t:tty:r~p.e oX.$¢E➔, ►, . ,Fu,rt.A¢1, 'ih~ n1a~1asi;µm. iO?l,

°tJ.taJ' ~a:ta.ly~E;) tJ:l~ i_qP~.~1='t~~~!9~. ~l a.t"~l'.l~ 9x:\.d~ ~q

P~8P--3."l-B.C3¢'ti:eJ.dahyd.~ ·fln4 tb.~ ~~Eli.m l_s.oine:r Ill3.Y' b~ ,OP:hiirl~---

Klullta.Scll .. ~d OUpp Jt~i) reP~~e,4 ~'t-- ;pp.,wl ln!a.&.lt:iSiUµ.t bX'O;mid~ ~ a.lµi?:V-l. n1~~~~l~ '.bt9,rn~d$ .f!}.t,re, . ' ' ··. '

.in ad4~,t1pn t9 :I:@.~: p;r.p4µc>~ :¢'.fgin the. i.~q~~~l:3e¢1 ~tY-·t·· ~ne Q'9td~, th$ P,rQg.1;1,9t :l;f}?4Q1t 9.qrN~P(?'.nd.B .t,9 att~¢k at the s~oo~d.~py- ~-a.r-P9~ .~t\?.Ai•, R{)fl~ and.-~~~ (~$?) ~l~o obta;;tt$d.. aec1Jng.til~ ~t.~1~~ tn tb;~ ~eac.t,:ton ot

. : ·,

~rty~E,nf), ()~(iie J~~'~' P®.n.Y:,t.~~~~yi~~e -~s~µl!l bl"?mideit !rhe. :readt1on1\l qf :etyJ?~:n~ <:>:td,4.~~ -~:t th G~igi~

teagen.t~ ~r(t r-~~a'f~~l:>ly .;L;J.k~ thgt ~61q. p~t$1.ly~ad re:,-. .. Aotio.p.1?_ 9f trf~Y~n~. ~-~4~. ~j, tii: I,E1Jw1, a .. be.i:JE;_~,.. ~m a m()Cha.r4~ti~ .view~1r.nt,, -~ ~~<1ttons ~r~ e.+inoet ic.~Pi~:l._()~. 'l'he (l~isnfi\~ --~~ent oop.tai~s the ,ieetx-o-PhiliCJ; ~.g-i-+ •· and. PU¢].i.,9p?tl.ltc, n~. ~1~~µ1:.s J..n thti, ~am~ mol~otµe.

@-c~~ ,~ lrz.

LllVI\

/u:~·i;tµ,a1i:v tlla t1;-~~9¢.1~t;to~ pf -~~- in Q~e~ ~a .~l'l.oiin,, is ov.~r~tmplJfiGdf W,n~, µ~µ.~i, ppa:~i,J.a.:t;to'¥! 1$ µ.,., te;rms of the aohlen1~- (.2~;,>')"· equili~.rium,.

LkV \\\

l:Thete tl'lG ~~: 1 a t11ou,.gl1t, to ~-oc,r.¢.1:ne.: te w;t tp. thf:l ~PP~Aet ,<n~g~:n .. !l-tpm,.,, .... ::,~.)1,0~~- ,,;,r :s~ew~·\'./ ~- 'Qbbe;..\ lPh,4e (g~?i.)., i.n.~~~-a..t~s,.," -~ov,~¢:r.; ~t th.a ttlfh;y'l o~ ~eyl SZ'Ot;p,, ;~a.y ~~- ~t8Ai µp· Jp;_ ~- con,p:ie~; ~➔:on· 'td.'ttn :t:r~~ m.~e.s~µ:lll: '-:Pn,e. ...

E• . 'tr.he'' ?~bars1;U:on ot 'the . §ti;tb:ene!~\ .. ' . ·' ·' .,, . f·'' . . . . . .. . .. . . , ..... J)eity~:rat~ipn __ o~ ~:~S:l'bsti:tutad: l).i.9.':~letriano1r~~;~

1-,. µ.sefµl' !tout~· :fo'!! t~$ a:r.n~h~ais' ot ,;,.;.,~µbs~i:tu.t~

:~:~~4.::;::=~~~;;~!,o:~~!~~~=::~;r .. ~e ~$.E?-qtJqn. ftf.: ... PtJ1uJ~~-tt.i'.!ut~a. :ba,nza.l<J.~ll1dps ,n t.l:l. b~n-"· z;ri ;n~r!S.t~m. gllJ1¢.tid~ ·r:01..io~ '.l>y d1f.'11-Y¢itatto11 qt tp.e r.~~u)~tat?-:t.. 9.J.?-~+.~·t.,.1,@.Q:l,.t!_~ · .. · .~~- -~rt4,:tb~n~s.;,,111q ~e;u '.b~

:.,;Q~.4ip~ ... ~Y P~-'.r:P~P.11.pic· ~gic.\ \9 :tb.$ ~Pr~ppt1Jn4i..il$. ,.:~i:ie>~4e,a.~- .~~ s111t~~~$ .. W~fl %?~4;ot$.aµl-;~l.t· ~QriVEi,~len~ t . . . _.'

.bte?..4B:e 't:ti~ . p\ire ... ~tl}MQl$.. .a;$ .. '.N'.~.t:t. .. as •im.~ oJ.ett~a.' ware #.eeesJ:J~i. f:Q_:r· '1:4e · 4~t~:~~l?-~t1,op· ·qt ~ p~r,o~n·Ati~:~1>1n-· '

-... PQ~lti~n., 9t ~}~ .. pr9~µr:,tFJ tr~m ~~j_ :r.-1. ~uni, ·$,1.tµni,r;,llll P.Y:.~i4~ ted\t9t4~*~ :-~t tli.~ p--$,;\bat;~tri4 st,~lpfJrt8 p~des~

lit, t+½.e .spqctf,1.¢ ln~tari~~ ot t~ uat¥ q, P"" . ' . .. . ... . ;, . :

m~~i'b~n..~y,J,. mtte'A~$hl~ b~1t1~d.~ 1 .. , th~ tn~thqd fo:3.rlG;d. ''i:l~e,t:1\l:tre of t,h~ $!J~f;ld. W"·th· wt4·ch, th~ (l-r1$,;i~X\'.l. ~e-~g~n.t, ., . ' . .. . . . . '· .

,eottpl.eti.. ~e p~m(;::ti;.;r:t,$i!l.l/t>¢.f1¢.,. h9t-rev~,;J·• -vro.~ syritn~~ eli~ed ,by debyd.t'tit:to:p. 9:f .P~#Jet~lP~~nY:l·~en,~yl. ~~~1n..., ql, An ~te~tiv~ route· ~ ~i~- P1me.tll1l1Jenztlf.'.c p4eri..yl Q.~bi:ni::,:t Jr~s prov-1·dC;'IC\ ·}:Jy' th~ :raact;ton ot ~tN'·~I t~~e ~l4cta with p~~n~t~l~ie:py-1 lithlu,m: a~ described ill the ;f:;;pe1"irn,eµtSt'.l s,~qi:4911. ·

., • • !' ' '

The .4.G:i::,l{J.r~tto)1 of p...:r'-1,~thylphenylp&t\ZY.l. -Qa:J?'b1nol Wt\~ :repp~ted (?12.} to ··pt-9,~~~d. ~:moq_t,lily in· ~queou.t)

.,:.~~;tfq.X2tl.Jl ~¢id.,,;~~~ :i,l,9.. .d1#f:lf!aj.j;y ,,~$ 8_!lOQ"tUlt~:red Jll. '.tµ.~. Pt~var~t,~,on.,.:9t :P.~Al,~i~t,+l.q,E!t,l$ by ~.$-· DiS~O¢,~

p~~h+<;)l"Ol)p:~ny,1.1?.~P.Z.Y~. q~bl,n9.i., ,,p.ot-t:ev~~~ )?~$~St~~ ·de-• l\Yd~at:ton ,ri ~ 59%, ~qµ/q9:r4~ _13µl.t11110. ~,C,_14:•• E:ri;~e1l~nt 1.1.~;iq.$. JJ°! tl;.f) p~o~QJ'Qift~lb~n~ w~~e c,bte.~ned. JJY

aoet;y_:t.~tl.~~ oi' .:trii:t e4¢Q:b.i,1. _f¢1+~t~. 1'1 ~;eJ~Q:t!tpb."ttit~on ot ·the_, ·est-er· uhti~r- ,the, oonditiorta · ~bhrted. in t11!0,

• \•. • • ,., • •• ,•-. • ·'" I • ,···• • •,• ••:. ~ ., • - ' ;_ ,.. • ·;• ' • •

~xpet-11ilenta.+. ~~¢.ti9..:p;-._1._ : . .. - :··

.Kp:n. ~d $p1t?kt.t.t (2_2$) we~ .e:pl~ to ~t,.b1t 't~~ the.ta <t$}W,;;l,1.,?1,t,1pn., ot 9;'.'"1Ilf.i't,.~lpl:i~1/b~nzy~ eo.:rbitJ.6l wit,h Ph.0:$:PltoNa 11,nto~t.~~r .. ss.ye Wta :t~~:-st~Il.lene. The ,ro~k r~wrted b.;er~in h~S:: etsta~+isb~ ~9, f.~Qt that t.be d$.l1;y'dr;;i:t:t:o:n Of _:;pf1?;$~lph~cyl,pf,lnzyl ~~cµ P\'.t ~~o:N>pll~:o,1.tbe1nty.l ¢tt~b~11<>la ~lso -save t~n.s ..... trtJ..i,-, ;b_$l'.lEHh ihie. )'i'S..S .prt>v$n 'bY;. ¢~.d mel. ti~:"'po:tnt,s .wi tl:l j•,11~ q~n~~spe>nd.1.ns st4lb~n~s- (t'bt;~~~eA :t~om, tl1~ }~ee:r-:w~111 syxr\:.'q~s1,e. trhich .~1~¢ ~ffp~,~~ ~~- t,t~$~OJ.etin.~:.

!t.1, iih$ synthesis Qf f ~:mstb.11~~11:.P;h~nti Q~,-'.b,.ll$74. by th~ .G~gne.:r-11 ~e~Qct.. th~.tr~ w~-s i epia ted, f;JQme p.-mert11Yl;b.e.1izylpl:l.fng+., ~e-wn,~h '.~e $:~de . .r~e..ot1on l'fas -n9ted qy ::3~bttt1er anct. Mµrp.t (~~q.J (J.'Q.d ~tu¢tiea., 1;,y- :1'~$J.?.aJ.J {22'7). ~\i~, -~ ,;r.ea¢t,;on. ot _p,e_nz.eµ(le.-1

ey~e 'l1i, ~ n1eth,yl ~g-p;~~l~ ... i«tic:t~ Y+eid.~'~ µ1~~-

e.0$to:phenone. B,oer1-\le':i1'¥ £.V~e{?l!h_-•0 'J•f{;'J~rv1~in; :a.u.o.µne;t- ~ :'VM

»:mm tel" (22$) eon~~ns~d. ~-~,r~pa:t/? .,.llU:b~t4iut$3t11-~ ,(J ~ ·· ,ur.o~a.tui"'a ted ~d~JlY.4~:s ~ ,~B..~~~s ~. ~(l , ~-q~4,s wi ~ a,eyl 4'-a.zo¢.um s~~ ta ·t9 pl;):t,a.&P./t.l;l~. ~~z,r~spp~;l~s. mit,a~u:-,rated derita'Iµ 'VE(:'.w.i:t}1. t'1a: 't1.r-JJ; · 11.µ~l~u~ ~ t.t¥t.ol:leq ·t<> the. o{ -(farµon. Atp:m·. :Xp.. ,tJ;Le .Of+~~ qt Qi ,~O; .6ttl~d.$.; th.et Qo~a,p9.I~o4ne· ,,st.,1l'.l:ll~J;:tett ,t~t;e ·i$t:?.1$.te« .. 4ue:,-. to th~ :eaa.~ or , ~$~~r1>9qlEitton., ~t\El tl'.i~y -~~fe e.b1E1 to preptµ'e -~e 'J?""~~i+v.\.-, p-·<;,:lllcorq-l· $.Tld P•:o1t,:,o$:t:Llbemea, among others f in _yiaJ.d.a ti'h~on,, ta.tigf)d .frqm 49~6-'9%. b!;l.S~d qn tlte qinn~io; n.Q,t.d o-oniumed.

.~n ion.le !lle~hail,is,m bas :been, prqpo~ed. by f.ieerri•rein.-Bu¢~-::.er and.. '.ran .~Stijr (?~8 > ,'.1hi,Qh irrtrolya.s the add.1~

. _j:,_+P.n qf' ~ acyl..,_ .t;P.t!.P:1'.l t.Q tl;t~.: "{ -~-~~r'qqn ~tom o~-. _t)~l\l,l~~q ~-~i~t-, T111i~ v.:iew ,t~$ ~'.U!JP~Pt~<i:' b,7, Bar&,rqari..n -~n~. SJ1e.,.p_~j;,q (22Q:) ., ~{9'?:l;~~.h,. hO,"tf~&l",, proposed., ~ free t~t,q,~!. m~c;b.o:,.~_$Ili,,_ w:iw~- th~ ,l;!.r.1+:..$rPUP a.dd:e, ~o the

o(~~t-1:)q~_ .. i:t~oni ___ Qf q~~~q,. ~~'-d .l?.e.¢~_µs·s\ pf ••;r»esor...a..".l.(),e Ert~l:>ti.t.~atlo.p;. P~. t4.e 9fl~ .¢l~o:t1~9µ !~ t1:tep> --pp;e1~l. .rt~.. ·tro1;1l,~P.A .. {?)9) .rE>9951µ~ th.?,t. -ate;c:t¢ fa~-tors Jll;l.Y' 4.~:t~X>!?~:tri~ th¢' ;p~-+Pi;lt; 9f: ~:yt~ck.-. ,H~ ... t tll~ e.eyl Si"Q.\_1p a tt,~¢.ks '~!-1-(f) /3 -.q~,;p9_:n, i;lit.O+fi. of .. .m~tti--3l. a&~J11Zte, 1th¢.r~ tiie4--~A~"'~.q~. ~t.Qm i~ l!;)Sf!: $'b1?riqal.l.y }-l..1ru:te:red·.,.: ~e;rt;tn,~1n ·al.1¢1. W~.1 znw~p, (g:;~J ,P9,~~1t;~ o,ut, th(S! role· of t~e- ,1.:t~z91µun! flalt.. iP. -t.i1~.- :r.;e.~ott..~n; ... _11rts;hi:t~~a:tton of

;'• . . ..

tne. _.9,.eyl :9.?,t:1:i:n1, ~p~a.re.)1tl.y ,. is 1mpq;rtant s.in,ce die;..-· .Z9:tl~ed p-aintp.obiph~1-xv+ .y~e+4~ .12% of· p-ph~ny:ls·til-(' be11.e- co.rnpez,ad to 1",~% ot $~i:q.:>e1'l.e ·1 t~eJ.f .,,,-. _FuJ."'th.er •. -~~s\(b1:1tit14t$d. a.n1JJ:Qes aµJiQst ,teya;r$e.b1y- :res'ui t in-lowe~ y1~1.ci9 or 'th¢ .flti~q~:n~ t~-f4~ th,e cct'responi:t1ng p-_st(bsti tut~d ~"'P.,.ti11es,.

.1-:h.e cond.:11;i;1,0;n~ o:t: tli~ ~ae.ct,ion were 1=1tutt1'.~<l by !1Ea~~~ei;n,. -~®:1;.11~t ~'ld.. Vfl.P-: ·Em~r~Erl'" (2.2.8J ,.,.~P d.et$rm1.nea, the;_t, ~h,e _:re·~c:t1;.911. i~ .... ~~ta..+Y?1¢4 l,lf cup~+P. $fl.l.t:s s.n.d t~a:tf t.,he oos.t. Y:1f.},1.d$ Jt:1;,:r~ .. QJ;,t~t:i¢d ,1.n. a:qJ:t<9t?µs· .e,(JetQnG when t..li.e s¢lutio:n wa.s putre,:cied. with sod,i'!.,lill aoet151,,tef.

.E'.oe~sch (2.:SO) ~AA tb~ J$~P~iPn ·at Ji. p!l ct 6,- ~- ·ex~ tens_ive ist:udy ot: · 4',1:1.e .r~a.~''.~1'on ~pf)ear~d. in,~: P/'il.'t$nt~ lt. :~a.a ~pq#t.ecl t;h~t.. ·e,14_ Qr ~11 +'+. 1<tia ~µ1po_r:t~p,t · _and tJ't..a.t. ?l'.Llm:~~1,i~ .SOl'V,~~t~ ~u~.h ~e ·e4¢oho_li i:LC~·&1Q ~eid,. ~1~ me~·l,¢n.~. ~lilPt,id~: ,1,t~r~ sati~,a~tqry ,. ;~~- P,atent ,rgp6rt;~ va.ti~(,)ti$. 11~·t(;¥ -qf wea.1t -acic1k! 1th;t·q~ ,-,ape· also tou..rj_d tc be. eifecti·,ie -.. , . , .. ,. ' . ';, :: . . .. --~

Ill. th~-' !\ttempts- a~ 1ri.qr~o.ait18 t.he f;,~lg,s a.ti t~~

P,Qr,i;;eq.,, in, ·f:h~.-<f?):P~rim$~1.i~l ,SE?-"Ci:.:tO:t+4,,. i~t w_fy-~' ;fQ~: \b'.e;_1tJ:.ll$·. U:!3<? J#,. .41.o~~e:t- ¢.h&P$~_$ iri. t~~ --9~.e:i:" ot ~44~t4P~ ·(;rf .:t~: re.~g1?:qts _1. i:,~e tirtt~ _qt -~~ct1on,, th~ ~ · , · · ,i:.,:11· _;~ \! f· . i,t, • .'·~tr'' · . · A. ' 1· ;~eJlli:~r~tµr.~ ,:_fi't: ,Jn~-•Jt$s.;e µ~Pil,, e.~n.e;~.s. +µ. t-41~ mo .r.~ -~tj.tm<>£.:t~B:~·- ~~(,\:t,fµit.e*" -~, th$ pµ.rit:v .. Pt tb.e. .. ~~, e.g~P:t$: P.~.d. :,no~ .. ; er~~tJJr . e,t;f~.~:£· tltQ ·Y1~l,~:~. u..tia.ar, the ~p~14.ttion$., u~P<l~. J.t ,1e.,P.,.f,qµPi4;. t1ih/1:; ,~ppr:'):,(im~t.~l.y ·t,he .f3.~~: Y'-~·1-.4.~. w~r~;. p,1,,;1:.a411~.,-ri.t.n. ~u.pri.P. ·s11+.:t~t~ .~'id. th~ s\ilfs,.te of :the- ttiµ:l_i:µ~ · ,~~ \f'-th. ¢'U.PrtQ ~h~r>.~i<te ~n~-tb.~;,:;1"~4X'P¢~P#4~}~~ 1t4$/;~e-\+:~;:•:: ~;:'.:~r.a~~- •~~-'~-iEQ;.~ft •~::·., ~~ -~•~lt.~~, ::,y_,.f:; '1'~~\,IJ,~~1$~a~~c;,:r, /1,Q.'t'· l:ma :a:~:::;::~:~:::,~~4 ·mq

lNPIEAP10LOf St1Jbene Oxtgea Prep,u:atjye . !4Jtf;bgds

!)ecompos1t1on 9f' oh,ql!nea.- .. An excellent method . ~ .

for the preparation ot,- s'.t1lb$ne oxS:des (195•1~8, ·232)

wh:tch appears tQ, .. -.~-~ stereo.spec1t1o is 1llust.rated

1n the sch~e below... '!he: am1no alcohols are ex•

hauat1vel7 methylated and· the quaternal"J -.ammonium

halides con•erted to the base with silver oxide and. decomposed. Thus, the erytlU'o-am1no•alcohol g1Tt,S

rise to th~ .. ,~ans-epoxide and the threo'.'9amino•aloohol, ... , ...... ,,.~· . .;.;__-

the c1s-epox1det. the method is particularly well

suited for the synthesis ot opt1cal1J active epoxtcles.

LXX.

-96-

Ji,t,:,oua~',oid d~tnatipn oJ:, am:t,no~@l"'ct2h2JJ.~~ ·Tile a111thes1a of' stilbene oxides by means ot th$ nitrous

acid demina.t1on. (196,,. ~32$. 933) <of the amine-alcohols

is a poor method-, Generally, 1 t gives rise. to mix~,

tures or the oxide with the hydrobensoin and ald&hydee~

,Peh;ydutlon_ot gl7eoles11> - Another method wh1'cb

does not appear to be general or useful was reported

bf Mueller and Kraemer (234) and -involves the formation

of atilbene oxide from the r&aotion of the gl7ool with

hydrazine. In tact, the recorded melting-point does

not ag:tee with. the accepted va,luea to'C either w- or

!ran,_- st1lbene oxide; but ma7 b~ a mixture.

Psm:td~halogenation gt baJ:ph:tdt!n1 .. - ~ha method

of preparation of et1lbene oxides from the halohydrins

1361. 137, 201 • 213) by the uso of alkali a~pears to be

stereospeo1t1o. ~hus starting with the ev;thro-

chloroh7drin, trans-stilbene oxide was synthesised and

trom the thre,2-ohlorobydrin, the 0!1-epoxide.

Persoetic acid and monoperphihal1o.a.o!l:de- The

oxidation ot st1lbene with peracetio acid has been re-pox,ted (235) and the rates ot reaction with cis- and

trens-atilbene studied. The, reaction ot tranp-p-

meth7letilbene with pe~acetio acid :reported 1n the

experimental aeotion 1n ohlorotorm solution failed to

g1ve e.:riy isol'ablec .epoxide,. .aithough enctl:y the

-theoro'tieal.' quant1t;r ot pera.cet10· ac'id w,s oc;,nsum$d.

Monoperphthallo acid was attempted and discontinued

as an epo:dd:t.z1ng age11t because, ot oontB.lilination. with

unc~ed phthalio anhydride.

P,erbenzoic a.ow.- 'lhe moat trequentl7 used, method

tor the preparation of stilb"ne oxides :ts. the perben•

soic acid oxidation ot th& corresponding stilbenes.

The ~ynthesis was relati~ely easy. quick, a..~d th6

7:telds quant1tats:,e, at leaat in the case of p-methyl-

and p•ohloroat1lben~ oxides as reported 1n the expert'...

menta:f section.

Perbenzo1c acid gives the epox1de by 9.ig_-add.ition

of the oxygen .(34,236). Hence, .S.t tr1ay be concluded

that since the t;rang.;,oletins wei9i, used,. the epoxides

w~rs of.tro.ns-cont1gurat1on also.

:Taub (237) prapoJeci the following mechanism wh:toh

a.g:tteea w1,h, the analysis of' 'epox1de tonnatioii made by

Swern {B38)s

~ '" -c." I\ -~ ,o I ~ \.\

LX.XI

I

Q.ondenaatfon of 'penzxr cl'4b:!;!ides v1t~b b!QZB;\Asm;rd§S~-

The s,ntlle$i$ of epox:tdes b7· tm, condensation of bensyl

eblorides andben~aldeb.ydee was ~laasifiedb,- Newmann and }iagerlo.in ·(239) as a Dar1♦.ens0like condensation and

postulated, .probabl7 oQrrectly, the lollow~g mechanism:

LXX.ll

Ber~ann and Heney (218) a2Jswaed the existence of a methylene radical, NO, (t\\__~\-\ 1 • but this has ., \_:_I '-been refuted by Kleuoke:r (240) and by Hahn (241) who also showed that some structure assignments b7 the torme~ autb~rs were not correct.

.99.,

The s1P-th~a1s· i~as origiliallt d.evele>pi.?)d by Hatzig

{242J. Barrow (243), and Chi-zs1nsk11 (244)° and. later. -ext-anded by Kl~uoker (245) mid l\c~gmam,. and Henirt _(218) •

In the preparation o~ p•n1tl'os~11bene oxide• two isomers ,vere repo~ted in the e:cpe:rimental section. '?he melttng-

po:tnts agreed :f'a1rly well with thoae reported by Chrzsoinsky. ~he work 'ot Kleucker (240), Bergmann and Re~vey (218) and Bod.forss (246) 1ndioo.ted the isomers . l

lfe:tte the ili, aild ~'tE!A§ forms. '?he higher m~lt1ng p-nitro-stilbene ondo was probably tho j;rans•epoxide since s.t:.e1nmeti1 (SOO) reported the aae melting-point. 'l'he latte~ oxidized p-n.itrostilbenei prepared by the dehydration of the d1Qeyl $thanol• ·a method. which

usually gives th$ t;r:ana-oletin, with perbep.soic acid. :Bergmann. and. Bel.'vey ( 218) t~1ed to extend the

spithesio to include bsnzy1 chlor1de as well asp-end o-nitro•benzyl chlorides vrhiob usually gave good.

Jields of the epox.i.de. The, unsubstituted bensyl chloride did not Jield an epoxtde contraX'J to the ola:tm

ot Bergmann and Itervey (218),A.s deecnbed in the ex--perimental section of th1a tbt;sis. the attempts to con-dense benzyl ohlor1de and p•chlorobenzyl chloride with benzaldehydes tailed to give any 1solable epoxtde.

•·i

--100-

Xt the proposed met"Shaniem ts correc-c,1:-t would be exp~oted that an eleotron-w1thdraw1ng group should tac:1l1tate the reaction,;, and ·appat-ently this waa

proved to be th$ oas6. The J'ieaotion· appea.ra to be

of sutt1c1ent 1mpo:tttanoe to warrant ~tiler study.

In the condensation, the st1J.bene oor,..espcmding

to the reaction ot two aoles ot the. benm7l halide ocoas1onallt was isolated., Xleuoker (240) pzt0posd

the t'ollow1ng mechanism:

SOmetimee ~ the ether wh1.ch corresponds to the

benz7l halide used 1n condensation- wae isolated~ Kloucker (245) has shown: that since the reaction is run 1n alcohol in the ~resenoe ot potassium carbonate., ,, '

the ethe~ probabl7 arises trom a s1mpl& d1aplaoemen~ - ® -reaotion. c." \ 0 " + c.o ,- ~ ,. c.t-t ~ o -i- t\ U>\t

HO\ '&~M 1,, UL~(...":\ ~ NO,_ §,(.\h,,()C..t\ ~-\- (I.-

I-~ >c.1 V

Kleuckei-. :(24ti) noted that in the reaGtioa of

bensyl ·ohloride w1th p•ri1tro-bensaldehyde·Jer~-and Hervey (218} obta1.ned a product whiob.melted. at 187•189° they sugg~oted that this was not ·the expected

epodda but Q oblo:rohydI'in, slnoe Cbrzes1nsk~1 (244)

reported that he had isolated the i8!>met-1t p-n1tro-

st1lben& oxtdea. m,.p 122° and 74-t;f}•. tJ?he Sllggeetion

of ohlorohydr1n tormat1on,appeara reaaonable; aincewe

probably isolated• chlorohydrin 1n the reaction ot bensyl chloride with p•ohlorobenaaldehyde as reported

1n the e:xperil::aental section.

In the reaction ot p-nitrobensa1debyd~ with

benz7l chloride, the methyl ethe~ of p•nitrobEmZ71

aloohol was obtained as reported by 13fJrpann and

Heney (218). In the reaction of benmaldeh~e with

p-ohlo:robe,nz;rl chloride_ as reported 1n the experim&ntal

seetion~ there was isolated some p•ob.lorobensaldehyd&.

tt was au.ggested previousl7 that th& produets ooulid be

accounted tor by an. attaok ot the base on the Mng

carbon atom followed by cleavage ot thee oar'bon•oarbon

bond of th$ epoxide ring. Anothe~ interesting side reaot1o~ is the formation

of a. carboxyl1o aoid whloh oorreepond& to the benzaldebyde

used 1n the oond~neation. One posaibl& mechanism

may involve• pl'&l:lmmary t1s~henko bf an O•a1kylat1on $;

G::> ~ 0 <..tit \

t 0.. - '(:)--t..~ 0 -)

~~action followed

()

+ (..Q_ '8--e..'' .... 0 E)

LXXV.

The, poatd.b1l1ty ot a Cannizzuo reaction oarinot be

exclud~d ainoe•_p-ohl.orobeneyl alcohol'Jt' 'although

1n ·small Ji.eld, was det1tt1tel7 proved. Special pro~

oedures to exclude moisture trCPA th& reQot1on mixture

tailed to prevent the fot'lmation of the -acids• The

mechanism shown above provides a second poss1ble'routie

to the fol'mation ot ethers from the corresponding

aldehydes.

lJ!29.f-af st~tp.~! ot . p-m§tbxl• ·aµd· 12•0W,ot9•

sttibe¥. oxidO

Parbenzoic acid 1$ an tfteotive roagent for ~o-

version ot olefins to the oorreaponding epox1des. It

has b~en obse.¥'.'fec.1.• however, ~hat .. a o,u,'bo~7;l compouac!

~a:r 'pe formed -r~'.t~~r than the epox1c1,. ~u• Sal:,,~ (247) tou~d ~~$ 3•♦•d111J'dr<>•6-metho=,-~n•phtha1ene

,. ··1 •

ga 1"f 6-meth.Qxy•~ ·•tetralone on o:idat1on. ws.lh per-

benzo1c acid. Newbold an,d. Spring (248) obta$.?ied 41phen:,lacetaldehyde t~ l,l-diphen,-leth7lt1,t1'1et v,ith th$ same :reagent. S1mS.larl,-, ZattSSt Pre1telder.ani!l Horrom (249) reported l•phen7i-2•tetralone t.'J:'IOll. l• phenyl .... 3,4•cUhydtto,..napb.thalene. Wtlsenbomand !au'b (250) obtaiped trom l•(~1phenyl71)•3•4•d1h1dJ.'onaph• -thalene. the corresponcU.ng 2-totralone.

Al'though thfll epe>dde ot p-~tb.1,lat!lben& md the two isomeric ketoneo have been cbaractort~ed 1n the . . \ . : . . \ ' .

lS.t~~a;t;l,U'e:i the three. ce>mpQU:nd.s ~ere synthe~tzed., fhe -~. ···.-¥.'· "_:.

physical propeJ:'tieQ p:re~luded the possibil:lt7 ot con'."." ,: , I

fusing the, epox1d& with eithe~ ()~ the ketone1:s. ~

same mq bo said fo~ thet epod.de obtained by ~he.

perb$nso1c ao1d ox~~atton o~p-ohloi'ost1lbene.

Apa;J,yais ot Red'2ct1on Product, of ie~Ohlproatilb_gne.;Oxide

PteTious ~gl.7ttc 4 ap;nlio a t1on1,~-~ ~:ii~ ot ·the

major problems: .. 1n determining the ett~~-~- pt a aub-

st1tuent on th.e· d1reot1Qn Qf ring opening ot epo:xides.

is the quantitative anal.ys1a ot the isomeric product$

obtained in the reactions~: Analyeie b7 ,quantitative separation ot isomeric •1xturea is usually difficult

due to the e1m1lar1ty .in the_physical propert1e~t Praotional d1s'b1llat1o~ has been ui,ed successtu117'by Chitwood and ·rreuve (6) in. the :ri,aot1on-ot prop7lene· oxide with ethanol. Separations have been mad~ based

on ditterenoee in the rate~ of ester_iticatiori ot pr1Jna17 and secondary alcohols, Thus, Oox, Nelson and Oretohe:tt ( 261) weret able· to aeparate and iden t1fy · the.

1aomerio ether•alcohols obtained 1n tb.e ·non-oatal1sed

reaet1on ot propytene oxide with n•px-optl al.ooho.l.

Guss (26~1 263), howev~r,, indicated that thia method

may not be quantitative. lt 1s poss1bl.e, 'also, to tranl$form the isomeric piaoduots to derivatives suitable for trac1;1onal orystall1zat1on. Ettlinger (2),, fo~

example, was ena'bled to separate the mix~re of amino alcohols obtained 1n the reaction ot butadiene monoxide

•105• with ammonia b7 :tpaotional crystallization ot the

oxalatea. It may even be neces~ary- to subje~t the 1oomer1c oqmpo~ds to a BE!l:'ie$ ot eh$!110al reactions and to separate an~ identity th$ end p,:,oduota. TQ.us, Adams and Vandel' Vlert (56) succesotullr ot;,nvert~d the

products o~ the reaction. ot butlld1en~ monoxide \Tlth

aoetoa~et1e» ester to tho isomer!@ alcohole, 3-heptanol

and 2•ethyl•l•pen.tano1., wh1oh were s,parat.ed quanti•

ta.ttvely bJ t~aotional distillation and identiti~d by ox1dat1cn to the knowa k~tones, Sep~ationa such as

desc:ribed ar• limited~ hc,,wever. part1cultu.11l7 it one

o:r the isomers 1s P.l'~sent in small amounts. !J!he quantitative Qt).alyois ot isomeric mixtures

without actual aepara.t1C>n ot tl?,o ~omp911entl!! baa

physical prop~rt1~s of the isomers falls in.this ' '

eategoX7. .thus, Reeve and Ohr1etoftel ('78) found

th.at the isomeric ethe~alcohols obtained in the

-reaction ot styrene oxi~e with JJ'leth:"1101 ~ould btt

analyzed b~ virtue ot the differences 1n the vis• coaities ot the primacy alcohol:•seoondary ether and

the secondary o.loohol-primaey ether. In general,

refractive 1nt\1oes and d~neitiea "are not suits.bl&

between the is~e:-~.1 . It may be possible,,! al-so., ·to make uae ot the·phys:tco~ohemical methods 1n the same .manner$, Halperin. and Van.der Wert (254),. however,, 15·ere unab~e to ua~ infrared data on the isomeric butylene b.alohydrins obtained 1n the reaction ot the s1m1larfty in the spectra. -In the speoial case of halohyd~in isomers· such.as obtained by Smith (l09,S66,256) and Paul. (l.15) 1n the rea<>"t1ons ot .a.lkylene oxides with

li7drochlorio acid and by Swem. Billen and Knight '(69)

1n .the :taeactio,i of ep1t)hlorohydr1n with all7l alcohol,

it was possible to analyze the isomeric mixtures due to d:t.f'ferenoes in the rates ot reactton with alkali.

Melting-point cotnposition curves have been used eatis.f'aotoril7" by Gu.es (252,253,257-260) and his students. Thua, in the reaction of styrene oxide with naphthol which yielded an isomex-ic m1xtw:-e ot aey-

&ther-alcohols, the analysis was made by- use of a phase d1ag:ttam constructed by plotting melting-points against composition ot known mixtures prepared tram tbe pUl-$ isomers. The melting-points of the mixtures ob-tained from the epoxide reaotions and ot the known mlxtu~es were. observed und~r crossed polaroids in a

-101-

Beolanann•JJ.ko apparatus with a oalib:ratted tl\cr.momet~i''/

Baimond (ll2} used the liheinboldt method in the d$ter .. . . . ..... ; ·, .

mination ot the isomeric 31 ~-dini t:t'60'benzoatea of the

ohlorohyd~ina obto.1ned in th$ reaction ot propy~ene 9;d.de with hydroohloric acid. Skau and Wakeham ( 261)

advocate caution 1n the prepQrat1on ot phase d1agrama

by the Roinboldt or capillary method as 1 t is cal.led ..

n1n 'the .f"iret place, ;tt does not veadil;r permit the . ~ .

atta.inm•nt ot a trufl equilibrium between the solid and

liquid phases. and. eeoondly, the technique for th$,pl."e ...

paxaation of specimens of k11own compoaitipn inv,olves ~

conaidettable sourc,e of ~r~or~"

Rh~inb.9ld!i rp.etJ1.o.s,· Whe oapilla17 method and ~ts

moditicatic,ns W$X'$ attempted be<uius& of the apparent,

ease of manipulation and the small mounts ot material

ne"ded. Analytically pure phenyl urethane derivatives

of p•.ehlorobenzylphenyl• and p-ehlorpbenylbenzyl. oa,:,binol

were prepared and. fifteen samples which ranged in

composition from 0•100% were weight?d out to the :nearest

tenth of a milligram on an analytical balance!I' 1he

samples were weighed by difference fx-om a weighing'!

tube and tranate~red directly to -th$, bottom ot a teat

tube without touching the i,idee. An intilna.te mixture

-10s-

th" aolid:was. tr~sf'erred to an agatetl'lotor and pestle

and ,finely g:rroundl; The melting poi:tlts obtained by use

of ca:pillat7 tub&s p:roved to be poo~ly ,X'eprodue:1.ble'.,

Better results we:re obtained bJ the use o.f a heatihtl

stage and observation og the melting-poin.tas und&:r a

mierosoope le3ns. fh$ phase diagram constroct~d· from

the d.ata i.,o obtained indicated solld solution formation

;r.1th a m1b.1mum at a'bou·t 93° o. B.?ld a composition. or

50-60% of the urethane 9f p .. oll,lorophen1l.bens11 earbinol.,

The ends of the'phat1e diagram a.ppt,arc,d to be satis•

faoto:cy:, buif the points 1n th~oenter ot the diagram,

'between 40 ... 60% did rto~ fit the curve an,d,, in fact, were

not easily rep~odu~~ble. ih$ us~ of a Kofler heating '

stage m:l.cros<sope with crossed pola:roids ind1oatl$d that

the compositions of the m1xtur'es proba'bl'J were, not ·,·

unifonn. The .method was abmdoned in favor ot therinal

measurements since it was apparent that the Rheinboldt

method as applied to the anal7a1s of' the reduction

produota ot p-chlo1~atilbene oxide la:oked the necesaal'.'y

precision-tmd accuracy. Thot'mal _;analxsig•• It was repo~ted ~- the ex-

perimental seotion that the vedp.ction of p•ohloro-

st1lbene .px:td·~/:ga,_t;_.iiQ.~9 ± 3~0% ot the ~r~thane ot . ., ···•,, ... ' ,• . .,

p~hlo~phen7lb~n2171.·carb1n<>~ and 59.,,l ~ S•/J'% ot the,

isome:r:-., The ip~ects:i:on,. then,,. is approx1mate1'1 5-8

parts per h1.1ndtt~d.,, W,~m th$ser drtta,, 1\. was assumed

that the catwb1n9ls ·t.rom whic.t~ the u~et4anee were derived were prea~t· in th~ aame rat;3.Q•,

io ch$Ck the ass~pt1on and to .establieh th, accurao7 or t;he.·method,. a.. sj'Yl.th-,tie mixtu:re .of oar-.

bin.ola wa,s '. prepar,d ;1th $1.4% of p~eblorophenylberistl

~at-btnol ,and 3~ •. 6% of· 'th• ieomer~ The ca~binols weNS . ' •.. ., .

oonve11t~d. to ·the urethanes @d analr•ed b7· the pbase

diag1•m method, ru1 was done to?' tho unkncnvn ~uture.-·

the ex:per1l!lental dert?em1nat1011 showed 64. 5% of p-

chlorophe11:1lbens7l car'billol de~ivati/'re. ~a ·in•

vol'ited an ~rror ot:. $,.1%.: or about 6 p~rts peri hund:red~ . . • !. ,,,,

~he accn1raoy ot th~ methr>d. mar be o.onsidered as es•

tabi1sp.ed sinci. thr -erro2." ~v~lyed ,is no gpe~ter than t~e ~ttidnable pi-ec1s1on.

The- phase-diagl'am indicated solid solu,tion tonna-tton wi:th a m1n·imt.tm at ?7.s0 o, •. and .a composition Qt

57.f}1' oz the. ur,ethap.e of :p-~hlo~ophenylbenzyl oarbinol.

Apparently .the &leinboldt method wa~ even more tnaocu?.'.ate trum o,t first suppot:ied since thtS m1ntm,tun appea:t-ed. at

-110 ....

93° c. in tli~:·:~4t~t:e1fmethod... Soiid solut1on, fomation was to be e:xpe:~ted/beoause of the siliila~itf in the molec:ular strue:tµre.:

~hemQ ;~-~ithot'i-~ F1:tte~n ·acottrat$lJ weighed

mixture&- ot: the, analytics.llj pui,• phenil urethane

der1vnt1voa ot the 1some1-10 p1athylphentlbens)'l• p~meth}rlbenqlphcn71- oar'b1nol• we1e p:ttepa!ted and. the Jielting-potntl.l tllld. t~eoz1ns po1nta dete•tned. 1n the manner d~so:t'ibed tor th• thomal anal.ya1o ot th$ iso-meric p•oh.loro•alcohola. Onl7 heating ~u~•s oould bfi obtained. Once the #lixtur& was .melted,. t t could

not be c:r:,Btall1zad aga1t1. even on standing and seeding._

~h~' phase diag):ib indicated sol1d solilt ion .to~~tion

tr-om. gQ~lOO.% ot p•m.etbylphcnylbeMJl o.,,.'blnol and a ,eutectic al eo.-&0 'beitwoon o and 50%• All •utur~e b&tiT~en. o .and eQi $hQYte4 a tla.t at appro:dlrlatoly so~a0,

but th~ .upp$r points ooul.'1 not be tnt~rpreted. Iti

m.1ght have=· be$n ,pos;ttbl• to iuk~ use of the area

bet\"loan 50 and .100, tor analyt1.oal purposes# wt becautJ& of ouit inability to 'b1'1ng about crystall1sat1on ot moltenm1xtuXiea and bf!)oauae. ot unoe?'taintiea in the phase diagram, the thorinai method was ~andOned in

favor ot a oi-;,ooacop1c •ttbod nol prevS.oualJ.i.it'epol't&d to, uae vrith aolld eolutiona.

Ottoacpn:.t.c AAal?Z,t1.is 11 non~,eolid solut:!Qll f'onng•.

ti.on •. - A ge:r1e;tie.lt.z'ed met'1od, develop~d b7 the But~~

of Stan.dares (.2_6~J to~ the detem1nati_on ot t)ie per-

centage com.pos1tt'tW, ot·a. knOl'l?l compon-ent hi a mature of unknown eompo~it1on oons1ets 0:f the det.enn1nation ot the treezing""'point depretesion with a fJQl"en"t whtoh .is not a component of the mil!:t.ure and. the tree:&"ing•

point depreesion v,1;th the known ~mapone.n~- .as soiv.ent. Binet the treei~g~point depression. in the latter :ease

will be due tmlt to ~ose oom~o,:,.en'l:e ot the mtxtul.'8 which. d1f.f'e;tt frc,m: :tl:ie ,sol.vent, !fi bi.,oomes poes!bla to

oalc~iate the percell.t•ge. -.,ompos:t.ti9n ot the kn~mi.

·:,comp~p.-~t~ , ,~ ~!~~d- ~a been, ~PP.:ttpd. to the-; . .

\).~aiys~~ ,9tH~f.;~• T ~, i~om~:r,r (2~;s) •

The total numl)e;-- ~f: moles ot all components.ilia one gram sample of the unknown m!7!ture~ mt , 1.s solved

for '.by use 0:t equation 1:

(1)

-w ... 0

Ws • A ~s 1000 •·•~•~ts

the •-W~18h::t ot solvent,, a,. w~eh 1s krl~wn ·not to be a 0.0.mponent ot the unknown m~xtµr'-:,, 1.$., camphor o:r.e triphenthlethane. tree:d.ng,-point· depression ot so-l-.rent s.

ltts = ceyosoopic constan~ ot solvenii JJ•.

"m = weight of unknown m1xture •.

In a. similar manner., by means ot equatiOD. 2,

the total number of Bioles ot all components ex-

clusive ot the known component, •x II in a one gram

sample ot th.& unknown m.ixture :may be solved fox- with

the known component as aolventt

(2)

.. • weight ot solvent A kn~wn to be a component ot the mixture.

= freeaing-point depression ot solve,nt A.

: ceyoacop1o constant ot the sol'V'ent A.

= weight ot the unknown mixture.

From equation 3, •• , an appi,o:dmation of the

tote.l number ot molets ot component A., lmown to be a component of the mixture, in a on& gl'm satnpl& ot the

unlm.omi mixtur~ may be obtained&

(3)

The weight of.component A in •m g~am.a of the unknown m1xtttz-e, W- • A , ma:, be obt?~1ne4 from equatioit ·4 •

•A = molecular weight of oomponent A •

. 1,. m~re pr~c1se valtte of 1lDx and mA may be .. <:>bta!ned

~rom. eq~at~on~ .6 and$:

(5) (~A :f- ~• A) • b ••

·, ,1000 • ·,,_. • It,;

!fhe percentage oompos1tion ot component A in the unknown mixture may now be e•aluated b7 means ot equation. 71

'l'h~ equations are based on eeve:ral assumptionis:

(l) that the solutions are ideal and Raoult'a law holds 1n the range ot oonc&nt~at1ona used.

(2) that the treestng-po1nt depression 1s •all.. (3) that· tlle weight o~ solute 1s small compared

to the weigbi o~ solvent. (4) that the latent heat ot tus1on ot the solvent

ia not a tunct;1on ot temperature.

(5) th~t on oool1ng the m1,:~c,~ pure solvent

solid aepuates, 1.e., eol1d solution ~ol'matiOD does not ooour.

In 41lute solutions, the ti,..st tour aesumptione are usually Talld. It., howe•er, soli4 aolution does

.occur, the method must be mod!..tiad.

Cn;qscop1canaix1:L• o~ solid aolptiong.- It oan ·'be shown that equation 8 11 valid to~ a two component

system. which forms solid solut1ons1

(8)

' xc,4 ~ 01.7osoop1c constant ot solvent A. X'tA: apparent ox,osoop1o c,O!).stant ot solvent A..

: molal1tJ of B 1n A. = d1atr1but1on ooeftioient or B between the

sol1d and 11qUS.d phases ot solvent A.

The oompos1t1on ot a g1"fen mlxtuN ot A and B

ma, be det~1.-'l711ned it the\appia.rent f,l'J'Oaoop10 fonst~t

oan be evaluated. <m' method t>f obtd.ning th& appar~t

Ol"fOsOopio oon.~tant ts to detem1ne the .fi-eezblg-poi!it d.epreaston ot known mutuNs of solut, B !n solvent A and graphing o~oentration vs. treesing•~o:lnt depresa1on tor three ,,,, tou aixturea ove~ a Nlatiw-e ehori rrulge

o~ conoent~at1ona. !he apparent cr,-oscop-1o constant· • •· • ·' '', ' I

ot solvent A maJ then be eyaluated, not only tor the prepared ~btures. bnf; to• all ~oncentratione over the. range used11; A. .~eoond paph mq be ooutruot~d by

plottini the treesing•po·ln:t depreea1ono 11'r.s. the apparent

or;roaoop1o constant. 4f'ter determinatioft ot the t:reez1ng-po1nt depr~ss1on ot t.he unltnon-n m1xtux-e, the apparent oryoscop:lo oonatant.ma:, 'be obtah'led dtreot1f trom the latter graph.

l'or a three oom.poneot syst••· A, 8 11 and O, which

tom solid aoiutiona,. the generalized method fo't' a

ci7sosoop10 anal.Jaia previouel7 described ma7 be used, where equation 2 is transformed 1nto equation 9:

(9)

The ~pa:t-eut. c~aoopio constant, K't.A • ta now a tunot1on ot· the diat~1lntt1on ot the-oomponente exolua1ve o~ A; 11\'e~,. B and C_,. bet:weon tbA!I solid and

l:lq'llid phasee ot solven-t A~

It ma7 be poesible· to app1'0:1d.mate lt' tA b,- aaeuming

that th.<, d1stnbut1on coett1oient otC: 1n A 1s th& same as I 1n A. th., apparent O:ti'Joacop10 ··constant

can then be evalw&ed at the ~xpel'lmentally dete1'n!ned fre-,siDg•point depression b7 means ot the graph oon-straicted from mu.tu~a ot solute B Sn solvent A as desox-tbed above ~o:t two oomponeDt e7etems.

tne pt'()t)edu~e.tor detemmat1on ot th• percentage composition ot A 1n a muture of {l; IJ.,, and C 1~ other-wise 1dent1cal with that·p~ev1oual1 deecMbed tor non.-solid solution formation.

Disougs!Q:q.52[ 2m,9gcop1~ res~lta.- 131' use ot the ol'7osoop1o method tor the analya1e ot solid solutions a• desor1bed 1n the pr~ceding pa,.-.agraP,hs and ~ep9rted. 1n the expe~lmental sect1oni 1t was tound that p-met~7lpb.en7lb$s71 oarbSnol was present ae

20.1 ± z.1% ot the total mixture and t~e isome~ as 42.0 : s_.oj. !he precU.s1on attainable 1n the deter-.

mination of the peroentago compo:d,-t1on waa approximatel7

7-11 pe-11ts per ~drcd.,. The laek ot bette:r preo1s1on :ma7 bfJ due to the fact that the f'reez:tng•po1nt dc,press1on is the ditterence. b"tween two la:t•ge values •. o,:, it ma.:, be due to the ~ssi.mpt1on that th$ apparent c17oscopic constant of tl1c oarbinol~solvent is tb.e $&me fo'!! the non-carbinol-solventa. as to~ the carbinol-solute.

'rho a.oouraoy ot the method was checked by the anal;ysis of' a synthetic ¢xtu:r6 of app,mxim.atel.7 th& &ame oompoait1on as the unknown mixture. Thus_ a three component m.ixbur& ot p11ethylphen7lbena7l ctar-

binol (26,6%), p ... methylbens:,lphenyl carb1nol (49.0%) and p•methyistilbe~e oxtde was analysed 1n th$ sam& manneJ'· o.s the unlmown mixture. 'l!he d.eter.mination, as

,.t-eportod ill the expettimental sect:t.an __ gave 22.,'7% ot ----p•methylph'enylbenzwl oa~binol and 44~5% ot p~methyJL-

benzy:lphenyl o~b11Clol, whiclt. :tnvol.ves en e~ro,_. o't 9•11 parts per hundred •. It appears ,hat the en-or- involved bl the --o~oeoopio analysis is not g>.-eate'-1' thm· the

precision attalnable., i.rhe accu.t'acy ot the method is ;sufficient fol' the purposes sat forth; namely., the

deter.mi.nation or the ratio of isomer-a for.med in the lithium aluminum hydride reduction ot p""ll'!eth:y'lst1lb~ne

~ll9•

lt was assumed prior to the analys•1a tha.t the rtt~•.

dUots.~ produe'ts .consiatedma:tnly ot _three c02nponenta with unchanged p!'"methyl.stilbene on.de as the th1!94 component~ i~s vias ve:rJt1e~ by oaloulat1on of ;the

ave:l:iage mol.e4)ulue weight o~ th~ i-educt:ion produo·t• by

arieans of equa:t1on 10 ( equati'oll 1 tnv~rte,a) ,

Th-., moieoular w«i,1gh'C, was found to be. 218• Since the

mole.oulai- we1$.h1; or the ca~binols is 212 and the

moleoul.a.* weight of the epoxide, 210. it appoa~d

t-easonable to aaaume that the e"Dod.de wae.tbc th1?,)d ~ \ . ~-

,~pon$llt.

'!b.$ t:1me.-tem.pe~atur~ ounea tor the mixtures, as i1iustr_ated ·1n·. the experimental. a,eotion, Diagra III"

were typt.ca~ of s~ltd solution. :f'oi-ma tion., ~1s was tto be· e,cpeo~.et1f be~ause oompounds which ha:te sim1Jai.t

stru.etu.rea s.re ~cognized as COJrJ.pounds wll10h generi?lly

tor= sol1d.solut1~ni.,~ It is evident trot1 Diagram IA tha.t the appa~en.t

er,'Osoopio constant is not oonstant and may change by

as muoh as 15-20% even in solutions as dilute as o.o&

mole t~act1on. ,.Ae, ~xpecte~, 1n. V$~ dilute eolutt.o~~•

henc~ f(!~ small- ti'ee:u.ng-pout dt,p:,;,ar;a1onitl: ·t!ie o,on-

stant ~o~p ... metllylpbt1tn-,1bet1.S7l,Oar'b1Dol: app:,,oaohee a

OOX1$tant V$luc, ,of e· •. fU~. !the de•iati~· trOFJSt 6e,M 1Jt

m.ore ooncen'.bz-~ted solut1oae DUilJ' b$ tue to dev1Atton~

t~ Raoult'a lia.w.. Sim.1la19J.r •. 11· was :fo,unl,l that th~

a.pp,-re,nt o-17osoop1o'. eonstant ot _p-met..bylbens7.lphentl

ca24,in~l'approJoho4 a o~ot~t Yalu& ot·'1.l,&.

flu, Bure~1,1 ot. S-and~de • met.hod wa~ ,iee~. t;p det;e~-

m1ne- th~ pe~ent•oomposi~l,on ot n~»•T• 11Somel'&~ lfQ

mention, howeyer, was-made ot the .tac~ i;hat tho isomers probablJ·fomed solid aoluttone. fhe method as

o~1g:J.nallJ de~O:t"ibe.d was 4et up only t~?& the- ana1yt;d.s

ot··mi~t.ures 1n wt.a,..o~ p'@~ aolvi&nt solid s&pa~,tea w~

the a&iU?pl$ Js. c.,o~led. 4'\~ni1on was calle4 to. the fact

that the 4ete~inatt~a. ~t tb,e,. "cJl'J'oaoopto oonstauttt

of the· ·.iaome~a 1a~ka4 pl'~oision. th1$ wo.s attributed

to the use ot ~ 8eokm9Jll1 themomete~ !nstead.ot the•o• \ . ·' \,\,__ . . .

oouplee .. trom th• marited Cl:'lango ot th& apparent oi'7osc*10

J~

constant with ohangea in oonoentre.tion even Sn what mar

be considered ·as the range ot dilute solutions.

The c17osoop10. constant of' tr1pJ&ny1W\ethane was

deto=tned1 g_s rep_o1>ted 1n the. ex.p~l"!ln~tal s~ction, wi tb p .. me'ehylphen7lben3yl ea~binoi alf the ~olute~ The value _ot 12.3 Qloaely t.lhecks the:, literature value of 12.45.

EXP~ldr:At. ¼l'EOt!OM .... :'~herm~l .ktaii;~~'.'.~'.~~b;:·:~~ti~t~:o~, ··:~oducts·.;.;;.'

::_,,.,_" · < of: ·P;:::Ohlb:ros:ti-lberie- Oxide'. ' · ,, · · _.;:'.'.:~f';•~'. ·'. :·· ' .. I ' ... ;·· __ ; ~ "~- ·., l · . . _ '.. . . , _ ,i

.e.i1d .. tqu,~q i1i'~bin the· :1im1ts or e.rroz-· bf. 'tq.~ ~:na'l.ysis;. ·we~e _.µs~d-;J'n the preJlS.ra.tion '6.f the phase. ,lt:te.gta.'111,.·

• '• !" • I , • : • •

:_q!_ll~- reduction :P~Qduot.a were· ;Pre!)<~;red .tdr -&1a.iy;$,\s ::·\::·' .,: .

by soi1itlon tn ;metho.p.01· ·to :re.:no·ir~ l.m:Ob.~ed. epo:d.de,--'l'he ni)i~ure of· -carbonoia ,ta.$ t~~a.teg., wlth. P.Jtentl f sq¢y~ate,:._ and, tile ur~t,bAnel!S w'pr¢: -~;~i~~ ll.1:f g.ea+

;· . . . . ,.. . ...

cbtl. b~d.- the. ttn.¥n?wn m~x,t,ui-.~ eo ·prepa;_red.. w.a_~ :found . . ' ' . .. ' . ~ .

t.o c;onsist, soleJi; :.o; \he desiped. 4I"etha.11es pi ·_¢e.,:,bo11

and hy~qgen a.p.f;l.lyais ,t A .synethet:tc. :mix'ta.1~J pt·, .P®o . ' . '.). •' .

a.s· d.~term~ned tor the, µnk11owi1 mi~t111 .. ~.. Th.e ca.±-bl.n ...

ola 1it~1:.e ·. c011vertect to 'the rsomcric ui"ethttnes f'd~ :· . . ·_:. - :_. •: •. '. ·_. . ,:, ' . . •. . ., ' . , . , y;"". . < ••••

e;ii SS..,'IlJ?l<:is afe carefully cieaqri be4 in -the s~G~,f9n on -~-. :- i' . ' . ·' ·'.; . :

S;ttrth:e:tio: 'l'rocedure~ -. Detail$ e,s to th~ oua:ntI't,iea . ·. \' . ::- : . ' . ...,. '•. : ·:- :

er~ g:t v e11 .. -

.~Jl: 9,a.TJ1ple$ wera weigh~d by <:lifrezt~nffe dfrec,tly ·-·/.'i_· '. : ·. -:::_~\ <~.; ' ... <t->>:_,:,___ ·', . . . . ·J.nto tlte:- ~.¢plnn9.n..'1 cellf_

:L~')2l?§:ratua~, ... Time ... temperature eu'.rves vte-pe i:.alten _,,;·,:· .... ·,r. ·.",1 -.

Jt'l1.)i jj(d.dlfiea' :E3ecl<:mann · ce11 :,Tittl Eb ~a.:tib~~te~ ¢oppe1" .... ·-:-·;>_' : ' . ·, .- . . ·,.

#.Pnst~1;ta?f ~hermoooupie, ~sed in OQb.J\i;ne§£01;1, ir,t~~t a \:···,\ :'.-:-'..:: .• ·, -·, . . . ' .'·i .· ·:->.~::·'

Model, ;St t~sd,s e.:nd Northrup Miorp;,iar.:, ittitd;Jl~~i.e ·re-

¢oro,;~g ~oteritiometer. A. typte~.1 heat1ni . ~uW~\:~nd cooling curve is reproduced in 'D:ta.~ra.rn A•: ~h~ curves: ¥ere inked. in on graph paper whiob: vte.e· aubd1y1dt;j~ i,n

111.tervalo .or 2 degrees o. and 10 minutes.. The design

of th~ ,:Seclonann cell ia sh(:!wn 1h Dia.gram c., 1'hema.l equilibrium was attained 'by means of a Spi~l shaped glass stirring;_ rod a;titaohed to a. soft iron eore and

operated a.ct 80 cycl.es .pa~ minute 11'1 ver,tical. rnotion

'by a solenoid e.ttaehed_ to e. eircui t brealtei:'-. t.rtie 0 hot O jtmntion o,f the asbestos cqV'el:'e,1 oopper--c9nstan..-

~ri thermocouple wa;s. plaaed 1n the nanow e;la$s tube

ti:on:¥;t·,;_-+ns·t:t'.umf)nt~l ,o~11b~a.t1ona ·w~r¢ -map.e ags.ii1.st t~e ·ux.-~.~'h~i:le,$1 ·;b~nt-o-i.c ~eic1,ar1d th¢··-~ee""'.pot~~ )t~th

·.~p . . .· . '· ,:. i:

·hllet :~~t~r,~11de june~lon:-$'ti 09nata7J.t ~dorn :te.:rt»el:'atu.re. ·. ·; . . _;°;·.

A caJJ,01..'~t~cl 'aleqtr:toaliy h~e.ted otl~ ~th vf!\Et used · .. , .. ;. . : . ..

'to. 6¢xitt6i ·the ~te of ll~M.ng t;r.om 'O'.~$'. to: .1.5· er,. p~:r nt'in~t·¢l

:~:~ec~!alon .. gf me:aaur.ements~ ... -Botti ¢:opi1~~qtt_:rves .. _)·.-}· ~- . ,l . . . . ! . ,· ' ) ..... :·~=)<

:fi~d ·11~t:i-ri5,-.o~~es were ·l'l'b~a~ne<:t; ~ct .~u~.6~e.t'.iqtii11 tooo;a~~ ,a. Q.E3Scribed+ ?he; lQW~:C .,tr,eJ~z1~~:PPi.rii:s ,.' ,, . .. ·. . • ,. . . • .. " -••. ,_ : "t, ;' . ·-,·,:, ....

;~J(?l.'~: Jq·qx•e $~$11.1 :11ea.d ... tt-~ the ·cqq4~-t-Q~$s.::;:an~ i<)·re ',~e.lJance, was pl~aed, upon th$SEf ;41'µ$·~ -'W:~"~- ~r.o:re

';_ ;'.. ;.~ ": " ,• •' • 1· • I

r,aprodll<;}bl,e tg .1*0 p~. dn a.nr siv-eh· $at11pl~:;, /~he tjpi:>or.,.rnel~in$--P.01:ttts w.er$' o'bta1.ned/:f"rit>ta lte~.'.t.1.ll$~ oul"'V'e~ Wit~ a.i:!f-io1.1+ty. DUe to dec0rnpbsi tipn,_ ,o:n1y

tb.l'9ee:-- <,r f ow.'t cu1,"'Vee ver.G t.aken on e:~y Qne a·~ntple., ._;. ; . . ·' :··· ': -~ ,

~);~as e. die.p;i:-{lm ~-~ ·~en a~tr1P+ ee o,f.· ·a.nalr~~~aµ.:ly ,, !Jt,We :"• :'.'

urethane derivatives o:rr the isomerio carbinola w~~e .. . . . . ' ,. '· , ..

prepai-eci ~i th cqmposition$ w-b.ich r~nged .r~om ,0 .. 100%.: -~ . . \.~-

'.fq.e a~·pb,sit1.on or the ls.st mizj:ilU'e t,o be etnp1~.r,:~ ·wa.$ .· _. .- ·: ·--.

chosen: to check the mim.mum m~lt;t:n.g ... ppint.· o:t tl'.i'& phase

:4ia~. the de.ta was recordE:td_ ltn T~bl,_e ll•ft [it,i.e l)~S$ <l.'lagr~n ;+a shown 1n P~agram :a.: .. '

A.rtal;vsls o:r ti'.n1mo,wri ·mtx.ture"~ Thb unici:bt~,rtd,~ttil:r~ Was ~4acd to the tti"ot/futne oi' p~ch1orophe11t,lbe1t~f.1

d;ai-blrtol, quanti t~.ti v~;,r, and. the n1elti,nl~"",poi:nt.! ~cl

t::i:-eer.ing-..poi1it obta;ln6d.,., The new ml::-:t{rre·'~s, rib aµclt,

oompositio1t, to brittg 1:ihe cbm:nosit'idn lrtto,\i' )fo{i eail;i,I : .• t - • ~· . •. '. ' ., ' ._ '-:'- ... ,,, .• :

Jbrs.tect. 'iection of litF> phase d.:l.tagrain,r B:t tilti.~~'.l?.P~c>-,;~1at~ csh,otUe.ticms, ths perc~ntage-eompos:t1tfio;<ot' -_;:_ . ' ,- . ' . . ' . . ,· <} ;;! ,/-;:· '

tho W?eth,e.ne or p-cl;lloro'b011zyi;phenyl oa1--'b;,.,nol h"a.s

det.o;t"Inin~cl. J\ sj.:m:1.).ar proriedurie w·a.s empf oy¢~i:t',&t the i ,, .,,, .. •, C .;•;

a.nsltsis ,ot the ·ui-•Qth8.rie of 1, ... ,ohle>~phenyj;t,,~1tztt par-; :· ; ',, . ' . ·,• .· . :· -.•. ·/,i. i· -~ .' ..

'i,ino:t·... Th.a· dat.s. a'..&e reco1~ded ln. Table ·1:rtf''. ,_., •· '

.Wt

!! p¢rcHnit-cotn!X)S1tio:n, (:)f 'lJ"."Ohlop9 ... bettzyt:phetiyl .. dei:-i va:tiv:e · 1n ,th$ ul,'lk,.'1.ovt.n, 1n1xtw."'e

peroe;nt ... com;poaltion ot p~ohl:brq ... benzylphenzrl oa.rbinol dap1vati't,f'f): 111 th.~ new m.ixturo ·

::: ·totltl, m~ight. of unknown mixtu'X'~ an.a ·t.he a.d.ded. p-chloro.phenylbe11z;rl d,eriva.:M.Jt~

Ana:Lya1s of si1?-thetlc mixtw:-a.- c:fb.e ;s.ame pi::ocre¢.ure 1 ~<-.

·ienp;ored fol? the analysis of. the unknown. mi~'t,ti.tt~;·,,as

1.tJi.~ibJ}1t'~- ~lle S..lle.ly~.1..s .... Qf the synthetic I!ll-~ttlre ~ the

,aat·a. ·are :tteoo:11ded in Table IV. ···-.. ; ..

TABLE l:I -~@.e. Dias~am.t ,. B!na.;rx .SysielJl.

·' · · · · of· A··

sampl~t'Wst,,.Qf.L- Wgt. of ~QOltlPit %Oo.tnll•. µp~~~ .. Lower ll . .A B ot 4 ot 13 m.p~ m•.P•

l .... ""' 100 o~o -· li!3..5 2 5 •. a1 1.21 a:,.o l7-e> 104.o 98.:0 , ,:;.,47 1.,49 10.0 $0.0 96~0 a1~0 4 .2~9'.5 2.10 :5e. •. 2 41.a. ~ 11: •. 0

5. :,.61 :;.37 5l.7 48.:-; 96 •. 0 e2.o 6 3.24 4.as 42.0 ,e.o 106,5 ~2~0

7 l.61 4.95 34 .• 6 65.4 ll~t~o 99.5 8 1.02 4.26 l.9~, 80.7 124.o 112.:0

9 .... , - o.o 1.00.0 .... 1:;0.5

i'AnLE :u:l ··. . P::Chlorosttlbene Or..ide .

Analysis.of P.b.glu~ethane Derivatives ·or, Reduction•·• Produets

Pb.ew1iu.rothane qf p ... ql:llOJ:'.Oph(:JUylbe11.z;r1 Oal;ibi!l~l (A)

ihenyluretb,ane or p-Ohl.oro'benzylphe:l'lyJ.. Oarbinoi (B)

J?e:ro erit-composi tion o:t ·· $olvent~aolute m1:2etu.re

(l:tlaae. Die.gram)

Pe:roent•eomposition of Ul.'lknow:n mixtu:re (oa.lo~lat~d) ·

1.~96 .1.97:;

78.!5% 21.5%

57.8% 42.z(

J2~aio 1.972

6J.9$ :;6.1%

60.9 ± :;.lJ.t, ot the. phenylurethe.ne o:t: p-Chlorophenylbenzyl Qarb1nol (A)

39 .1 ± 3 • 1% of the phenyluretbane of p.Chlorobenzylphenyl Oe.:t-binol ( .13) .

·TAl3l.$ XV · ·. · : ·e(· ·;c::·•Mixture <it

· riv.at!ves of·. , 1· Oa.l'."b1no - A

Pe.roa"9t,~cr.~position of S;:lcohols;• p.Jhi:~r;p~e11.1l b.e~t?.tt carbine,l i p"'a.~:to.robenzylpllenyl ·oa.rb~olt

•. ! •. •

W'a1gh~i- :of ~olvent .:s, Weight ,ot· $oittf;e (.phenyluretban~ . d~t,vatl11e1i ct_ tlie . syn~b$1:t1¢

m1xttU-e- .or ~loo~ols),;

Lower, melting ... po:t~t o-f · '·aol:vent~sol~ u.te m~xtur-~;

Pe~ent.;;.qompos~ tion. (bt· Pbn,ef.}

d1_agra.m) Qt

Peroent-oompositiion (ca.loul~t.ed) Qtt-

~+,4%" 1ta·-- 6"' :.! l • 'i'

pr,yosco;e10, Anq.lysis .'0£ hed.uct~·on 'produgt.;q · ·· · · of_ 12::Metl1Ilst1lbene:·onde. -: · ·

,~e:ar;rations . o:r; siynp1 et\..... Tbe. 'µnknp~ ~~x~ure, sm· oi1i Qbt~iiled. 'froin ·the ied.uction; c>t ;p..,.met.hy1:st1l.-.

, ,,_ :i

than iit~sl:µng:, ;ritn tr~ter a..T1d dilut$ n'.tk~:ti.;- :~~M, ', ·;,; ·, . '

~a. eo.~~$nt,~t1ng the- pro-c:iuo.t" Thi:3 ~ef'erenoe at4oholµ .... ·, ·•·._;. . .

we~e -~yntl,{~si~e,a '.by ·tlf).e -Gr!~r4 moth:od. tn tho pase

o·t p,-~e,thy~phmiyl.benzyl,; carbtnol. ant :01: tpe, :r~a:ction ; • 1:

of: aty~eµe. .. ()~de •wit,.h p..methylphenyl 11 ,:;btum 1.l+ the :•, ,' . . .:_'. . . ' '' ~~:' ''· ;-,:

e.a~e ;&$\_).~-m~thyl.be:rizy-lpb.enyl. Ca:?tbin()l t ?_ti~:: ·a!laohol.a trare :;PUrit:Led. by .traotional d~stilla.tton t~rough a.

~ , ,

' . .. . ~' ' ' ' . . . . ' . , t'ltfo~toot qolum:n packed with. glass l;)eads :t;ollowe:d. by

s~~:r,;t; r.eoryatal1iz~t1ons :f't-<>m Skeq._:ty~olv~,;- ~t,;e

a.:tai)hi>i:ia oonsid<3red pur'11 ertougti to~ U$EJ ~h:e'!:i :r·:tve X-$cry~t$tl.l;za~.1on:s e9~oeasiv.el7 sb.ow~d. UQ' ·cJlange in melting;..pbint e.nd tb.13· carbon and byd.rqgen ,()ontt9nt

. '.,, . ' . •:

was within expe:rimantal error. Deta.ila as· 'ti() t..he quantities use<:tJ ·th~ yields ~btained a."!ct the: anaJ. ...

yti~e.J. data a.re given in the seotion Qn t;ynthe~J,.e Froc~d.ur~a.

A~oo.:ratus.-. All meitin5-poin~s w~e taken in a modified l3ecltna.:nn- eell \ti th a platinum :rt:!s1stanoe

thermometer,.. !rb.e design of the Beckman.VJ. cell is ·shown

1n D~~s;r~m o,. ·Tb.annal equllib~:tttm. ·~as .eat~b+-~sned

bf meMs or a. spiral~shaped glass stirri~!t i'Ocl. $.t-,_,

.·:- ' . ·,: . ' ts.ohed tc> a soft iron core, anc1 operated in, vert.1,otil . . . . : ~-. . . . . ': ~- '.

motion $1:i, :so- cycles .Pet- m1n-qte bf a ¢o1enqt'a.. ·~i,ed ..

t:o .a ~i~cµ,i.t breal';:el'~ Th.e d.1mens1Qna -~t Jn~ 'atirre~ W'ere .GU<)b. th.at it did not touoh the J3,1de~ of' .. the Beak ... . t .,· ·'... . ' . . ' . \ ., .. :,

ma.nn e.~l,.i ·:o'-.r th~ thel."'me>m,~ter so··tui 116 ~vo14 me.cllan..,. -:;·

ipal ~h,<>~lt ant\ ,h~at efr~ot~:i ·due ~o ~ric~i~::ti. ·. 4-, cal'!!' tbrat~ el~otl'ically b.e.at·ed. o~i_ pa.th was ,.uJ11ed; to o.on..,

.'. ·:, ··,:_ . .,_ . • 1,,. :·'-

t,;-ol. '1th.~ '~ate of heatlrtg w1t'.tdn o.,p;t Of 'j,e~,ntlnute o:r tb' ,;proper- adJustmeri:G or· th.Q two· ;Va~iaos ~oi.ifiecsted in .se~1o,~

The :Pla.tintlln resistor· tb.e,miom$tax, ,ras, ti!Ml'tl'fe.c• . . . . .•. . ~

. ;· ~-.

tured ::by the L~eds (;J.nd Northrup Oompany .(S~,r'itii: No.

683834) .and (?alibrated by the aurea.u of' Sta.nd.ards (N .. B~- a. 958}. fh.e t.o;tlowing Qonsta.nts were used#

steam point~ o:,; 0.00:392488, ~ul_fu:r p61-nt~ = ~ .•. 492. The resistance at o a. was, found to be e.l)proxifuatel;y-

2!:i-. 447 Absolute Ohi11Eh. ThEl ebangtr·.1n the rea1etsnee wa.a alm.ost e~ctly -o~ioo Ohm per degree Q. Tb,e tb.e:r-

momet·er its elf had a tour lea.d. oa.bl~ and .consisted

or a. ~yI"ex tuba 0.-7 om .• in •d1am$ter artd a:ppro,t1ma.te11,

46 cm. long. '?he sensi t1ve poJ't1on was about 2·:: om,:

long. All Jllea.su~ements were ma.de with a. ctt~rent of'

~hO m.tlli~pex-e~ tn ?Q~juno'(.iio1i fii;th a ·L$efl~ -~d

No:rthr.4» N:o.; 2~a4~d f3Jle as (falvon~et:~r "(1,~h .. ~, ·son~ .,,. 1 (; -. ,.

~-1 t1~£~t;'t?,; 9.05· UVf S.ild :a• :Qalibp.at~d :'Pf1$'. -9~2::.

MuGp~ Ilri'¾e (aer~a1 ~!>• 'ti!Q,.547),. ffi~;'~l•~~e,i; ~,t:,nt1:L..::--;ln absoiute 9~'31., '\d.'t,h the <:6nµn1.1,a.tor::.-i# tbe JYI~~rma±) pqs1tion¥ wei-¢ ·o,onv~rted, t~ ~esrees ·<l't by'i: ~:e,~ns 0£. the O~ll~nd,ap: eq~t1.ort; ~-· . . . .

Ji:~itine;4-poln~ prop:~ct®e .,and pr,egi~ton .·ot. measttre-.--;.:,:: ~ ..... i '.· '· . ;. ~,. • . . ' . ,. . . , • • ·: .. , ·. . -.• ,'. • • .. .

,e11tif'\1: '?be '~e:re:rred eoo11ng.-.our,t9~ o6tj~~ .not :!~e ... :-: . .. ' ' ;,,_ .

obt~1,P.~d :·l:>·ece.µ.se ~:r tb.e iwohounotd- tend.~n~t,d'~r- super• ~f oii~:>~¥ tad ·1#· tile 1<lQl!IE!l.'1tl p,.mijttri~i al ..

hohoia. /Iih~ sample was weighed by di:t:teren,ce ·a..i:reot.;;.-•.,_ _;,

ly 1nt_b thQ .Bec1trna.11n cell end melt.Gd 11?- ~ Oil bath

a.{· a.,.'·-t~~~ratu:re oniy: :;o.or · .. 4 .de~e~s , ol:>ov,~, ?e~Jl;fue1t~ 1ng.;.;point. 'ilhen th~ $t1rr:Lng beaem~·f la.bore« aa· the

~ample orystiallized, the voltage oont.rO:l. ·t:tas e1.djusted

iio a.a tt'f raise the temp~ratl:U."e at the raie :~f .. o.··01. to 0.07 Ch ,pe~· minute. ?he heating cu..YoVee,. an e~Ple o.r wh:~eh i,o glven 1:Q-Di,t).gxte.itt l>~ wo~e o6nst:rttcted by a- graph.- of rasiate.noe vs .. tim~.,

the meltins!-p01ntf.1 W\~>~e obtained. .from the beating-o.urvea at the :point or. interseoti~n-. \there the rate

ot h~tint{ ma.r.kedly cha.ng~d• The obange 1t:i th.a rate-

at heating tndica.ted the disappearance ot t:he solid

phase_! A visual ehaolt was ma.de) attar tho btetik .1n the curve appeared to be certain. ..~ mini.mum ot two

t11elti.ng~points were taken 011 any given a~plet) The averee;8 de'~1at1on n.e-ver exoeeded :to.,004 ob.ta

(to"o4~a41) and the .rnatimtun deviation .ne'iier exoeeo.ad io .• 00.1 ohm. (%.0.,07°00). Gene:cnll1J th$ a-verase dev1at1on WQS ±.0(1002 oh.ta (±0002°00) and the maa:1.luum. ±o.omi ohm (tt)oo2°o. ). One, #latnpl_e• in wlliob. the l!leltins.._

point ~at ta.ken without still'ittfh showed• tor six

dete~.adna.tiona; au average dov1atio.n ot t.. Oo 009 oh.rit

(1:.()~09°0.) and n aa:d . .n1wn ot ±t)~Ol8 ohm (:t.Oi,-l600t )o

:A,m?~t!4~ c,rz2J1q.q210, ,c,gn~~l~n.~I Ina . .! ,.,funotio.a

,o_r, .,t~~ ,tr;,,!e,7:i1At.~.nt. ~dep~e,P,a,i,qi1.i•-The malting J?Oint of pure p-.1.netb,ylphenylbenzyl ca:rb:tnol and tlie t.hl.'ee

ldxtures with ita iao.n1er as solute waa recorded in lJ.'ei.ble Vl From the data. a meltins--poirrt vs\') oompo0

aition ,)plot, Diagram :m, v,as construot;ed& A second

grapht> DieJ}rom Fa was conat~oted, 1n wl1ioh the

apparent cryoaoopio conntant 1 oaloUlated by mea,r.ts

ot .equation 8 ti'obl the data 1n. Diagrata. v and 1-eoorded w~ plo"eA _

in Table VI,"ega.1nst treezing•point depression. In Table VII wa:re 1teoorded the melt1.ug 1101uta ot

l'>tU·e p•m&thylb$nzylphenyl ca.rbinol ·Md th~ee tilintures with ite: isot1el'" as aolutee Diagram. Q was oonst:ruoted tl'O!Jl the duta in Teble VII& Diagram. tt was ootu3truoted

trom the data in Diagram G and reco~d,d 1.n Table VIII,. ~s we.E> done tor t;he: i-somerio oQ.m.pou.nd•:

q,r,:q~,o,opi_~-_ oo.n~ta11~ .ot,: t.r;1~~eil.¥~Wathaf¼tl• ~ • f • I

The cryosoopitl constant of t;i-1phe~l'W\athane was

datel"mi.ned with .P!"metbylphenylbeniyl ·Qarbinol a$)'

the stolute. :$quatlcn ll was ~sed.

(ll) x:r:, fll . 'Mx ~ Wa' •At$ . ' . .

1000 • "x

Kt$ =· or.10.scopic constant of triphenylmeth~e \Vs a w·eight ot t~1pll,n.ylmet·hane

Ats •· free~i.ng point depression of triphe.nyl-

methane

wx " weigl1t ot p-.methylphenylbenzyl carbinol

Hx •· moleQular. weigllt of p•.methylphenyl •

benzyl oarbinol

1he data was :t.'eoorded in Table IX.

Anallsis or_ t;het .reduction pr~duottro' ~- All

accurately wel~hed sample of the unknown mixture 1

W.ra.• was placed in the Beokmann oell,~d to this was added analytically pure p-Jn~thylphenyl.benzyl,"'oaittio~·•

WA, in large eno~h quantities to bring i;he.moAe fraotion of the solute be·tV1ee.n -o an4 0.06-. The

:treez.ing-pe:int depression was- determ.1.ned predisely as described a·bove. The apparent oryosoopic oon.-

stant was taken trom Diagram Eat the determined

freezing point depression. The data thus obtained were substi tut'ed, in equat10.t1. 9 to give the tot-al

nwnber ot moles ot all co,.ro.ponents exolusive or p•

methylphen_.vlberi.zyl carb1nol in -a one ara.rn/~ample ot the unknown . .mi:x:tur·e. To obtain the total nutnber

ot moles or all components in a one .g?am. _sample ot the mixture, the :t:reezing point depression of a dilute solution of the mixture in triphenrlvnethane was deter.mined and the proper values inserted in equation

1.. The peroent-compos1t1on ot p-.methylphenylbenzyl

oa.rbinol was then found be mea.ns ot equations 'J-7. The data for two ditterent sa.Jnples was summarized

in Table x. The same prooeduse was t9llowed for p•methylbenzylphenyl carbinol and the data.recorded

Jn Table XI.

Analysis ot tf1e synthetic m1xtu;:e. ~~,-i syn.•

thetio mixture or p•methylphenylbenzyl carb1nol1

and p-methylbenzylphenyl oarbinol, and p-.rnethyl

stilbene oxide-was prepared with approxiaately

the sw:ne composition as determined for the unknown

mixture, The synthetic .mixture was analyzed .in the

same manner as the unknown mixtue ana t;.D.e aaua

reco,:ded in Tables XII and XIII. Tlle total number ot moles ot all oomponenta, was, however. oalcU:lated rrom. the known moleoular weights and the weights ot sample used and recorded in '.table XIV.

.. sample no. . ,·

"·•n•.

II 1

II 2

# 3

iABLa V

ho Component s1stem Keltmg-poin1t Oompoaition., l>ata

We:1.gb:t_ Weight Molality· m.p. ot solvent S,R,l\ll~ ,ot , 'M,xtnre - go J: u.3t!,o;f grgmg iE&m~. degt~esO

' ·4.620 (>.2270 9.2314 ·es.vo ,.zo1 0.4084 o.2a;5e 65.41

V

7.301 o.4606 o.2971 65.04

Dle.P• de-pZ'£!:J,§1,2D d~Ws 0

l.61

:'l.'.90 2,,27

:-!ol•!f:1 tz .:.-.'.. · ... ·:i:~:o,oo t>,()800

'0.:0900 ·,0:.100---

'.\- ,::.:•·,·F(

·:t,-i120. \-}.

.::,.:0.1•0·

'.\i\~--~..,,.

_-;:<>~::200 °t).i22(). ·(h.240 .0,.26(}')

lt'~ .:. A-a /:--~.

·6to C--· . •·

o.5a o'.st o .• 66

o.v9 o.9a o.99 1.0.e

'1..sm 1.$6 1.61.

l.69 1.a,

l't <i'-60 6.50' 6.66· 6.6Q

,;·

:9·~5~:; ..,

6.6V

6-61?;: G~.~,:; 6.$'1

6.76

·¢i-~~

'7~03

~-~·20

* Da~11 obtatnecl tra llelt1ng~po1n:t; Com.poaitlo.ii Cune. ~1agram.·B.

~$.lll,ple n.o.

#4

# 5

# 6

TABLE VII '.rw~ Oom,ponen~ Systezit

Me).t~...,i;,o'-iii; Qomposi t_ion Data

We~t; s,2l!ent gram.a

7.945

8~'230

7.543

0 lll,•P• 45.64

mol., wst • 212-. 3

0 ••P• 67.31,

mol. -wgt.: 212.3

Weight Molalit7 solute solution grams

o._2oa2 0.1222

0.3154 o .• 1aos

0.3724 Q,2326

m.p.;of' m.p. de-,~1xture p~on degreesO deg:reea 0

44._'76 0;.88

44.26 l..38

43,78 1.as

T,ABLE VIII 4,pparent owooptc, Constant .. ot »-Methzl,benz7~ph§DIA.01~binoA*

Solute:

1101a1itz

0.0200 I

0.0400

0•0600

o.osoo .0.100.

0.-120 ·I" •

,•.-0.140

-0..160

o.1ao :e.:0.200

0.200

0.146

Q.~90 0.43p

0.680

0.,26 o,.sao _l,.03

1.20 1.37 ·~ .

,.25

7.a5 7~25 ,.,25

. '

7.3e-

7.4B ' .

'7.;61

7.70 s.04·

* l?ata obt.iined tx-om llc,1t1ng•potnt ~ompoa1t!on Ourve, Diagram o.

fABLE IX

Ottoscop1e.Constant.of Triphen,:lmethane ' , ' ,•, '•. . . . . '

Solut~:

llelting•potnt ot- tr1phenylmeth~e=

-~~1t111g-po1nt ot t:'l!'iphenylJnethane-solute· ~ixture

-93 s--0 ·c ' . .... ..

TABLE X

Reduction of p•Hethy;lstilbene Oxide cnosoop1c Data ot Unknown M1xtureg

Solv:entl

J4ol. wgt.

67.31° c. 21.2.3

Weight ot solvent (grams)•

Weight of solute (11Dknown IU.xture,, grams):

Kelttng-polnt of solvent-solute mixture (deg. 0~):

?4elt1ng-po1nt depression (deg. C.):

Molal1ty at treez1ng•po1Dt depression (see figure )t

Apparent oi,osoop1o constant at molality:

Peroent•compos1t1on of solvent 1n unknown mixture•

·Sample II 9

7.637

o.,3866

66.:J.8

1.1a

0.170

6.65.

25.0 1.'

Sample II 10

7.63'7

o.4991

65".97

1.~

0.19a

6.76

31.l

Aye:rag91 28.1 ± 3.lj of p•Methylphenylbenzyl carb1nol

Preo1s1gn; 11.0 parts per hundred

!l'ABLE XI

Reductlon .. ot,; p•Meth:yls tilbene. Oxide· 6noscop1c Data of' Unknown M1xtureg

. : ( '

M~P• 46.64° Kol. wgt. 212.:s

Weight ot': eolvent.,·.(grams) *· Weight_ot.·aolute (unknown

mixture,.· grams)

Me1t1ng•po!J.lt of solvent• solute mixture (deg.a •. ) a

Melt1ng•potnt depression (deg. c.) a·.·

Molal1ty·at treez1ng•po1nt depresa1on (see figure >•

Apparent oryosoop1c constant at Molalit7:

Percent•com.os1t1on•~t solvent 1n unkiiwon ,mixture,:

SQJJlpl& # 7

8.73&

Q.2990

44.9'7

0.67

0~009.2

7.26

~9.0

Sample #8

a •. o'7~ 0.4930

44.56

1.oa

0.0146

7.40

46 •. 0

Average: 42.0 ±3.o, ot. p•Methylbenzylphenyl · · oarbinol

Precision: 7.l parts per hundred

TABLE XI:t . .;.·

::~hree-Componen-t Hhture • .• • ••••" ,• • •'. I •:

Solvent.&

Composition ot solute• . r :i, p•Meth7~phen7lbona71-

oarb1nol ' p•Kethylbenaylphenyl · oarbinol

p•llethjlstllbene· ' oxide

\Ve~h~ of ~-~l.u te • --,_.

We~ght of solvent;

14elt1ng"!Opo1nt ot· solvent ... solute mixtures

Melting~point depressions

Molal1ty ·at ~-•P• Apparent oryosoop1o .

· constant· at molalityt '.· ,. •• • ! '

Peroent•oompos1tion of p-met~7lphen7lb~nzy~ carb1no·1-..experlmen~ ~l;

Errors par.ts per hunJl;x-ed

Sample II 12

0.0497 g. cas.&%> Oi.'0964 8• (49.'1,C)

0.0480 g, (24,V%)

0'~1941 tJ•

4.167 g. 66.19° o,

:z·:1.12° ,o. o.169

·tl-JU ·,,,

~2.'1-%

11.3

fABLE XIII ~hree Component Ml,xture

Solvents

Oompoe1t1on ot solute, p•MetbJlbenz7lphen7l

carbinol p•Mehtylphen7lbensql

carbinol p~Methylst11bene

oxide

Weight ot aolUtea Weight ot solvent:

Uelt1ng•po1nt ot·ao1vent• solute mi;ttur~ 1

Mclting•po1nt depression•

Mola.l1ty- at =•·P• I

Apparent cryaoaooplc constant at molal1tya

Percent composition ot p-llethylbenzylphenyl carb1nol•exper1memtal:

Error& parts per hundred&

46.64° c.

Sample# 11

0.199 S• (49.0%)

0.101 8• (26.0%) o.Q9'1 B•' { 26.0}()

o.38s S• ?.653 S• 44.~8° o.

o.9&0 o. o.i3o ,.31

., --145.;/

1'¥'L!:,XIV , , . p•Meth::,lst1lbene Oxide

Total Number o-r M9les of· All OOllU)QQehts -- in Reduction Products · ·

Wgt. ~f triphen7lmet~ane (solvent)i ·

Wgt., of solute (reduot'.ion products)

.•- I '. ., '

14 .. ,p., ot triphenylmethane (solv:e~t)-i

:.' \!'.:

M •. p .. , ot _solvent.•solute mixture .. ' :>1 ;_- . . !

' ),,;- " Kelt1ngfpo1nt depr. essioni .. j~ '

Total no•- ~i. moi'es .. of. all components., 1r1 one. gram samp);e of reduction products:

Average molecular weight o·t reducti'on pro'duots;

0~:400 g., 0

93.51 a.,

~o~s1° o •. 0 ,2.'70 c.,

'

,0.00458

218

30

. 2 0 z ::E -w 10 ::E ...

0

30

20 . z -~ .. IJJ 10 ::E -...

0

80 100

TEMP.,°C

120

HEATING CURVE: COMP.,34.Q 0 l~A

80 100

TE MP., °C

COOLING. CURVE COMP,; 70,0¾A

TIME - TEMPERATURE CURVES

-146-

PHENYLURETHA~ES OF P-CHLOROPHENYL-BENZYL CARBINOL (A} AND P-CHLORO-

BENZYLPHENYL CARBINOL (BL

Diagram k:

u 0

13 0

120

~ II 0 0 Q.

c., ZIOO .,_ ..J UJ :E

90

80

70 0 20

-147-

Diagram B

PHENYLURETHANES OF P-CHLOROPHENYLBENZYL CARBINOL (A)

AND P-CHLOR08EN2YLPHENYL CARBINOL (B) ------- ----r--- ----~~--------

40 60 80 1"00

WT. 0/. lA)

I J-1 ~ ...:J I

I ,,

14s

LJ

Diagram C

MELTING-POfNT APPARATUS

PLATINUM RESISTANCE THERMOMETER

(FOR THER MOOOUPLES

-148-

10 mm o.d~ SOFT IRON

S 29/42 MALE

It/

CORE

~---i I SOLENOID

r/ 29/42 FEMALE

"STIRRERJ 2 mm ROD ;

en ~ :c 0 ... l&I (,) z 4 I-en -en l&J a:

32-100

32.00 0

31.9 0 0

Diagra•m D

TIME -TEMPERATURE HEATING CURVE

I SOLVE NT: P-METHYLPHENYLBE NZYL CARBINOL

SOLUTE P-METHYLBENZYLPHENYL CAR BINOL

0

0

31.eo o5L-0 ________ 6.J......0 __________ 7L...o---------e..1.o ________ _.9-:o---

T IM E, MINUTES

I I-' IP-<O I

w a::: ::> I-X -~

LL 0

I-z -0 a.. (!) z I-.....J w ~

Dia.gram. E -150-68.0 0----------,.--------,--~-------,

67.00

66.00

65.00 O 0.100 0.2 00 MOLAL I TY

MELTING POINT - COMPOSITION CURVE

SOLVENT: P•METHYLPHENYLBENZYL CAAIINOL

SOLUTE: P·METHYLBENZYLPHENYL CARBIN"OL

0.300

► .... -..J 4 ..J 0 ~

0.260

o.,so

0.100

0-02 0

Dia ra•m F H

0

0

6-QO 6.40 6.80 7.20 7-60

APPARENT CRYOSCOPIC CONSTANT

P-METHYLPHENYLBENlYL CARBINOL (A)

P-METHYLBENZYLPHENYL CARBINOL (8)

-151-

8-0 0

-152-Dia.ram G

MEL TING POINT~ COMPOSITION CURVE

SOLVENT P·METH Y LBENZYLPHENYL CARBINOL 45.50 ---- ----

SOLUTE: P·METHYLPHENYLBENZYL CARBINOL

45,00 w a:: ::> r-)(

~

LL 0

r-z 44.50 -0

a. (!) z -r-....J w ~

44.00

0 0.100 0.200 0.300 MOLAL I TY

J2• :Mathylbenzzl Bxiomid~ . ,. . \' ,, ·. . .

The eanpou.nd. wns prepa.t'ed by a .sli@h t modlti• eat:ton of the. px•ooedure of Atkinson and '.tho~pe {254)• To 1000 mi, (8s1 ·g ... a·.;12 mole$) of p.;)qlene maintElin• ed at 1so0 t there was adde<i;p, cb:~opvrisG, 544 ml; (1710 g~·-, 1oi1 moles} of b~on1ine. The ... J;'eacrtion m:t.xttwa WAS re-: ; ' . .·· .

fl~d un&~r vacuum proouoed.· o)t a wate:t> pump tQ remoV"e ·~· .

dissolved 11,-d:r:aob~oniie acid. Diat1l1ation through 'a '15 om. -eolwnn l7aoked vd. th glas·s beads yteld$d ( l) unchanged p-~ylena, b.p. 32°/15 n-un, 35°/18 mm. ~re~•· ported (2G5h so0/s2 mm.l, (2) pil"'bromOJtylene, b~p. S4°/1s mm. (repo~ted (866.)i ~05.501755 mnl',),:, (3) p~ nwt}J1lb<,nz!l bromidef> trl.2 Eh (.411.5%)t b.p. ·t3f0/l3•f!JJll~';: 99°/is m;mf, 111°/2~ ~m•;, 114/>/2s mm • .,. 121C>/41 nun. (reported (S,6-4) * b;p.~ ~1a~20°/t40 mm.) Whioh ·cr1s,ta1~ lizecl on ata.nd:tng, m~p. 37.;ao (.tteportod ($84:)i m~p; 00°) tiAd ,_(4) the residue v1hioh oona.isted mostlt ot p•xy~1iane dibrarnide.

A yieid of 45 ;s% of p.-itlethylbenzyl b!"omide was obtained on r$peti tion of the exper:bnant •

Allraiitte potS:Qium permanganate ,oxida.t16n of

s~1 s~ (s.;12 moles)

712 g.;

(,3.:S5 moles} '1t, ~iel.d r: Moies, of p-met41ylber1Z,z:1 b~~~~,e ;1Q,<?, Wfo!ea of p-xylena,

:: s.as .• 100 = 47~5% - s.m · Redu.et101i ot ,P•tolu:i.e .acid_"

cl¢ I 4 . . , . .· ) .•

To 87 ;o .8• ( ll/1 mole$') ot finely grround lith.imn

8lurnirtUlll hjltl.:t>ide :tn 500-ml-.' of d:ried ethev,. iOO gl {0;735 ni.Qle) 1>f p..;toluie aoid tv~s added 1n srnUl pot>• tions.. Wt.ten the e.ctdi tion was c.omp1eted,., tl;le reactiO?;l mixture was ~yqroly.)Ced with. wate:iJ and 4,.lu.te h~Q~

oh1orio itcid. The ethej,'l laj1',;,r was aepara ted and the aqueous portion extracted· with freah.•A4:1olv~t; The ~orilb1n~ ether s oiutions were ,uulhed. .tuecessi-vefy vd.th wate:r, lo% sodium hydlto;ide aalution,. and wa.t~r• The ethel:I we.s dried over Drier!te and ooncentrated.. 'Jl:?.a residual was dis tilled to give r0;11,,1 g. of' ~ oil~.

b~p. 210..;.g_:o1731 mm.: The oil contained sonta. p.:mirthtl• benznldeh~~• The 2f4: .. dinitrophenyib.yfu;taione .defi•

va.tive, m~P• 2:,9 ... 240;5° ~- showed nc depwsaion 1n a

mt,c$d rl3$l t,~~1101t1t ~lth Utl an.~•n~ ••to• A ',i:~.·

cord t'l1r.u1tton W$.~ t>lli;11L-1eo~ 'b~P• )tt'l-4°/U ~u .. Pi ~eh o~~:l.tL!z:ed.~ Tb~- tae~ti'n$~Pt>lnt•t 4f'f»~ l'e~rotdl.~~ tio.n tiom $ffi~Ol.,: Wt.ill 6$~0~~~ (tePOi'~ f()t• ~~· ~~l. e·tbet · (1&7) • l),pi s.10~11°1;: m~p~ $1;~.s~i,;

A\\'-· .. a~~~ .~•1! o:A.dt18o• c~k ~~t~t 11.# e.02~ ~ ... ~ ...... .ill M 'i!Si:'! ''"" t'- -ff·. ·t'1J (,4.,_ ~~~-*" ·~J; ,Qi)._~,., .u;. ~."~"':

~..,1tf.lti.·•·.:".: ..... ···.~.1'm.' ,'.l.S.· ~. · · ~h..,~: · -.Q ~ • Jit <~.tft- ,,_ rt:-,~~-- . -~_!9.-~...,,.

'l'ttt··.'.· ·"'•-..,.rt~~.: .. ·4. W6 !: n .. ffn~~d b~ a.·•· $.l:"'"" .. lt --~.-'>P.1·,_ •£,l(a' Y~iiw\J~ .. "t •• ,il"~,_. · 'ii. · · . · ~ ·· J,tt.~;,f,,.4 ~ •

¢,a.t1¢.tt ~I ibt p~~~~ i>f llaM and itml$~ (26$) .-l1~tr•·twij ,$1"• <ii<>f ~le~r) of t.;:nJ~~p~()),ffi'i(IJ Vlflti -ded t(f a t/!Ulittt!tm ,¢ii -~'ii g, '(),JOO ~le) ot . _: ~. . ' ' . ·• .

to tl1fl ~az.m tedrrtbion. ~~e,. th~~ w~s added s:b a~ time 185 s~ (1.oo mo:t.e) ot P•fht:t~rl ~~de,-• 'U1.e ~ae~ton ~ttu.1e \'ffa£J:: ~U:t;1Wed tQ 1·tw.'li.

to'h 4.~ he®if., .. eatend~d ,,-!th. $thtr, w:~elloa w.iocias!W,¥ 11 with. ·wa~, lo$ $0d$U:tt.l h~~~!de, ~- \V~,te-ri'';;~ !bf i'ttl~r 410J.u:t4,¢n Wtl$ dti~d (tVS~ ~~1tt tUl4 ~®Q~ . ·. _. . ~ . . . . . ' ' :

izr4too,~, D1$tilltiitio». .Qt 'th$ le$14u4. t:>!1 thf'Ou.sh, ~ VG ¢m~· ¢":1urtin x,e.oka~. wtth glat13 be,att~ ¥.t:!a:t :riea"~ ',,. ,. 114;;1 s• (79,1%) ·"t _p .. ~tt1:r1h••l4thyd·f>.~-· ·t>••tJ.i:''$$~f:'jl :t;.$ $~, •. 99~3.020/~ lWi,t 2t4:~W;tt-Ql)l1tn.1l.~1tbit~~-·-

•·- , . ' ; . . ' '-~-

m.t, ,¥ 1139,;;~o;oo (!>&p:otsted (etm), n1i,,>~.s~£?54'.tlei),

semicarbason'1~- mi1:t~; Bl't(0-..2:.L'r;i• (i;~ported :(2~0) t.,

ni~.~-~ .• :~J5°·,, 2l9-~220~)ff,0

t ·y1e~, of iOi9% -~ 'p~~e:tbi~b•~e1d~h)'de watt "•J ·\. • ... • .

obtained -cm ttepettt!ti.n or,:~a" eJ:~:r:tanent~

185- "• ( . .. 0.

(1;:00 mole)

%. "aelcl.,;

. 0

"'B 'O rn l'1 • d~

( l~04 moi$~) ·94:;9· g.

{Oi191 .moles}

MtJl'e$: .ot. l!~'.metb.zlben~el.dehm·-·~-100 I

lfo1e$ 6f p~metliiioe,n~tvI bra:a~ ' = o;7sl J¢ ioo = 79;3$ 1.:00 · .

A o()?llmer6141 sample of p-msth:,lb~tldehyde;. ••p:ract:i(')al grade", was .tou.ntt to oonta:tn a lft,:-ge e.moun'b <>f tlie o~isome,;-~- ~~ 21 4-.d1nlt;;ophenylh.yd.t-a1h~1e

• • • ., ,!':, .. _.\r··:··'"·f:f

wasf reoryst~111J.ed $evera.l '.t~J from etb.~?1• m;l? •. l85-.itL5o (reported fo~ deriv-ati1Vf> (Ja71) m;p; 195¢; . . ' . . ' .

deri'7'4 tiv$ (2?1) m.p. 25~;5~~J,o.,f: 1!39~6 .. 240;$01 ··e39;0~. 40~5°). !Iha semiearbi:l$o:ne was rec~stall1te~ on.ee tr<111 ~~ol~ l!l~~:•· e.11.-12° (rep(Wted tor d~r;vative (S-1~l 111:•P~ ·21~0; tr/I! det'!vat1ve (a70) miPif ~15°,, 2l9t2t'>o ~ ·e:t7°) •· A~al.1%1$ h~ogei'l pe?io~id$

oxidation: of th&"~~e.hY4e,, y:teldecl. thG 'ttlu:7.e a.cid• m~P• a5~1Q0° (tiapor:t$d ~~ d$ri~at!v& (278) t m:ti~'c 102°1 fov der:tvat1V4't (~73) i m;pi 111<>) •·

'l"ne oolll!i$to~l p~$tb.ylbe1waldeh~e, so,-e$lle4,, was condensed with ·beM7llllagnes!um ¢hlo:r1d.e as· des otibed "hi the prep~a.t1on of p..,.mettey-lphe:nytben¢t1 ctu.,binol ot, le~~ A~ Pehyd.ration ot., th~ e~bmoij) as· 4.J1t:1cl;'ib,ed in t.ha prep~~tio>:1 ot►methyl$t:Ubane '.' .· : /·_:, ... ,._ C, . )·/

l)t,:rne.thod ~, gave ·,~\~ail. J.nlount ~£ p..\nethylstiibenei\. m:p, ·1,1,9.;20?· atd ~~~;ger amottnt :Of .a ¢0llWO~

m~lt~~ at 41-fflb (repo~ted ro,, me~Ut!lbene (229lt lll•;P, ieG~); ?:t't~pm7ation ot the pl'le)?-:r~w:-ethan~ cle1:>iva.tive e>f the oarbino:t GC.V~ a m;:p; of ;t.oe;5.:1,0S.il" (.reported tor der!ita.t:tve (21$) t 114;<>1.);

' ' : .- . eia;. Ct!-lod • .for g~2¾1N'2= a, 79.73%; H~ 6~3~k'

F9ttttd: o,. 7g;a27'; Hi· $;4.$%;, p.i:Meth,-lphen:rlb<3n$7l ca:tibinql

Method .A;• The etewd~d techniques for the ·pre .• , paration of a Gfigtlard reagent. wa~e used~ Tw't> ·hu~$d wi\. ' . ' ' ' $.nd th~t;y-"(sos s-:"• ~.oo moles) <?f redistil1ed benz.r1 · ~hioride was added to 48 ;a g ~; ·, ( 2 ;Oo moles) pt m~e$itinl tu.rn~s suspended in 2 l+r of aodiu.m dried ether~ 1i'he t'~aot;ie>n m.txtttite was alloi.ved to a tam tor $8V<r al. •' •

: ' . ·?· '

hou.ru~. To the ether ~olu.tiott,:<~e're. ·was addGd drt>P~

·w:i~e 1so 6 • t1;a moies) of f~$hl;t dit1t!1iea '-Q~. n1atb.ylb~n,ai¢~h:yne~;; A;'te~ several h~~).: the ~aotlpn ·m~~ \Tall i,i~iyt,ed, at P~loO~ With .~. $atwjated:; •Qniµnt, ch;u,r:ide $o1u.t:t.mt~ nie. ether so:r.uttpn W$.s s,epa1"a:~a ai1d tlie ttqu.aouti portion e~tt;-a<:ted vtith ~ther, 1be: c()mbined: efu~ tf.01'qttons

we~e .washed. auccess:t~l:r ·witli wate,.-.:, 1°"• sodium I' • .

. hydrb4Ciat,.,., and wate~ ~· 'lhe a.that-• was ~1$d over Drie~ :rlte an~ ~9l)o&nt1?a.t~d. /l'h~ ~e'Qidud. o;J.1, on dis• t~llatiPn through a sb.or:t v1grea'U!l( 09lU'llm1 , :y:tel,de~ 4, small e.mount of tt.1be~yl and 235 g., (7410%) ot

' ,!-"· ·" ..

Pimtth:,:;pJ:?,e~y1be~,.-1~ca:tJbino1, h;p; ;f.48° / l;$ Itmli,

orude ttltP~, ss.a~a8;2, :, . . A y:te:t9- of 80;5}( ·Qr p,.m~~:ylphetiylben~yl earb:tnol.

We.Et obta:iJJ.ed Qll ~epea.titi~ ot the e:tpeXi1m~:nti Po~ the. ,Put'po$~s 9f c~yoseopt.o anfiirs:ts, the

c~;z,bino:t wae rec.1,ti11e,4 through a. oo Qw.. column pa.9ked vrith g:J,.asa beads, and was then reery$ta11Ued. sev~~~$,l ~imes .fr<l1i Sk~ll.y O ~ finally from methanol.,'. The ch$]Se$ ,in ~l.;~ll!ipoint wer:e f'oilo~fllt ed bf means of the platiuwn t:1e:s$.atlini;,t th&l?l11QmeteX"• . . ; . , . ·. ,(., . .

Vfuon s add! tion~l ;,e,¢~yat$1.l:J.ization$ $)tQ\Ved n~, rise in. the m.p~, e'1;oa .. a11;'5lP, .the· $,ample was anal~ed

:tor 'etz.:rbon .en~ hydl:mgen; (3?$p6.rttted (1l74i~J:.5) 1tt;,,P, ts0 - 68~) t, .. . , j

~~~ct,_Caled~ to~ ~15lij,e<H (J~ ·S4~85%l Rt 7;'~ fcrt1ndt c;, 84~87%1-:11~ '7i60~~.

.253 g. (2;00 moles)

180 s-.-( 1;e,o mole$)

236 g ••

(li11 mole$) ~- Yield = -~~oles. ·pt ·>2_~~e-1t,en~lhe~:Jl.c~J?.:!:Pzof ,c. 100 llolea o? p'"1ne -· I . enza!ae-n · .. e .. . .. . '

.: 1;u·x 100 ,74;01' "" " i.ob ·" = . Phenylu:retha.ne der!tvat:i:ve;~~ ~xture of 34;6 ~;

(O :.:ta$ mole) of p-methylp~e~ylb':n$fl ~a:rb!nol pre-pru?ed b7 Met.hoc! A and 18 tnl •• (0.,155 mole) t>f rec11s·• tliled phE>l;iYl :taoc~te vt$re waximed on a ste~m ha.th fo:r l hO't.W~~ Th~ oil c:rystal1is~d on standing.'1 ~e ,, ,,.

·, ' !

solid waa trit\u:'ated und.er S~eily O to l'emO'tJ'f;. the unchanged is OQfAAt te ;, dis s oved in _ ,o&rbOl;l t_~ waonlo:r~~ e • e.nd filtel?ed to r~move any diphen:ylurea. The

; : I '(· •

so1ven t was relllOted and 42 .;o- s • · (84 .:0%) of the ,. . ,• ...

~etl::Le.ne, r:eopv~~d. Th~ produot was reocystaU~~ .from. Skelly O a.nd from ethanol,. lll~P• +14.;S-115~)3()'

(reported {2JJ5): m.~'.!).,_ 114°). A :t,ield 0£ oo,~'0% was ob~ined on l'Opeti tion tne.

oxpe~ilnan~ w:tth ;leJ.1ger.' qua.\jt:tti(',tt of. the e~btno!t. ~;:. Qal¢tl;,_tor, '-%u; ~21M02l a, 't9;73J ll~ G;39%~

Fottnti; o,.,'19;;92.%• x, 6~'22%~ Metb.od .B ;. 1.1:ne usu.al te·caniqttes: tox• the pl"epara~

tio!l osr a Gr:Lghal".Q. -:reagent ive~e ompJ~oyed. One· hund.~ed iulct f:tt1;y.e!g.~t ml. (219 g._,; 1.ea mol~t) of p-b~OJnoi-, .· . . ·,,_ . ·' :

tol~e 11as .added {Wopw:t.se ta 3.116 g, (l.;3 moles) t:Jt .· . . .

ether~.- Tb.tr l'oaet:ton ni:tx.tupe ,1a.s allowed to stand trill ·an ho~. t.{lo ~e· e.iz:tet s'Q:+1,1tion;- the.re ,vaa ll-ddeq

140 tnl. ( 143 s.,, '1~10 moles i tJ:t freshi,- dis till~d phen7laoefa1i<1eh1U~f Af,t;ei~ -~~Y~ts.1 hou'.!;"s.~ the ~eaeticm mixture \Ve.s V/OZ'ked ·up aa ¢lel;l¢rlbe'd :tn Method A; . ', .

Dist;;uat,io¼4 ot · the o!l. •y!eldei as.a g_ •. (2ltl1&) o:r p-methfipheny.i~enzii cdoinOlj m~P•~ after severe.i 1-ecrystaii:t.zat;tona,_, se;5-.67.:a0,.. ~e phenyl~~-th~n.e derivative w~ prepar~d., a,s deso:ribed .in Meth~ A,, .m.p. artax- ~evera.1 recr:vsta.J.luat1.qns i"rom Skelly' .a·;, 109;$-:t4;;2o• A *ed melting point: With tb$

au. thenf:tc ana;y-tieally pu:re phentlu.t"ethane . ~hovtt3cl. no c1epros·sion;.,

r,-,~ .. ' ' (1) ""~ \, .',-c..~.,c.."o + "k,tG\.,.a. ... -"> l"i-;\ h . \.:.t 'C:11 r ,, ' '-C.M ._...~ - ~ '• . '}-C-\\2 -- · Q-, \.\ I;() .::,_I · O\f \::;_,I ->-

l4S g ia: Si9- $•; 55:,8 th (J...~9. molet) (i~28 mo1e·~_:y (Q~~P~)

%: Yield ~• ;~~::. :} .. ~£=-~~~ffl;t~zl. -~binfll. '5 100 ~ . ' , .

110 th.od . AZ '!he standard te¢hniqueAr :eoi" the ...... · ·. f .,·

preparation of Grigna:rd tea~nt were USet4 with th• ~1J~c:tpt!o11 that El. t~ntaiu.m \v1,:.o- .llirtu1'berg. stirrer wali &npioyed~ Ono bun~cl and td.x.ty..,se.ven S•. (9;·9~5 mo.le) c;>f ))-meteyl~ent71 ·bromide dissolv&~ in ~oo ~• of sOdi,nn dri~-- ethe~ t1as added l'apidJ..T to @.;(l _g;. lo .;.906 n10l$} gt mag11es.iunt in.u'n!J:)g$ $US pe:nded ±Q. l J5·

.. - . . . . ~ ...

:t,. ot e~e:.r co.olect b. an. ice, -wa.tert. an.fl s~tr-bitth.. ~ . .

T('r tlie l'~~tioti m1Xtu.re1, the~e :"4$ added ~0:.,·5. ml,

(9~3'~Q ,Sf ·o~.s~ ~oles.) -of! freshl:t o.~t.1ll~d. benis.ld,e•• hycto cl!$~01vea :1n soo m.1. Q.:C ~ ther; M1;ex- severol.. liotµi~'i the ~eaeti9n ~tu.re ,ras ,i.1.Qll~od up a~ deacti.ib .... ,.,

ed -~- the p.ti$pa,ratiQ?i of itte: iSQmeri

_.Addition -()f methanol to the ±-e$1dual 011. ca.us~ . -. :-•· ...

pl~d:iinethyld!phentlethane.~ Wh:f.o:h. We.$- ~0t:1$t8.11Ue4 ·. se,te~al times from ·nietn.anol• :m~p;. Sl;4~8$ ;·4:o: {~~

' . . ~ .. .

ported {275} : m,P,

Ana~~ 9alcdt .tor qi~lt3 a~ 9_1~,$7% tt,; s;6~~; Fottnd# q, 9l;Oo%J lI, 8~$~%.:

Removai oi" the m~thanol and distillation ot the re$ !clua.~ ,01i yi~~ded U.YLQli~ed ben~a1deh~rd~1 bip;· s26/2;1 n1m •• 42.'.5°/o;9 mi11t (repor,ted, (27:1)' biP~ 17~()} .e;t,td -2'7.i? s~ i;l:t: a J1igb;e~ b<tilftlg fraction,-· b~P•- 110~113◊ (0,03$ mm~).. Addition of $kel;l.1' Q

•. •"· . . .

to tha latter traction cauaed the- separation 'Qf

p~1iletl1yl'ben;z7lpheny:t. ketbJ:le \'tl'l1ch Wa~f feoeya~ai~.U• ed sttv\1ral tinies · from. 8k¢tlly o, m;p.i: 95 ;S-.97 ;5P~ 'l'h.e sanrple t..1ttis obtained., vi.hen m1Xed ,11th nn authentic $pecimen er the ketone,__ shQWed no ¢1 cprest:J:ton in th.~ . . ll"Al ting point~

Removal ot the Skelly C fielded 2.0;~ g~_

(iO .;7$) of p...:mathyl.benzylphenyl cat'binol \'.\thteh was ' . ' ' . . ~ ..

ret?rys t,11;tEJd s,eve~al times from Skel.1:r A._ nt~iJ. 44;_5,-46;20.

Anal. Oalcd. for c1~R1'-lot C.; ';e4;85$; II. 7:etr; ~ · ·• v o "' · 'I" .,

Found: C• 8~;69$; ~-- 7.SO,t.;, A yield ot 68 ;·~% of E>;ytn .,,;p ,.Pr "'6.:tphe1171.

clipneeylethane;- b~p. ,_1oe~ ('0;2.0 mm~l,: was. obtained

·(o.sos mole) (Q . .:.esi, xno~<f>) .CO,QQ~2)

% Yield--•· Mo1eti jsf fi~t1o·t11~ibentzit:h~;:z:i::. }~t¢b,ino~i -x .. ·100 · tlo1e$ · of e1_1Zal~~e\ .. · · · ( \' · :.• · · · ·

• 0.0962 X. 100 s 10.'Yf'fo - ~- ·'r:i:i;J!~'"~· . ' . "

Ph~£'Y;l,Ufe ~1la,ne .~;~~~v;'f\ ~ve ~:--· m:te ))hen~l:uva th~e <;>f p~m¢·thflben8;J'lphe~i c~~inpl ··was pr$~~-<! as dasei·1bed in the p:r~~ara t1on t:it its isomer, ·iJne l!telt~_-po:!,nt,. ~Gel?J'St$.llizat1on ,tom. Sk,_t,~~ o,. •asii' 9° ··o.:9s :·sQ. v•. · .. -~ . . I

tu 500 m~! ot· £Jodit1111 d!ried ethe~ ·t,a~ adcietl'f t:tto~ise,, to lS;a 1£1r (a.;2G .moles) t>t· lithium. $b.t,t ~.u.ape~ed . . . ' . . . {

ad s.n an: :toet tte.ter ~-,.<:1 eal t ba'.bh ttld .!15 ml, (:;:eo s¥, 1;00 mole) .of' i'1"eahly tits t~J.led $ ey~~ne «cit1e, bf Pf 1e0/10 11t'.ll~•~ added ;tlr-opwis-e1: .A.fter sevef'-al hOtt,r$.~ 'the reac:t1on m1xtu.t'~ waa }.i'V".1~011ze.d. · nn4. w~kec:\. up e;s p.reti<rut~r dese.t"ibed: rw~ Gx-~Zit ~~~ct:t.ona •.

!Jlle 0;1.:r wan .dist:!lle-d thro~ a ano:t:it ·v!zre~ ,•

coitt.mn., Wt~t>e 1:as 011t:ait1.ed 103;6 g;. (48*8%} 61 .. ;·~ .. :• ._. _. .. '. . .. ' ' : . : . . . . . . : '. ' ' . '. '

»~metltflb~nty;phe~t ea,;r'b:tndit b ;p 129° (6;~2$ :nmi) t: ~ructi; '.{ii;Pr 40.;0--45 ;2°~ ph~"1flt:Wat.b.Sll':'l. atte,t'i re.;; cey-~t~i1~~~J$.nn frQJfJ.-methM4l,m~P• gs;e..,:;100~-~0 ~ A

i1.: .

~ed tnelt!:pg.;poittt w:tth an ~uthent:to sttii-ipie or the p'.l,1enylttrE1th.sne,- prep~ect ~s in Ma·choc.1. A,. sh~ve;d :no ,dep~es s1on.

A y!elr1 ·ot 6G;l,( -vt~s obta.1~tt.ld 011 p:rapara.t;to:n,_ i:>f th~ oarb!ln$l ~tro;ttng w;ttn 3;0 mole ot f..Ji.zytir,na ox'ida.,

fo:;.,. iifue puz.po$es qf cfy()~oop1c anal7!'td.$~ tito ¢.~b.:tnol i.VB.$ ~edistil..l~4 thl"O~h a !30 -•Pltl\!l <>Olumn p.s.qkod w:tth gless be$.d.$ ahd ;ceorys,t~;J.i2;tl& .seve:i:-al: . . ·,.- . . .

ti.man rrom Sltelly A.; ~1e. ch~T¼ge!t, in the' n1el tin.g~ poirit 1:ve~~ . f.ollovred by :me~i.,:ii o'.C ti).q p:Llltin~ .. tesi'a, tun~~t ihefl,tio.'ilete»-~, V~t~n .ft·ve add:t.tto~l ~aecystal.~ :t1zat.:t..or.Jf $n;OW$d no r:ts~ ~'1-. ,th~, mel:ting~po4nt ot •15 .ealllt,

;...,;!5 ;.G4-p, iP..~ s ejnpJ.~, was ~h.al;r?-ed 1' o~ cal'bon: e.~<1 11~-rch'-ozeri •.

';. y' '

120 g.

{1~00 ~oi~s) 1,8i'/ g;

(1;09 -moies}

~ .. eno J>X .

·,.• 0 .4S8 X iOO : 4t8;a,t . -L1J0--- .. . ...

ll""lle t.i1.;rl.ph~n1lbenzrl ·ketone ~

:t.ot;e g.

(o.'.4aa mol¢)

Metb.od A.,-. Fl-om a m.t.ictw.-ie t>:f" so,:o th (0~141 ...... ""' ·,·· ~.-, ..

mol.e) ·9£ enrbinol, ~a;a _ g~ (o.141 m.ole) c,i' &luminu,,n

i~H,propo.1;:ide nnd :too ml~ of . oyclo11ezanone, WEil'Dlerl

in a ws:ter ~a.th _tor ;a hou.:r·$ at 6o~ao0 • there was

obtained 2s.2 g. (ao~·o%) of tb.e ketonEl,: crude m.p;;

1ort~2-111;0° • U.he product~ reon-s tallized folll." times , .. ·{ . .

from methanol, tn];, . ..,,,,;, )9;2;110+86, on dupl.ica.ta o.t1alj$.!.t . . > }'.:t-: . .• . . . . . ga.ve low :results i'oli carbon. :F1, ve add~tiona:~ :re-cry!' Eitallizations ga1re a pro4uet, in.p. J.09~:11'.;11o;ao which:

¢n duPl1cate e.na1~1s :tndieated high r.e$u.ltit f~ . .

o~bon._ t.l'he semie~buone fas pr$paJ:1eet b;r the methQtl.,. . . ' . . ,· __ ..

of Shriner and :Fu.Bon;. ettude m!p.; 164;g..;3.55;ao~. ~e~ crystallized. f~om lrl~thanol, m;p. 170--17:1.8 (z,epo1')t0d

tor the s~~oa,rb~Z02:t8 (~76).,,Ine}?'!I l5$;9(),. f<JXi the ltetatine (~76)~ m~p. 172•173°-l•:

!lhe «xid().,,t1a$ prepared. bf the method t>f Shrbla~ and Fu.son (26Gb) c~ude m-P~ 96~Q..;98;5°:, wlito~. ®

a ta.nt'iin,s l"e.verted to a, more s tabl~ t<Wttl, m.;p ~ 127 ;o..-l.3l ;Ot'.l, Wbe. ~;,cilzte wa.a reocy8ta1J.:t~ed 0110$ f1J<>ttt methanol, m •P • 128 i(}~130 .•50 ( :reportec! {277,.278) :. m;p., 131 °, 150..;131◊) •

50!0 g~

(0;141 mole) 16.;9 8• (o.;oaos molel

~ Yield i!e li()lea . Of ◄E•niethyl~het\;y:J.benszl . k~,t,onc X !9.£:.· Moles o:t p•meffiy J?lieny).oem.yI oar'6Iiio:f · ·. f!.. 0 .0805 .:t 100 ... 57; 'tel . . ·0.1.~r . . - . J.//1

Method n; .. A mixture of 30.0 s~ (0;141 mole) p~111ethylpheeylben$yl e@binol and 28~8 g. (0.141 mole)

pt al.uminum..i$Qpr.o}?ot:1de •±u 150 ml-,. ot m,.ethyl'·eifhtfl 1tetone}1ta dried ~efl,~ed fotJ 35 hours, h~oly~ed with ·wa,.te1, and. J:1ydroohlo!!'ta $10'4,- ~nµ ~~'tct~d with ethol"i: .The ether was. dt-!ec. over D»:ies.11-te ~d ·oon.•

. . . ·_';,,'.•.::··;:,:·:.. ,: I,' . . •. ·· . ·: . . . .' .. • ',.,,. :_· ' .. · !' ! : :,-· ~'?tt~~Jte~., A y;J.e:t.d of· ;!.~:, ~i (e':(;1$\0 yt~s pbtaine4," m,P·•~, &ifte:¢ ~eceystail1$a'l?io~.f1J~ ~i;h~r,1,.,):.09;6• .lll:,:1° tr,pox-'t~d (~9i280i<~l~) m;pi l08~110c, a m.~·p; 1:to'\ ,m;p; 107 ;;s·(j.) ~

Ana;.: c~QQ. tor c19:e:14e, Pl-as;esi, n., a;71%. 1ottn.a: e1,. as:a47'J a, e;4~%;

~~1!$.thzlb,$ti~zl@$Ql,, Jt:e t¢n,&,, .!~thod ._Ai, A ~~ 9f,. 1s.:1: g; (o.0915 , mola) pf .~•Xll&1phyl'benia:y-i-pheeyl c~bin.t:>l and 1a;s g. (o.;0915 l'Jlqle) of ~luntlnum :tsopropxide in 100 ml~ of dt.ied. methyl ethyl k;et$11~

wa.s refl:u.:ned tor 35 hout.f}~, ·TJ.te )leaetion niixtttt"e yras

hydr◊lrted with w~ter and hydl?oeb.lorie $0:td,. ·'?4~ ~queous portill'tl. wa.s ~tttr,aoted wJ;bh ether and the ether washed With water, !he' ·solution was dl.1:1ed ,•· '' _. . . . .. , , ,· ,, -. . . . '• ' ,·.

(>'~er J?,iex-~ts t;md <:ioncentrated• ~~--' :re~idu.al tttl, 5~6 S•· (29;()%),,_ '~ras: difl.soive~ 'tr. mef.b.11no1, ~ee.4~; ~ l'i1lo:r-y1rtall1z&d. ft-on1 ~th:inol . .,. m.p. 95~3.;gf•s·<> lrepot-ted (et78), m~p,;., 94°t;: \~en tnixed with tht

-~ i'

ketone obtained in ti?,e P7:el)arati6n of P•methyJ.'befulyl..,, phenyl carbtno~., lll•i.?~ 99.¥s.=97.;5<>• the ~!ting~po~t

$hOlJied· no deprrJ'a1;1'ion~ . .

Ana~~, Cl}ied. f:o2i '9is~:;.it'lt a, 85 ;,S6%i H, 6~~3$ Found.: :or ss tt6%t lti ·eiee~i.

tIEt~h9d c •. ~ ire, 19;';.l g.;; (1;45 moie) ot e.l.ur:11nun1 ~hlot-ide suspended bl. 200 m1. of to1u,ene,·. th.el:'$ ,vaa - . . . ' . '..

f).cidecl lOO .s~ (O;eaQ mol,e) of phenaoyl chle>I>ide dis .. ,. . . ., ., ,, ,·

$ol,wd ~ 300 Xt11, ~t toluene, The r~~etion m:i;t~

was retl:o.xect for l.f$ ~®rs a.;pd then h~ol:r~ed with c~aoked. ioa &'ld Qoneen tra ted. hydz,o0h~or1e acid;

I ' : ~ . • ." • • ••

Th~ tt>1ue11t $olu.t1on was separated an-l dried bf ~$6t.itop1~ die tillatiQn., 'lhe r,erd.d.u~l QU waa diat1lled t11rcn1sh tJ. small :v1grewf ·column end ,re~ distilled througl.1. .t\ 60 Cin. ooiunrn P,ok~d with Sl~~$ bead$ yield.:tng ;t.6;4 g~ (12;~)~ ot ·ti. lllt,tt'Ure 'f):t ~.~

ducts,. b.-p. l39~140Q /38 1nm.,, crude rn,p~ 78;o;a11 ;oo,:

-1s9..;· tJ.we1vG racristalliz~tions from ~thanol. :raised tlie mel~il=is~p9mt to, 9a;s.$)9.;0°~. ~is ·~ampl$.:t· When: mtzad with an au.~ent:t¢)· ann1:pl~ of the p4methtlbfinz:r:i.•· . ' ' . . . ~ ..

.. phenyi ketone (m.;p,f.\ 95.;8•W.;56)., $.h();Ved tit :~is~JLfirjt

do~esa:tonJ: ~d m.,p .. ~. ~5;6--94.;69.~ 'lb,$. p;i;-o4~~t: is ev~~o.en tly .~ \ e::-!so:ra:e:r ot p7meth;rlb~~lph~n,.i+ keton.a\t. B~,- the srune p~oceciure, Stl:'se:teclta (2Sl)

' '; : # ' • '

rept>:t-t~4: 1i ·produot which me:fted ti.t 57° and Collet (~$2).. ~;ported tt rnelting~pi1it1.t ~f 84~tl; "/1::. 1ll$i:hzlsti19ene .:.

l,t~thod A •. ~ The uau.e,l:i techrt1quei £or the prepare.• tton or a die.~oni.'Cilli so.1 t were employed. A solution

. ·! . ~

o:t 160 g; (2~00 moles) of sod1'11? nitr:tte in 30-J ml. o:r water was added to 2i4 g. (2;00 moles) ot P• to1uid:the in 400 mi, of water ~nd 600 mi. of oonc·• hyd:roehloi'ie ~Cid cooled to ot>; To the didotiit,a. solution. there wq added l 1. ot dio;a.'l'le,. 440 g.11 (3~24 moles) of sodium acetate and 85.;0 S•· (0,500 n101e) of oupriq chio3::i.(1e., Tq the cold solu.tioni 1h&rs

was n9w add~, 148 g~ ( i;oo mole) ◊f 01nnnn.i1e tt<~id.~

4ne :re~otion mu.ture was e.llowec:1 to stand over.night vfith s ti~l:'1ng at room tempera.w-11e. The oil which

' formed was seJ?a»ated and 'the aq;u.eou1 portion ejttraat .. ed wi tn a tha.t-4t. The. ·•11ten:;:iand oU ,,ere combined and

lHi.sne<l. ;ru.9cess1.:vel1 wtth· wateX'ji, ditu.te b,a~o¢i1lo!t'1C e.c1di1; ~~tci:,:,~·ced ·atidiufu bia~1>onate :itoititi<m•• in% $Qci:1ulii·;li~t~:tde eoi,tttion, ~,;.a f:tnaJJ;~ 'id.th sa~a:t-

~ ' '."· ·.

ed0 ~,dti:tura ohlotiide · solu:tiort~ '-ih~ ~ffl:1eSt vrarr dried ove).-. Driiatiite and. .. __ ottnoantrii:t;ed~. ~t, i"a$id.tml . 911. Qµ distillation :r!elci~tl ~.,, ot1:r :~Qiid, 'b;p·. 212~22a<> /38 timlhWhieli on 1~tl~t~i:bzt4.tit>n fr·orn ethaiiol. gav$ ss:o 5~- (28;81l of p-me;th;:tsti:tbene, m~P•• 1.isfi'\121°, A m~ed 1neltin$~poi\1:t 11110itli p~mo~:,lr.l'tilbe:ne eibte.b~ .. . ··•.,. . .

e<i hy dehyetra ti(lll' ()~. P•IUG t11ilphet11l'ben~l car~in61 shtRt~d tlP dePi~t-$S1Un~

..... .. A yield. of :?0•0% ~it .P•nlethyl.$tilbeno was obtain•

ed ·bn, repe'ltit:J.on of tne j,cpal~iment Urider ~pprox:Unately th$ $SIA~ ooncU;t:i.o)lS, Th~- p~ijeedur~ pf ¥~~meinj : . ,. ., ' . .

Bu~er and. van Ems~~ (228.~ {repoptedi 48i8% ?ield) aild 'tit B$rgmani1 an! Shap~·c> (S29) (teporte<it 40·~0% "!' _..:!.' ~ • 1 , ,'·' • ,.. •. '-:.;.-;· ..

yie1d:~;·m;:P ~. l,SOO) ga~ lower tt,eJ.d,tt than teportea, p~e.I,l vttttia t.tons #n the oond:t tl<>ns of· the e;tpe)?tm~ t such. as a' cha:nge in the- mol~ z.at1o··Qf 1:nt res.otanttJ

-·· c,tr the s 41 'V~nt,;. showed 111:tghtl:r iower yieldn pf

. ·t ', i, ', ,',

P•~th:rl~til'bene" :tn. sever41l e~pep:tments, 30;$.: '.,· • ' ; :•,- • . ' . ·•• .. ·!

76 ;5;,& of the oinna.mio acid Was ttecovered from the : ' . . ,.. ' . •· ..

a.Odium bioaJ."bonate extraetaf in one ~xpe,l?1.lnant1 ~7,i5% ~ , . .' :

-f,f p ... en10±1ot-Ail:µ.en~- \\rius :tao:tated,) l)·.;,p.; 1sa~a~ft3S mm~: µl.i& i'de1:ttiey· W$.S ~sta'blJ~:b.~d ~1' ();d.dntton to P•qhlo~o-be11~r,io, a,:,id,. m;:pft. 23$J~i4~0 (:uepo:rted (2"12) i m~~P-•,:

'\}:

~ ,several e:tpe~1-me1:·ts • -~ £¥eid,. ai~'11ned.~:t:o bt. $.. dW:rlae~l:l.¢ ~¢inf v,~ iti?l,ateo !'rem· tt1t1. ~M~um b.yq~~itl~ ~W~4'ts. ,t.-s..'P~~-,g iti1 ~l.cl.a t~om 23;5· tit;

~ . ' . ' , . . ... . . . .. ' .. . . ' ' . .. ,

~s;o%', .. · reO:ri[$_~1tte.it .. f~®l-~qtt~ott.~ tneth«n:ol, m;.-p; ' . '.. . .. , ': . ,·· . .. . .. '• ., .

l7Sf8-.;~7~iQ~.. »e9,a.t~"'-V+at:tbn bt he~t .1!,1$:tderl lJe:n$~1e.eb:3'J~. ~e 1de~ t1ty.- ·,-f the • alt't:ehida .w~a ' ' , . 'c. •·• ; . . . '

Pl,,?~d ht,~+e.,,:ir-11~'.f),xr~tttou ·Qt Ut~ se.m:te~b~~one aM: a, ·~cl 111,eJ.tiµg po~it Wittl. Jt'4 gu:tJ:H·nti;ie- $1)8¢~821 • ' •• • :•:• • ' • , I • , ,",' •.' / \.' '. • ,,,) • •

4:r. Jihe ,d1;1~iyS;tlveiti. D(i;q·ar'.1')~1fxt~cm. of .ttte .a~:td : .• ', , • .. a,' ·' ~

b~ :moruts of ooppe~ •f:Uld qubr:>;t~t;ne yJa:tded: a twQdu~t* ~Q)?ably st;,yi-,e1:U',.• 'b;p;, :;i()9/9~5 mm. (repoxite~ {272) t

b;·p., 5'3°/10 tmn •. , which ~i~ a poait1v$ -teat to:r -µ.nsa·tu.ration'with bol.'llline in carbon tEJeyaohlo,t\iae •.

' .~ . .

!Ille· ;prodtt ()'ta of thfJ a.eearb¢tY'1a tion were not ttJ.r.tlle:r .ed. ~n tiA< ,p,1r ... .i:I .., .i.. "' J..4,,-"~•

148 S• , .

( 1.;,00 mpl(:i} 1¾14 ~-~

(a.oo·mesl ' ''· . ' " ·~

56''0 · .. ' ..• ' e;. to ~~sa m<'>l{;))

·jethQtl:, B.~ p.:Meihy;!pheny-lb®A?Jyl . ea:v-btno:t we.a . , .. · .. ·.•, . . ,. . . ,'•

added to·~ ij'Ul.¥1a acid ('b)t vol•)~- r~tltt1ted t¢t:, .~evex-~l, ll,t\~if;' · 'lbs reantipn mizXttu.'ie· wa$ ~ooled., e:i:teniteti' with wa~:6· Anet sxtrr.uita4• wt th .. be~ene. !l.ltt j.oivexit tfa~ retnov$d and th$ .P~e thy.1$ ttiberie ;-eo17~-

. :,;i,iail~ed from $th«no.i , .. m.p ,,, ll~;~.;;:1.$;60 (~~pottted cs14;229 aas}: m~p. 111°-, .~001, 110.;so~:moo) • n-_ Meth:l:htllbfine . o,tid.e;. -;~ .. •' . ,~. j' .t al. • . .· ' •.•- ·•·•· .

Perben$oic s.oid~... 'thl::l procedure of Titf'+';meiu-. .., , . ·••_ilr~"""' l J It -~'- . · .

and tf!IVY {~12) Wal$ W3ed with slight mod1:f"tcatton. . . . . .

T~· a so.l:utton o:t 10~4 gl (0:4~~ .mol~) of fl'eahlr cU:t sod:tu.m diaso.lved in 200 nil. ·ct absolute methan_--· ol . . ' ''• •, . . . . . ' - . . . . . . . , .

a:tf ~ 0 ,, a so1u.t:ton ot 100 g.; (0~4l.3 m~l~) of henzo7l . ' .~ . ' .~ '.

peroxide :4l. 400 ml• of dr~ chlor-oro:t-m at ti' v1a~ added slowly and. With sl?,ak:f.ng 1ffhile; 1ile' 1»mp$l?atu.t-e wru, kept av .-50" to, o0 • ·'lb~ l;'eact:l.Ol\ ~~ tilt$ quickly ~t:eac~d tw1¢$ with t1. total. of 1()()0 llll~ of WA~~

!' ,··

w~th ~ tote;:I. t?t 400 ml,. 9t fee-001<1. chlo,roi\)~l To. ihe aquegus stiltttion, t:here· :this added 450 ml; of' l l~

$u1Mi,~-::ttc:tc\j, e6'.olo{! tt> o-t?, ~i· ·µi~V · wit:!.~: iJ+'i1hitri1tS:~c: , ,-,·, .. · ,'- .·._ .

~d .\Vas -~ni'iae~.cr t..~~ titl~~ wi,i;tia· uo~ Qf $r)o~®o·,·i ~ . .· . . ;'•.' - ,•; ! . , ,· '

-':mli<ttd' '.chlo~I:>ftiX'dt~ ~4t;r,;d:ii}:r~/Q~,:~elease(} iodine vf':Lti'i s6d:t\im ;ruhiOStt1fat$ ,·indic.;;t.ted /f{:y;t.elti. of 4).~$ g~ ' . ·. ' -', .· ' ·. -.,.. . . .. ' ·•

'ic,:,1.~~- i.11 650 ril.1° of· \·ie\ ¢lit9t9£or.ra ._~qltd.:i.on_i 1,, 'llte y;1¢li<la t,V). thG P-f#par;t~()n ot pe~b.en$oi~ ·ae¥·

:ht th¢ pt>()c~r.l~@.;,~~~~>r~~ 7~al$ t; as;i,i~ . '' ' ... '. ,... . . . . ' .. -:(: O,tid~ t1011~l'o~~q'~'?:~~ To;---~ co.+~ soJ.:u:bion .. o!' ·.. . ... · - . ·'·· ·_,·:

sa;s g~ (0;~79 m9J.~J gf p·&x-b,:h~oi~- :aoicl -~- 600' J+ll., ·'•·, .· '. . ·' '.' ·.. . ,' ·1 ,, ' ' • ... 1-. ~f wet cb.1oroforjnt tltap~ w~.n added ~- ~old, ;sol.,~t,1¢n

.·9t 4o;o g ~ (Oi2QB mo1eJ Qt p~~eif,.1l.a·t1lbez1a (m~pf ·11s .... :i.so"l di$$Olved 1 .. n 200 Pll~- of c111~x-cytor.ra~ Th.$ ~eactj,011\ 111:txture was a.ll~·Wed 110\ f$ta.ud. tor l2i hOUl?~ in a; retttfgem1tor ( e:e·>fmu.mpti® of aqtI:re o:xyg~n 01· ·. ... .',

' '·. ,_ '. ' .

tltl':1ti911,_ 9$;:5%) e,n,t'l '1n• e'!J,i.d~t:tonal ... 5 hottt'~ at ti.~~fom • :.· • ' , ' • • • :- i " ••

:b~ttlfE3~ature (ooi.1$1tn13.?tion -O~i a:c~;VE>:. rlxygen.,:. 100;0~1lt • _lo~--·, Th~ rema:t:ning B;~ St of perbem.!()ie Jtcid in 50 ml ► :=:..... .' .. ·· ' .

¢f cl:i,lo~o.r?~rn, used ® a. lllankt shovrea no 19:;.s_ 121 nqt!vf;l ·o:trge:n .to:r: thtt flr$t_)2 ho.ura~\ Tb.a ohloi-9J,,:, , . . . i' .> • . .:, :,··. •

'fovm solution v1ae ·~xt~aoteµ ;~1oe ~tl} a total of 5oq mi~, of\ 10 %. ~l'odittn1 4yt1roxicte,,._ wa.ah~g, with w-~~~t~ '' : ' . ' . !f ' ·. . ',;'

·Ill.Ad ~onoentra.te4 on the ate~ bAth• .on eod¢~~·-tlie x-esidua.l. oil erystallize~.. 'Jll,eJ?e. ~1a3 ~o-~ed

40,.1 g~ __ (02~~l ,c;;f.: p.inw~~tst11b~~ ·«ti4~, ~1:,P,r t~·:o~ao;o~ 'Ct'U~tt1 '.arter, ··r.eci-;ts-}'~U~ttt:1:'?:n f:P()nt Bkellt ,., (1"8PQ~~d ($~J m;.p~, 59~00<?},;

. . .... .., , ~,ti. n ,·. it,··#_,, t..n.~i -~4®• t.c:t~ ¢l5lj:1,40 ;: 0.,: ·:85 .a&r-?J ... ;•. G~ ~., toun<h c, ... 85 ~a11b J!f ~~~4%.,.

~!~ s~,: to~eq.a mo1,J

;l ·t1~jj;}; ••L 14o1et:J. ot l!•nt~tffl½'mb;en•; :~ido ,,zit 10~ ~9:fes ~r·p~.n{9.,, ~~,(~!6o•n~' .. ..

t{~d1:t.etion. of· J!~i~e6r?:liiti1o'em.. ,o,:·td.e .To 33Q nil •. . ,,_.P, •. o! •• ' ••• :1: 41· ...... l . I ·; ~ --~~• '< • ; ,_.l!llill¥..a. . ..t· >ti J( ,is:t d

~t an· !f.tner·- '~c;,1:at1.<>n oont~in:t:og :o,01so ·s• p~r,·•m1. (O.;lS6 mttl~'~ o.:t; lithium al~ttll 'hl~Mle,, -e;nalJ1$q;•· or··•a m~.fl<,ati~ or the g~.somet:ri.e Pt'Qoed$6 or j

r,t.t~'it.:i. : ... ....:i G'w.r'""'W,....,d . -t··n. ·ei"'c. \~I";!<. add·..;.A__ -.. ,_ d..i.oTMt-.t a .;.._ ,-J.v.~',;~ ~M . •'~' -~ -' . , .., l.'\<O . ~""•· _.i..· ,t'••.L_$,...'- .~

s 6lttt1on. ot e5 ;7 g • ( o.~:t~ xnole} ·ot p~metJ;ey-1$ tiibene. ~!de dl$tt:9lVetl. ~ .soo mi, of •Q4tum ~1e1i ,tne~~ ''ills ,_ .. eaotiQn ~ti.we wae; $t1:VrfA a, l"Q<r~ ~~~~•~

flJr ~ adaittcr>nal ia 11.o~;r$- ~- then hY4N1~~- Jtitn .,·

ws.t$tt ~d. satuwatea .. runm~ni$ 4tl~rtcf.$ ieH~1utton.. '.l.'lt~ . .

e~~aet~d w~th, ~e~h t~$vent,~, ~~:•;a~b-~ed, ~Jhin .. $.o;u:t;qn.~~f)r~r,\to:~ed wtt.'.li ~e,ttW~1te1t_ ·•~~i,m b,ilttwbona.t,;,\ ·s.lb.l.utrtPlii J.11\t~it -~-~J? D.X'~$.r·:;ta •$n.;l .:·c,:ttJte.an~at,aJ q;n r .,, ,a:·-st;eam 'bath ~~d~t ya~\imn.. .111~ .;-~s14ual ,o$l-. •~etsne4 ~~,,!:4; !!ho,, 1'-~oqne: ,pQ<> t~l>rl JAu :<i!U'li,fu:U:r ~ctoJt:ted,; ·t,:~ffe,.:, diiu~- 'hyclrochJ+<;>t:io- ~-~i<, ,~e; $lttr,ac.w.tt ·with,,

\it::: t;~;::w:,;;;:::4w:;:;;;~ 1tn~e~ va.euum, Ati. udq~~£it1~.t:); a.e g.. of 't;}l.o ,oi1 •~ . . ; . .

-01;>tet111~df- ·total reec>ve~f;.; $l1$ g,~ (93~"1%)· .. > . :: ,.. ·-

~,, Qil.wa;:•s.. ~:n.-o-1hl;bf:' ~osoopio ~l,a:ta. t:q:•0011.; ;f;a,ht ~8.1. ·t. 3-.3$ pf" ,p~~t.~ph~l.1),a~rJ,; ,entb~(tl,

•: . . ,.' , .. . . .. ··,-.

'911~ t-emai.ndet ,1as ae$ttme.d ·J;tt be ~t'jha;_l'.l.$e4, ·-'~~t,.~J'l• ;,, ' ,.·. '· \, ·.,.•,'

-~~lber~, o:ticl·e t ,A ll~th~.tie :n~tu.iit l)on)p~se¢t ~t. ;' ·. ' • • . ,,.. ! . ; ' . .. • .·, ~-': ·'

,$:ie%: ,~t. p.;m.etb:!flp7'.i~~:ribe~:r~:. ¢@blll:Ql,j,:4,9~0%. ot :·, 4'"-..,.-.l -- --- -' ·1· - · . , ~" : "' · ~-(~·5· ;,;3,tti · · ' ,~ · . .~ .; p~m.~ ~+; ,enz1 C-ari;.,..a.~oa. ~ .... ii,-.,~i"! (;Jf );)~th.7.1.~

eti')h:~e, ~~~de., ~lp.~tl bf the· ~"9.a~op:s.~._-mE'fth~r!tf.' wa.~ s;i~wn t.(), 0¢1:tlin •$2 ~'7%- qt ~.;mttt)l.1.-,-)~p~e.~lMn$.$Jl.-,c;ttibin.01 ml 44~15% o~ p~~'.fAJ"l~en$.J1p~etii1 ·et\:rJ11ito1.,.

:· . . . . .,_ .

c."18-c.. .. ,\, I~ ~Al~~C.k\ ~<-Mc."~['3) +c."~~\.:.' ~ "~<It§ '-' 'o' \.:.I '-' CM ~ , Ok~

P• Ohlor6bSAA:Ylp1?,en:yl earbinq_;_ Th& usual techniqu$s; ·'tor the prepax-a. t1on .of'

e. Gr1gnard li$agent were employed. !l!o 4811:t? g, •( 2.00

moles) of magnesium tu:on1ngi'J suspended in 1500 ml•,

ot sodium dried ethel"., ther~ was added, d.ropw1a$J

362 g. (S-.oo moles) of p-chlorobenz:7:t. chloride, b•P• 98° (lEham.), 104° (221 mm.). Tc the Grignard.

reagent, there waiJ added 203' ml. (212 g., 2.00

moles) ot red1st1lled benza,ldehyde, b•P• 174.sO ('740 mm.). The reaction mixture \"IS.Si hydrolyzed with En saturated ammonium ·ehlo~ide solution. at 0-10°, then with dilute hydl'oehlorio a:c1d, until all salts were· dissolved. 'fhe two laJ";re:r-s; we~e s:epaa,ated and the aqueua. portion e.xtra:oted with ethe:r. The com•

binedi ether a-olutiol'l& wex-e we.shed f11'St with wa..ter, then with 10% sodium. hydroxide;· and cll'ied c,vf/,r

~ie? 1 tee The ether wa·a: conoentre.ted and the :resid-ual oil, distilled through a,. ehort vigrea~ column,,

yield~d 310 S• (67eO%) c>t p-ohlorobenzylphenyl

carbinol.11 b .. p. 199-203° (15 mtt1.) crude m.p. 49.o-, 5107°, 1!1-•P•, af'ter t'ecrystalli~a;tion from Skelly o, 55.0-56,5~.

Anal. Qalod. for a141ti3010J o, 72.2si, B, l>,.~3") Gl; 15._24~. P(\und O., 72.27%; Hi 5.61%J Ol, 14.87%,

14:~94%.

362 g.,

(2.00 moles) 212 g.

(2:1.00 moles) 310 g.

(1.3°" moles)

PJioles ot p•ohlo:robeil.$·:i,lphenzl carbinol x 100 71:~li~ld • &i1es ol' ·p-9hloro'6enzj1:ch!~vid'.e ·

·: ·1.5~~6~00 : -~1.0%.

Pb.enzl lll',et:h.e.~e derivative.-& m1xt~$ of f>OeO

g·. (0.215- .mole) ot p-ohlo:robeiw1lphen7l carb1nol

and 25·.0 :ml~ (2'7!5 g., Q.231 ~le) of phenyl 1so••

01anate w,as~, heated on s steam bath tor 16 hours.

The product wa~ tr1tUl'ated under Skelly i~ dissolved in carbon tetrachlol'ide and filtered-. The solvent

was ·rE:Jmoved and there, was obta~ed after several

l.'ecr-,atallizations from Skelly O;, 66.'1 g. (88.2$) ot the phenyl Ul'ethan& which oorresp~ruis to p-chloro-benz7lphenyl carbinol, m.p. 130.4-132.oP.

An~l. Oalcd. fol' 021H1801N021 O, 7le69%J

B, 5.61$. Pound.: o, 71.ao~; 11, 4.99%.

9:'he. retraQt1vt iJJ.d.e~ _of ~a ureth~e d~r1va.t1ve; t~lt~n w~th Ao F1acherrielly Jiefra.otometer a~ i4.0°,• . . s~va th¢ 1'.t?llow,1ng :Jl~d~J ~c;l. lf~50•l~5$5; yellow; l(~ 555; gre$n", 1,~ 555-l.J563i vioi,t_, l!' !562-~. 570ii p•Qbloroohenyl'pftnzzl _- 11rb1J10,l

The µ$tlal tf)o~ques tot' the prepar8't.1on qt a G':ri~.- ~,igent. w~r.~. enipl,91ep;_., wo. 4,8.6 gi, ,(2.PO moles,} ()f: lY,1$~,sium: ~µr,n:1.pgs $USP$nded ln ·.lOO_O ml. Of' sod3.- d~4,eto._ 4:>th~r,, ~~ W~s ~ded• ~rc,:pwts.e; ~:;o mi. (~54 s~-• ~-~PQ. ~ol~s) pt ~d1.st1.ii~ ben~ _zyl_ oh,.lo~id.$., fe>. ~- J}~i~ r~Ef.Stlnt ~E3,:-e was ~4.~4 .:282_.,S• ,(~•:09 ~qlesJ qt t~~hl;y :re41st1lled p;;.ch.lor,ot>enze.ld.,byde <U.1:1solved tn 2.,0 ml-.. ot ether, ·Th:$! reactipn mi~t'Ufe w:as b;ydl"C)lf. &eel and w~~k~. up, '3-E.t de.s..cr1be4. 1P tne pre1p~ra.tio11 ot tit~ lsom$i-~. A _y;lelcl. pf 2.€35. _g., ((,l. 5%) ot p•c,b,l()rof ·pbenylbe_nz..11 oa.rbinol wa.a obtained, b•P; l5ft~/l.4 mm., -~;a-i:,,T/ao .mm .. • Dl~P,, fj.:ftar reJ()~stal.11,zs:tiiOtt fro~· ij~e.ii:v a, .52~5-3 •. 5~i ~~ ~~i~.~ t-.~'t:. Q;a.J:{1.e1;<fl.Q' 0;,,.,.1,? •. @~~, ll;, 5. 6:,%,.

Fot.µ1~= at. ... -1~ .,g§.%.1 ~. .5., 542'.~--·

2a~ g,. J~5!t .s~ :285' g. {2.00 mQl.et:i) (2!'00 ~o;J.es) (l, 23- moles)

% yield= Moles of_p•ohlorgpheny;lbenzy;t. g,arbj,n,ol _ lOO · · ·· Mol~e of p"P'ohlorobenzaldehyd$ x -

= l;2j x 100 _ 61 5tt1 2.00 - • lfO

__ ;rl1em;l;u,te;tha4le de;r~ya.:f.1y:fl,1,,~!, a ~xture ·of' 50.0 S► < o •. ~+5· mo;Le l 9,t p•ohlo..:rol?~~cyl_'bfµ.zyl c~:t,,inol ~ ~5 ini. (27.5 S,;,, Oj:2;1_ DlP~l9_). Pt ·,phenyl, ;1aoqye.na.te was heated on.a.st&e.m,ba.th tor 16 hour$. ~f>: p;i-9-. -~- . ' .... ,, . ·.·. ,. ' -·· . ·•··· -- .. . . . :· . . . . . . ... : -· ' ' .. ' ' ·. . . . ' : . :

duct ~a$- ;.:el'i tt.Wa.ted. under s~~ii:r A, di~s<fl.t'ed. in carbc,n tetra<thlo~d~ ~n.d. til. te~.,, ,:.he so;:t.vent lfas. x-a$ov~4 .. ~-- .t4fl~e waJt pbt~~n.~~, a:f"te:r ~evet-al ~ec.ey~t$.liiiat..19xit1 _ fro1J1. $)te~ly' a,.. s,. o S• .( 12. 5%) <>f. ,~~:. _pllew;l.~~E) .~0.~e.s.p~p.(lt.ne to p .. oh].orq~ .Ph~~).b~nz1l. :carbinPl.. ~•P• lJ.4. 6,.:L15. .. 6~:.

~- Ce.led. tor o~~B2.,eOlNOa: 0, ·71. 6.9%:t Rt !h;t6%~. F.ouna.i o~ 12 .• Q·:5%, 12.05%1 a,. 5.,20%., .s.,s%.

fl'l~· ra:trs.ct1:v-e inlie:t ot. t.he urethane der.l'f$;t1ve ,, \$ken /ti..~ a ,1~01'+e:--ie.i11 Rtfl'e.~tOm$tfZtr ·at. 14<:>~ , ga.v~ the to.l.lowtng ban,dl:U ~ed.; l,.$50-l,:5.5SI. yellow, i .• 555) ,e;;reet1, 1~.55$:111561;, ,t1¢i;Lett 1 .• 56:5-l,570. p .. Q!A9J!Obenzyl,pheny;l ketone

A m.1xture o_t 7!,;.0 S•·· { Q .. p2_2 DlQl.a) Qf P•!'Jbl.9X'O• __ })J:~AAYJ..t?~~PY.t ¢t1.pl?lnP:J., ,~,. J56 .• Q 6•. . _( P• 3~~ J.l\91_e,) ot alwi4.riUtn.. i.~C>PJ'9P9~<l,. in. JPQ nu..,. _Q_t d;r1ed .e~l'"! Ert,IXY:l;. Jt'9tone .,(a.a ~t.lu;ed. to-,:- 5 hours.. 'lhe .~e.otton m1~ure, Wfie.· ~¢t.rolyze<!l, w+.th w.ater tlnd d1lttt,e hyd~~ ·ohlorJ.;.(j $,Cic;I.. . n,.& S.CJ,W3.oµ~ po;rt.ie>.n. W~$ .eX,~aot~ wi,t,h e~¢r, tmd. tll~ ~t~e;r was:ne4 with we.tel', The etp.&;r eolu,tion on eye.pcn;1$tton ~epoe+ ted. ;L6.1 g. ot p~oi-µ:oi-o.be~zylphen.y-l ke:t:,onth ¢~d,e m,p., 1aa-1'-4 ° .• The residual oil on d.3.stillation ;rtelded 5.1.0 s. ot SJl ·01~. 'b,Pt l:;6 ... 146° /p~Jt.o .. o,l:iO mm~ Add:1t19n ot ethanol to the oil save ;.2 s~ ot the kete>:n,e; nt1p. :i,1~134°11! The ethanol 'wa.~ ;-~!iloved tu'ld. 47.8 s.~ (~:,.8%)

C>f th~ drl:rbinol.. wa.F.J• .rec>overe¢, .. ni.p .. 4s .. o-49 .•. ot.♦. • ~~-·

l):.Qlll.Q1;'P~~µ:tyl.pAG~l. ~E:)ton~. Wfi,S F~('!'l$tall;taeci .,s~v.e:r•• al t1m~$. t:rom $,~Q~,J m.,P-if 13(:i.4--137.-4° J;r&PO?ted J~f34--g8~J l11,• P.!I i,,t ., l;i.f$ I) ) •·

·•• oa.1ca.. t:<>x> o..,4!H~:1.010* a, 1a,BB%; a. 4~81%1 Ol, 15.J7%. F~tui.d.:s O·, 7::i.-l6%a ~. 4.84'%a 01:, :1._5~?0%, l.5 .• 26%'.

15,.0 $t .. (0.:,2~ ;inql~J,

~-g)l+o·ro'Plwntlbeuzil· ~vt2rut . . . \

c..,-'rA-'-k.~-f -I~ ~- - \.=I

i9., s~-(o,oa:,IS .mole)

A mi~tttre ot 75:-0 ·g!'I (0 •. ,2~ .mole) ot -P'!7ChlO.~-"' phenyl'b~l.lzyl ·oa.rbinol ...• a.,n4 66.o s~ (o .• :;22 mol~) -Qt'

alµmin~ ii:lop~poxi,dEt in :,15 ml. ot dr'-ecl, metb;V'l.~ f;!lteyl ketone was refluxed for 22 hours~ •ellQwed. to atall(l e.t X'OQpl t.einp&ratute fo:r;, several days., ahe reaa\1on mtxtµ~ ~as hydrolyaed ~1th water~- d1~ +utEt :hyd;rooh,lol;'io acia.. The aqueous _por,ttqn wa.s. e:ictra.o_ted_ :t'1 ~- ethe!' and t}.l.e .ether wash~ w1 th water. ~~ e~~ .. a.olµt~9n w~~ Qonpen.tra.tt:,d, ap.d th♦ res1dua.l otl pa.~tially Cr,yl3t.~l~.ze.<:i., }Jetlian,ol W$,S ~d~ .E3.114. J.f>li8 .s, (~_,2%.) ot p-~hlo~pllenrlbe~zyl lte~ne ob ...

taJ.~~,. m, p_, ·• ?f.t~t ~~V:!l!)te.l._ ;ttear;y-sat~l14.zati.ons from nie~ano;l.# lOtS~J+-+97.,4rr. (l'$.P.Q~e4 (2$#) !4tP~: .. :r..97,s.:)j

~. 08.l<J<:i~ fot' Ci:L.,Jii:,JJl.Q;, rJ, 1;2;88%,f''ii;· ''4.81%; Ol, 15. 37%. Founµ.g o, 72. 94%1 H •. 5.0~.- oi~ l,p~ 26%, ·.

75.0 g!' (0.322 mqle)

_., :lihS ·S• co.0685,m,ole)

% vield = Moles or p-ghlotoR.b,e,mi:lbenzy;\ ketone . .......,; x 100 "' · -. · Moles of p~ch,lorophenylbentyl e~rbinol · •· · ·

.Q.,0685 X 100 .- 21 6!Jlc a:::. .· 0~322 . - • c.,f<I

~ru1i,-p-chlo;co a t~3=11fu1e. Metho9i A•.... Th,G prooedux-a o.t ~[eertre1n, :aucltner

l;i!.lld Ve.n.Ji!Ill~.t<:,:r Wt3.$. _µ,13~~ •. ; J~Q .. r:a. ~oluii~on, c,f l50 g. (l,Ol moles) Qf ~1nne.mio_aoig. d1sl:1lolv~ ill. 1250 ml. of ~o~to11~. oogl~d, t,rr -2,.~. 'tP.~:re waa ad~sd. a fil te.red a9l.u:t,1c:>n 0.f d;l.~Z9t~z~ .P::'.':<l.b.l_o?'9~ltne, pr.epa.red. fl."9lll J.30 .S• (1, 01. IllOl~al,. 490 ml •. (Jt qpn~sntr~ted. hyi:J.ro~ltlor.1~ a.oi<1, 50.0 rnl,. pf water, and. 75.0- S• (:L.09 moles) of soditun nitrite ln 150 ml. ot water, To th(a reaeti_on mixture thf3N w~a ,add~d. J~20 g. (l. 62 moles) ot hydrt;1.ted aodlum ao~ta.t¢a a.nd. 42.$ g. (0,250· mole), of ):);Jd;re.ted ou.prio. ohl.oride in lOO ml.. 9:f'• ,1ater~ The rea.ct1op. mixture was ~llowed to atir tor an add.1 ti OP.al ;t.2 llout>~,, . __ Tll,e- oil was , separated. e.nd

e~am o.1_$':t;1lle¢l.. ~~- o..iiti:t.+~t~ -S~'t.l;!, ;9 .. ths.. {1J,.,,a%} or 'p41.1ohl9l"()oe~zen.&t. lllii-P.~ ,. -~terr, ·tteoeynt.s,JJ.!~a.t..\o.n tram m,t~an.9l:t 5~c4'7:5'.;;.2,~-, ~., __ .:t4,~nt1f;y•; tta~ ve:rtfted by a- tt4xeei ~e1ti!is~pol~t -W:i'th. ~ awtl:l~ti~ ~~Pl& <1t P➔.i.o.ll+~l:'G>))$µ~e!1.$~ -~Et _Aq.lle~u~ res~d.ue 4.epQs1ted ll•h o ~-jl .( Q., 5%) C!t· 9.i.111? am~.e. ~~1~ ~n1. t,OQl,1,ns:~:-. ~• 1i$n,~ ty wa~ "rit.t~.a :W a.c:~.;iteg,, -~~J. tJns.tP9:1.n;t , ,r1 th

•. · · · · · · ·• · · · • ·. vi · • · =

~- ~1;1.•~~ntti(t J_~pie _t;Jt. 13.µm,~c a(l·ia. ~- z,e.~1dtt.al oil was !:ix-tended Wltb. e.tl:lei'.' an<t ,xtrae,teet w1.tii"··.1.0% so'if!iwn 111d.roxid.$ $.olµtton.. · 1.J:h,e $t.,1'!er;r drie4 o~or -Dp.\~x-i,t~ ·'~- ~O:Q.d,~:rJ;1':r.~t~.f- ·1.'-"ld.~ 9.:, .6• \('4·~15%') Qf p'"!'chlotostilbent,. c~de zn.p. ,,, 1~:us.0.~~a9.o:~, n,;.p., ~.t~:r ~eo.:iws.t~~,~~tt¢n_ f~za methane~, 1~9.(;i~l;0~-2° (-;repo;rteq. ·(~877289) m.p. 127• • 1a9~).

~-- CJa.l.od., to-,...· 02.,Jt~.01, a-, .. 78,,68%1 -a,· 4.721&~ 'FoUnd,J o. 7a.c,s,:, 1e.:,oi,. a,, ;5,06%-• s.Q9%..ti

?:he sod;LUUI ~iiro,d.da ,a:xtract was tletitra1,ie;;ed w,~~ ~<lrochl.Pt1~ a.1'-i<l -~ ~~r~ct,ed 1,1t1t ,t_th$r·, 'lhe .ethe~ ,,•r~s d:r1e<t &ild. qq?'lQ~~t:rated on .e. st~a.m,- l)ath. Th<;)- .~e.sid.ual_ o:;t~ p~ <lt~~llAU.OJA t1el.4,eclr 72~,, ·g!t { :;:,.~%) Qt pfehlorQatilb$~e... .A m1~~a; n1el Uns point with the ~alytl<,$1 sample,. c>t p~~h;tq,%'0ei;.1J;µen;~ show~ JJ.9 (i$p:res1d.on~ .'?J:ie unll,iatilled. r-ss1.d.~e., ,,. , s .• -•. (1ons1 ~ted of -~ Inlxture of aci4s • cx,.ide ~•'P:• , l(SJ~.o~i.74. Q.0 • R$o-ry~tall.iz~i,i<>n. Qt th,~- mi.:ttu.,re, fr()m -a.queoµs a.detio· ~¢1.d gavt a compound; tll•P• 1.82.4-182.9°, eti.ftic:\,ent only tor a singl,ft •~J'Ed,s. ~e oo,mpound may b~ a p-Ohl-oro~dtphei\'Y'laopylio ,aoill.

~.. QM¢~. tor o~~-'il:U~;r,.C:LOa~ a, t)9"64.%J: lh 4.,)9,% •. rounch Q, 70,:,11h. lI, 4,27,&.

J,.!50 g. (1.ol mo,le~)

1:;o e;. (l.Ol mole£\)

$li5, 8• ( 0 .. -,e1. in9ie)

&!$i,hog _E.,• A ~o~u:tion of 267 s~ (;1..15 mol~s), ot p-¢hJ.proph~cyl.bEinzyl, -~~binQi. 1n ~50 ml,. of· e.et?)'bj.e aneyd.1'"ide ,{ r~agent· gr-a.de J w:aa. ;re:flu~ed for l.9 hoiu-a. Th,$ raa.1.1tio11 mixture.- was d:1.stillec\ a.t . ,•''. . . . . . . .. . .. ' .. , '

a.tmo~pherie p;r;~aatu~ to ramo_ve th~ unehangeq. aoetio anb;1d.rid~a,n4 tJ.t$ ac~tlc_S.d:1.d Whidh fOl'llle<l. On ¢¢101~ tb,e r-e~t(l:µ~:l... .. oil ql:'Ysta.lJ..ii~cl ta.ncl e;s.ve _2~8 g. {88.7j') o'i! p~¢h19~stilbentt1,. llh.P~ t a.ftep one re.~ t;uzya"balli,z~j,ion fr9111 ~t4a.n,ol:1 lJ!9.o-i:;o.,.01\,: A . . . ' . ' . . . . . . .

mi:;;ced., melting point with an autl:u.~nt1q· ae.m;ple or P"" alt1911q~tilb~ne prepared by th,e Meerw·ein zi,ee.,0tton .:::Jhow~q. nc, ___ . d.e;pi--esaion •

. T'ne uae or SO% sulfUJ:1:.o a.oid ga..ve a. mixt'tl.t'e of ca~b:tnol --~- atilbene.

CR.. ~ -C.\\"' /~ \_:.j 01' \:) --) t..\ ~C.11- .: t.M -~ '-""' ~I

267 g_, ~18 g .. (l.;t.5 l!lOles) (Ii.-02 moles)

itethog. JJ .... ~~ .. PX'll>O~ur~ o.t Wa.wzop.~lt, ,(~90,). to~ tlle . pt,e:pe.~tJ.,on .pf: ~,+arti a~l:1'i,9t11tri1$S. · w~~t u~$4. A l!Q+µ:t.,P~ Pf ·QQ41:t.t.~ ~t11,9!l4(1Jc:f ;p~ps.r~ fJ.'9~ ·7• 0 S• (o •. 3C>4, 1AA1;L~) at tNa~y~~µ:t_ BO~'U.m 4'--f3$.Pl.'t:~ ·in;. ioo nq.. t:f abtiJt>l;~te: ~~ol,..,.J1~• ad.4,eq.,, <!l•ppwi:$.e•;. _to .e. JJOJ.µ~on. of t~7. ct,, -.~C+.,-,0:Q. -~fJ+:eJ Pt ~~11+. :t3J.~d.~ amt ~41 .. s, Jl_.o.o .µto_:t~)· .. ,Qf· P""'.tl.11P,NltJen~~i~ebY4~ i.n. 6$Q nA~- of :~/5% --~ttiantfi. f.lle ~a~tiQ~. ~~t~ was allow.-,4 t◊. $M.r dV~$1.SP,;t, -~ ·•q'.JJ.~ lf-W-tin. f-0:rm,~ we.a. r-1,11,~r,ed •Eind;, .,t:r.i:tu:ta~¢~ Wl(ler ,,µ1all!)i.. 9:b:$.:C-$ W'~-~ ()bte4?.led ~l.'7 •. 8 S.!! {91~5%) Pf OC.~PP.Wtr'l,..- ~ ~-Qhl¢:t'Opl'l$W+ ~or,lQn~t~;L~, erttd$ .m.p •. 99,71ip.o:!, lll~ P• , e.t'te:r .re4eyata+l~zat1o:n fro~ methEµl,oi,. l.Ol,r?~ 102ia~ (reported, (~8.9): m •. p .. l08:!J.-··•-· . . ~.

&m!" C~led.•· fctr· Q~.~~;oC4lt O, 7.5.~J li .. , 4.20%. Found;, .a, 74.95$1-.. Hr :3:•_9o%tr

~- saine p~C.~Ul'Jlf) s~W~: hisii yield.a o.t- -~$

~o~e~po~~ p--ra$i:40~ ~c:,1.t1po1JpQ.,.; m.p._ 94"7.95.~ (re~ po~~ (291"'.'.293):m·•P• 9~~ •. 95,:} ~ -~ p-:d,1~~tl13'l~ ~11Q oom.r,o:un<1, 1'1.,P.,. 1,6 •. 2:-.l)G.,$,~ (~p()~t-~ c.:a94l: ~♦-P."' l.3o_:~ ).~

I-lyctro.lya1$ e~rintenta on t~~ p~metnoq -~ -~., P.~dimetJ;:wl.$nin9 o.c,,mpo~s. J'iitb .a 141.~tu:t'& .:~,f s~o, lilo~_id~. ;3.c.atte. t1ci.ti_, .An4· m~.:t$z.'i 91l lf:.1fJ'.t p9:e~~:~;µJT1 _:~~ tl_:r9#~~ in gell.os0,_::LiT$ Qt 1),ut,:yl <l$.ll.~a.<>lv~ pv.e, ·;t.ow

f1$ld.e <rt ill:~ c:o~J~i10,n.d:1.~- ~otg,s.,. ·1Jeµ~~;" EJ.ttempt$ 't,io _pre;par~ P°'"<i.hlPPQ.~_tl.l;\l$.n$ :by dl9,c~bo;:ttl?.tilt>n ot the a.ot;vlfc ~01~ co:rreapo?1ciing_ ·t9 0(--:phenyl~·A•P ... qlll.oro-:; Ph~:ey-1 ·att~iollt:t,x-i.te w~~ e;band.Q?lP.d 1ti. :tairot- of ·Methot s. iT.Moro!lti1bsna ~:JdAe;.

Me:tJ?.?&i Ali·· TQ a solut.1Qn ot 50,.0 3.• (0~2,4. ~ole) -ct p .... enlq~EJtil.bene. o.:taspl,v~ in, $7S P11. of (µ,l+Qr9--tom,: there ,t.a$, e.ctd$\ 48i8 g. (0,'354 m~le) :pf perb,n•· _zoiQ' acid in 700 na.,, ~t ~et, ohlo):'Ofot'l'll, prepare~ ~ F).ri:aJ.y~~: ,a.a· previo.usl,y d.,el:l¢.t';i.bed; Th~ ~a~tton .ill1x~ tur$ wa.s allowed :to s;t~d tot-fCJU,?t'_houra, t~ a~tri• set~to:t' and.. t<>r ;J.4 hour$ at tP<?.llt: '.t,$.:mpe~~/tttra.,,_ ./1..t. the. end. of 16 p.ou~s" 99.P%, r>t Ui~· ~eo:t'st1~al ~tU1t of' p.erbe11zoic e.~1d. w.a.s c~µsumed.. 'l'lle. o?µopotp~ solution. wa.13 e~act~~ with io% s«;>d.ium .llY~~xlde _solµtion; 11al}hed .. w:tt;ll W$~~r.t 4:p.i~ai ~- q0,_µ~ent:r1tt.,_., ~;i.~ ·r~s;i..p.;ua,1.__ o:t.+ t wh.1,'.c~ ... ~r;v-13,t~ll..i ~~. pn s ts.nd.1~ • 11.~:i4ed. s1u2 :€5• (96,.,5%). ot p~o11.lo~~~rh~.lbat1~: o~d.e,. ¢~d~ m.p. 9.5,-9f3+!i0J .n.i,'.P: •. , -~t,er .P~eey~t~lJta~ion front Skellt o, ·loo. 4~;1.-oif s:~.-. . . . ·-,:;

., ~, •. • .. Q:~l<!.~ .•. ,.·. _:ftqp:. ,~~~,1;;1.,0l0t 9" ,12:. $8:(l H,:. 4. e:i% •. Foµnd,; Q.; .... 73.1~_%:; l.ft. 4~ 7~%.

.5.0~0 $~ (Q,i_:34 mole)

48.8 S• (0~;354 mole.)

52.~· g-~ (.0 •. 226 mole)

Jiathod -~---- 'l:.h,e .a.t~1npte4. 'pa.~e- ~e.te.iyaed Q;Q,lid~n::-,, s.e.~:tP:t~ ;f;)~ ~ .. ,c,~rql>.~tal(lf;)~d$ ·a.?ld benq.l. pl.'llo~d$ .f$J.1ScJ; t9 ~giv~ p~o)i.t.p:®~t1;Lb~tt,E!!: o~~e w~cl1,_. :'-Q'Uld be :tsg4tt;a,• .The. P.r<:>_O$d~., 9:t ~~~a.ttr?-, Jmsi:. ;~e.:rve;r ,,;e.!3 u~¢a.. ae-v.~.~~l _e.tteinp,t, -~~e ~61.de t~ wh,1® tl;le o~-t.al::r.st auct tA~- -~Q+v:er,,t "1e~- ,r~:rJ.e.a. ;~ ~i ~a.sea,'. p-qhl.<>~];)en~¥114~ny4e·•1;. :b.~zyl -~h.;l.pr.;4e:i .~ , .. ,t'1~ .:Ca~ .... 1:r.~~ WC9~ µs_~ iu. :$. ~9;L~ r~ti.9.J>t. :i~-~t:,: ~li)+, ~$1"$1$·. ~x~,_$Jl .Qt.,. s.ctl.;v~At .. --~- ;re.:f):~e.~ fQ.r .. s,ev:e.~~;~9~~~ ;Fu~- reag$t1.t,_s, f~e~ ¢f .'.~t~. tpa~~a 9:f'; )f~tf:>~,- -W~.t$ \j~eo..

1. ~oJ,k'.\&S!"\am· c·A~A~e-me~n9,.l1 'l:1.1~: .-:~a.Q~Qn mi.:ict~e was ext1'nd$d w!t11 water a.TJ.d extx-6:cted.. 1dth ·. -~ . ' . . . . ' '• . ,, . '• . ... .. . . : ... · ..• , . '· . ' . . . ,··· :: \· . ·:' ; ..

. E';1,b.,e;,p., _fp,Et ~\b_(;):r l(E.\.~- 'WJ~~s.h~,- W+ tll ws.t~ri JiX:-1.,4 a.nc1. Q()?\\Qrmtr~tta~. Aft.,~-. 41~.ttll.~i~o:p ot ih~i ~owe:t-~ bo1J..ing trs;c't,1.onEJ, t.l;le~~- ~as i_a~l.a:t,~d, ffQDl tlta ·.re-$14u.&. 1;1.r,._ t1r11:den.~~i;Jta4 cornp¢>Wld,• ~-.,p. ?~9nfl,~t · 1; .• flog,1um 1imth~~~m~~i~ '11he Niae.t19~--nii.xtu.re wa$ e~tem·~-~ th :w~t$r ~- ~~t:rae-~ed. w1 ~ ~tha:tt. .Th~ et,1:J.~.r.. ~gs WJi~~~-t d~ied .~. ¢on~entn1:;~. Aft~~ c:i.1s,111a.tion 9f the. +P11ter~-'b,Ot1i:p.g tr~o~t,0.ne.,. ·the;-~ wa~ .iaolat~~- _:t;1i'Qµt the, x.-~_si«!f.ue AA u>µ.1<t,e,11;t.±:tt~ qornp_quna,, 111."P• iasdt92:f •

. ,.. .as<it!lm i:ftho,~:e~Ol~. ·'DJ.e. ~~:a.4~$.op; ~~~ ture lfa.s ~x~end~ wt.~.-.:w-~te:r .W14 ~~p~<tft~, With. other,. '.t'!+e _aqua¢µ$ por~19~. 9~ . . ~¢.td:t:tte·$it4,o't with 11,;t;i.ufit;ll- n1.-er1~ ~_(l;\~ .. -Y;;.~IL.4~ .;;,~~P:1-PX-<?b.sp._tP.,tQ,· ~.e.i~# .m.·p.

:?.$Q.~a4i ff;.. lt llli.~~ .. lI!-e.~ ~ m>i.:rl'f~. W'.i th a.~ ~u't;b"3nt1() s~:t~ .Pf,.P.~¢1\lo;rcib~nzcl:9' .$.Ci<! ·-~~o~. ;nq tt~p1-.esifj1pn,, ~~ _e.<tJ;.~«~(l _____ ·s.9lµ;ttp:~, s~ve. a .P~$~.t.1v.e tfst ~o-1:'· ohlq".:'. . . . . -, ,•• ,

:ride Jo.n.. ~$' ·et\le~ $Pl:µ1.,iq~ wa(!· w~,.h~ .wt tb :tf~t~r, - . ,,.

dried and _Qo1l:<)~nt~ ts¢. •.(\:tt:tt~ .P~t'\1$+ ·dt.s:t;!lllati.on •· '. . . ~ . . .

01: ~e i9~e~~i1~. f.~",att~ig~$.#, the ~ai<i'1$., aetn~>t; ai tea:. p ... ¢hlorobenzy~ eJ.~01'1911 l11. P• , ~fta_~ ~:$Qt,°$'t'.8.t:e lizs.tt.on ;ft-Om E3ke1l..)' P,· 7~.4 .. 7l.6~~- (r$p~:r-t~t !llrP• 70. !5·0-., 75°). J\. sodiWb; ~s:ion g~y$- .s; :pos1.ti:f8: t¢at to~ ehlorinE). " . ' . . . ... . . . ..

MM• oa:tea. tor c,.-.,a,o:to:: er., 58.96%; a, 4 •. 9'6·• Fc>ttriel; 011. 59•1'%, J:, 4 ... 84%♦

4-~ §..o,di,unt :met,p.Ott',.d,e-a:tnext Tll.$· .t'eact~o~ ·mixture Wit$ llfd.~1y~~ w:tt..ll. wl!ter_.., The. aquaoue port,iQ~ t1eldM on a.oid;l:f.'i¢(L~1011 l:4.·0% ot p;.:.t;tl'll¢);'0benz<>.io a.aid. !al~ t·th-4:ir 1:1aa <;1,.-.1.~ '1.:n4 c_o.:r;i~~~ated, Atte,r diE:S; tille:llt.,tJ. of the low(lt-~~0111:ng tra.~t,1qne ; ther~ ,-reia 1-Aole.i.e4 frQ~ tb..e. J:te!3!,4u,~ .~, s~~l:J.. ~c,unt. ·of ~ ootn."'." pb\ind.'1 px-cba,blj ~n tt.tlS3'lil.11lE9,tri~a.l. p,,..t)~O?'>OP®~lr· P4Et0Y)..~a.tJ:\tl~~e1h;t9;rqlzjr<;\f;!,~.,, W~f.).h'. ga;.v,e. ,a po.eit~vt;$ test .fQr oh1.o.;r.1rts a.f~t. boti1:ris :t'n ~CJ.'1ac:>ua ·aod.ium hf~~~de ~-oltd7,1~:ri,. :m .. p • ., att~r ~t~$t~:ia.U~n tz-om _:nciueous methanol, $4.o,1p4.g0 i

-~~ ·Oal*d• for 0~.'1i.\1Gll401· Q:_. 6~ •. 9µ%; Ii,· 4~52% •. foundis c_, t5,2 ... l.2.%J B~ 4.~~4% •.

5, $0,dtu,m, ~etb,o.~d,e, . ,~A-~l @t.Jaet• • -~40.t,i_on mi~uz,e yraa cyd~lyzed. 1ri. tlt wa.te~:., 1l.'Pe aq,ueous por;.:' t1on Qn at}idi~ic$.ti,on with d.11Ut$ m. tri.o ~pid y~~ld~ 67.·0-% ·ot p .. ehlo;r:ioben:ZlPi~ aoid.... Ttle 'butyl etl+at ·''WBJ3 4-Pi~ and conoant~a.t.~.. The ~s1dual. o~l riel4~ M un1dent1t1&4 .tr~ction; ll•P• J.99~20,:,/~a nun.,, wllich

gave 13.. J?.P.$1 ~~ye ~¢.st.,:f.C?,~ tm.l?.~t~'.l'4~tt ,r1,. t,:ll. 1?ota.$sium. :pe,:ni~ai?ts..te aJi4. b~~~~-. t~~r~. f$P.t:t:ft;i6i>;$~

Jier~ioc:! ~.,. 1'11G a~tempt~d. be:~:e .o:a~:cy"-tad; ~ont· dens~tiop; or p-chl.oroban.ey1 ~l..oride ~ bermzald9.? ,hyd.e. also tailed. te> ;yield. 1.so.l.~q1e 'l?-c~o;,Q}:Jt.1lbei:l.f) oxide.. p..,;Ohlot'9l.)enzy;L .0~0,~d$:, ·"'nz~ld.~eyd~, and .·. 8.1:lhy~~u~ potallatum. 0~1?0:na.:te ~1:,;, a lt.i.1 :t. n,.Q:La~ r~tfc> . . ..... . . . ' . . . ·,:· . . . ···,, ._ .. ,, . . -

W~~Eil 're.fl~ed. in. ~- +arge -~;ice~~!!!: of .~bsoltrt:.~ mathml~ o,1 tor, 5 days -~ $.l~o,~d. \q ~t.aµg. e.t ~¢11t ·tern:rere.~ t~e :to,.,. .an $#l.41t1P.~ .. 2: 4ay:~.. ~$ -~~act~® ·rn~xiurtj was. ~r$e.tec1 i'T.itl:l atiµ;·ta eyd.1-ioC~Pri.e. ~Ci~ ~nd. ~~=· tJ,aQt.ed. ~~. ~~t!ft''" ~e -~t:.11er. ,-ta,$ 'fl.~ane~ ,ritb: ;watet tn4 a~tu.rtt~d sodi'1Ji\ p1~~P9l¥!-t~ $.Olution, drted an4, ()prte~ntr.a.tecl. Zte ~ea'iuua.l oil on distillati◊n

.•• •,•: •• • • • • •• •' • • • I ' >ao ••"•••• • •• • • • •••• •• ••• • • • •• •,

y;t~J.aed,t (l) .a; ttaotte>.n,; b.:p,. 84 ... 88t/46, inril. ·• vth3,.0h pl?Oba.bly qon'ta1n~d ~'1:l:'eaatad. J:)em.zalt1ehyy.e·, (2) e. frac·tto~, l.>. p. '.l04.;.l05~ /?4.~~S lliiii• , in whioh p• . . ,.-, . .

chloro'be:nza.id.¢:b1a.e was ·.1d.~nt1f1.ed. by· odol.~ and tao,::. lated .e:.s the 2,4-dinitrop~nylbyil.).">a~one, qructe, lll.P. 251~25_5° (:repo~t$)d. (~71),- .ni•P• ~~:. ~65a)~ an.a a$ ~e sand.oe.rbazon~, (i:rud.e m.p. 2:;g~~p:,Q {~p,Q~ {~7:t.)t

Jn.p~ :2;0:J.. .A. ~Qe~ .m.s'.1..1;~. potµt, wlt.h _an ~utJ;J.~:nt;ifl Sa.!llpl$· at- th~ s$mioat-bt1,z.one $Q'rt~~ 110 dap;r~~.s,ion,; anti (3) pighet-~b.oilipg ~~e,0:~ionia w~eh w•;r• not. :10.e~~ ti:tt~-

Reeiust12n -- bt , P~mo~·o~til;Qene,, Q;,t~s~ 1'o 46.6 €5• (0.202 $Ole) o:r P'"l'Phl¢.;t'.'Q'$:t!lben($f

o;:tar;l ill- ioo· ~i. qt sq4,1~ ~ri.~ :~~er, ·tht~. ~J~s aiiie<i. $0.0· Inl, of an ~th.err sotwt.ign, oo~ta.1~11$ Ot0419 s:. r.ter m1. (2-.10 ·g.;:, Oi.,$54 mole) c:tr li:-• tp.:t.~ al~nUUl l'.cy'dl"id~t analyzed bf a l!l6i3lti¢a,tiOn> ot the pr9·o~U:("e 9f F:J..Et:1.l .I.\~ G,rµnwa.J..d... The ~act1on wa~ ~ld:Lf ~~~~-tmi(). ~ ~- e~~ N.tZt.i~S4 IIlildl:,-wit.hin a ·few l!dnut~s ~tier the adc;tltlon.. b t.-e""· • : . . -: ,·· -. • •• • • • . ·. -·· • •• . . .,. •· ,,. ' ·. • . .• ·• . . ., ~ i _,. ' ··,

a.;ct~on mixt~e w~s l:!tirr.~. p1.t ~qm• ·t~mpe~~t\l~ ·to, .l6 _hoµr,s, ~- ·t,h~~ :liyd.~olyi~ Jd. tl'l. ;w-_a.t,e:r ~ d1,lµ~e eo~¾O aoid, .~ ~:~el': \1e.t?. $~pat,tated.. -~~ 'was~ wt th w-~ta~, :t1ll.~ 114~e9~ .. P~~-t;ione sa,v~ ~ :£:lOSi:f.;iv~ ~at, ·fox- ahlt?rid~ 19~- Jrt:t:4 ~.~lye~' iµ.t.pa:t;a ~.Pl~t;t.o~, $lie ettwr. wa.~. ~xten4«i with. ¢h+qX'oto;t;vtt :~ .dr.i$d 'J;?y· Jzeo:, trppi<t ~t.~t111.a~i9n • .'.. .~a :rein.i<t.U.sl oi.l P?-r·I;iat:l,- t>'i/1.;_ 1:, tall1zea.-.. MatJ:Um.ol wa.s ~d.e4. ap.d. th~ .solut;l.on .. ,. ·• .-. . . ,: : ... ~ . '.

,ti.lte~. yieuti,ngJl+.3 g. .(;J0,,7%,J ~t unc11e.ne;a<i: .Pf ' . . . . . . . ·:

ah.1~ros.til.b~ne o:dd.$~ ~e 1ru1't:hano~ w~!. :r-e~ev~ trqm ~~ :r_a.1t~at~ ,,.~+~~ng ,o;i· e: •. (6.5.~.0%> ot ~- ~~t~~ ot p-Cl'll.orppht!l:~l.bencyl .. and P:""Q~orooenzy-lpl1.$nyi Ca~--binol~f' ' . . . .,

~1em;:lu:t-ethan~ de;r~Jlg/;'CJ.'V~l$.t:'." ,:r¢ 6*0 S,t: {O~Og6 .ntbl¢J of' th~ :red;uetigii P.z-oq.µet.s pf p+dhl.orcrat~lbarto· <lX1d$, the;re> Jta.$ 8,Q:Q.~. ,:,.·Q :no.. ... J:5i'.3 g. f o~.028 mo:t~) ot p~euy;1 1so~ya.ns:t:i$~ !r.p.~. re.aGtion .miztu~ was wa;timect on a s·taam bath, tor AA l:t~l.P='.. The re:1:jul:t.1.ns cr:t'.t wa.s extl."a~ted. wi t11 Skolly A to ;remove the 1i'l'l,-. ~- '" • > ,, • • ( , • • • • • • • • l •. , ' • ' '

changed. phenyl 1$0(?YMat~.. ~e .011 ¢r:yata'.4J4zea a.Yl.d. was th~1•i- t.Uss,plvect in oarl)on. t~t:t?a.chlo,;-:1.d.e anc1 f ilte;c,ect. to 1,-emtrve d.:tpllep.ylutet;;t;_ ~$ o~bon: tet);'ta"" ,¢h,jio~i<.:le yvas x-em~yed. ttnd,t:i.r va~tiwti. au.o~ 9p.e ''t>~J~t4,~: :!J.Ze<l; p1--oduat ttitu~e.'.b~q. ttrld~t. !Skielly l'¼.; Wha-411 yield.~d. '4,.€5 ~~ (iQ~'5%) .<>:t ~e: .. ttre~1an~ ,deii;\.V{:,t~v~~ o;f: ti,.e :tsomar!e c~i'bS.n◊:La. W!ie ;p~du.a~ 'f~.s ~a.0 lyzcd, 'ffii;hottt· ftu:-the:i:- -ti'eatment.

~j Q~+cd. fpr o~.,JI;i.,sOlNOat .a, 1:l.,69%; li:1 $. :l.Qii lf; ;S.98%. -Clf 10.0$%, Fo:uni!i;; a, 71 •. 42'.%'.;, .11..99%; H, 4.:92%,, 5.03%.; M, 4.,2.6%, 4.25%t 01 1 . l0i'>6%, 9.;$~;1

ThF' ut-etll:a.n~ ~e::riv::.tiyoa Q.~ tlie .fiEl4-uit1.cm pro;, 4u¢tEJ. '?f P~.Qb.1._qz,ost:LJ.,b~+i$ P.Zid:~., .we;re ~hown 1:)y :Phtllie O:te.gra.,i stud,.~.ss to c,on.tair,, pQ;9 ,$ ·!i.(!1% <.:>t tll;e -ur~, th,t;ll).(:),. corr~s,pond.ing,. t,o '.P~9bl!?N:PP-el1Ylbc;J;n,zyl Oa,~bµiol e.nn p9.l ;! 3.0% or the iwethane oo~espond.i:ng tp. ;p1"" ~hl.or,o1)en~rlph$ey1 ¢~rb~~ol.-

A synthat:to mix~ure of tne isortterio ¢®oin:Plst, 9'.onta.i¢ng 61.4% of p-ohlp,ro;phellfl,benz;rl ·ea:ro1:)ii-io11 50:·t~ a, 56.8% ,yield of the dol:1~$POnd.1ng ure,tllanes, 1:rhe ~ynthetd.e rni~t~~ pf un~es 1-ts.ra $ho~m 'tJ·:/ th~ phase. d.ia.g:t:'ant titGtliOd to C<r4ta1!l 64.·~·.5% .pf· tp.~· ~~~ *o:rres1:,on.d.1ng to p ... ohl.oropherzy-lbenztl ~arl:>,ir.tpl,,J wh1oh J.s wi·Uitn experimental errot-. ' . ' ·, ; ' ... , .... . . . ; ..

.:S~l?iif.rosiilp~ne- :Orld~. A ;sql\ttio~: ot· lop g._ ( O, 582· ·lll.Ol~) <>f :P~nltt◊~'

:t,~nzy-t ,¢rµor;l4,$..,. ~Qi<?.:.. ~-~..C§3.:9 5(j __ • Q .• ?592 lll61a) 'qt .t~~,$l:4.J~q~~t,i;:q~~- '.b.i:;.'l;~.~4~~4e -~- :al. 0 Si., .. (01t·_$82. mo;,J oi' ~.nhyd:rou~. :r;,9.t.~~$.iwt! .. ¢~1:)o~ts, :W:!i.B . ttt;l.~d. fpt- ·24 ;ttour~.. on tiC)_¢UtlS,; ~$~ 1.fi;ts ob:tai.ri.e4,. t,,;y t~i:tr~tlt,n ,'.~ tr.tt~~t4¢n ~-,,qe_~ __ .~ll.\'.t~ wcfJ;\t>.<sbl.o~l-~ ~~~4l ·7a.1.._ g •.. , (55.:6%) gf P~~tppsU.;ib~ii~ -o~tt-~_;, 1I1.p.,., a.f-ter ~e,itf er,stAlllz~ti9J:1 ttPm ~~ol:, l~$ .• 0--12,7 .:0° ·(,r~po:rte4 ,, . . .

t2:1.$l J~4o:, ~44.h .i2.s.;,l.2G!! :,, ~2~ l •. · J\;rlal. \1~Qct.. to;r. ,Q_:1;;4Jii~~Ps.1 a., 99. 71%1 ~, 4.60%.

F.o-und.J d 1i -£$9 .• 92%:i H., 4~ 51%, )The ~lcohol., on ,(:Jita.;._uora.,U..o.:n·-- yielded.. '). 7, ~- g.

Jl.2;6%)- o·t ar>.. 1_$0nte·'.i;'-1,o p~n.;t:roat.ll'J:>~ne -9~~e,. m.-p~., af t.¢r :r.ets,eyat~lAiz~tJ.;oµ, .f:r¢n;t Jlie t..lia.nol., ·79. ·q\7;,&0-~ !5,~ (_-p~pb;~~:- (~4.0,., 244) t ... m.~.1'4> 74t76~ )ti: . .,

.: -·~-- Qal,¢d,. tor -CJ~.4 H.1:1.NOe; ~.jS9/t1%l 1{1 ;!f.60%; . . . . .. •·- ·: ... '.

roun,l:. a .. 10.11%., 1o~~s%;· :R, 4.sa%J, 4.~ss%:-_Mew1101~1]~lfi of 12-.mttost,:[:Jabene oxi,s;t~: A ~ol;u~on qf ,10 .. 0 g.._ (0~041.5 m.<>1¢} o;f l?.j~\):'tO.~;

Jrtil~lle o#d.g ,, ta.p":. ~P,0~7~,. ~- O.;t.Q s-. (O~<:>Ol!;i. n,i9~e) o.t sodiU!ll m~t.hq~d~ was ~~_tl.µxe,<t_ 111 1$0 nµ, qt -~b$o.1.u.t~- metruµ1,ql _tcr.r.~ 5. ill.~_s;: ?-1.h~ _re.a:ctlon Jnijt~ t:ur.~ wa.~. a.li9wed. tq stancl ai l!'oom te~pa~~.t:u_~- tar an ad.cU~ tiona.t twq ·4ay~~ The ~:~ti~s m~t~l."1$.l wa..$ ~-7-

cove~•-. R:v:QtQ1ys1~ ot: ;g-,nj/~ostJ,lbm.~ .o'A,g,~

Hydrolysis· or ·5.0 3., (0.21 ll'.1~le) -ot_ p.-.Jl1t'l:"¢-.i stt:t.pen~ 0%1.ae, m.v~. i26;~121°, in ipo. ml;i 0.1· 1.5% e.qu~oua pote.sa1um h;Y'd~otlde tc,r l~ .h.0~$ ·$a.tr$ -~

011 which ,oo~d;l.stilled with wats1,,.. Th.Eil pil was iden--tifiett. · $.t). -~~h~-allt~ey~~ bf· ihe pw.~ara:tipn at· ~ts ~,,4~ ·dliµ..t,:,op~~eylblcl:r~iQ~e., .. m.,P,.i:, 8]4~~11t.... A mtxea. . -~~ittns p~t.nt ll:L'At ~- ~µ;t}~~n:t1..c.t $aIU:p~~ 9;r,: th~ d.~rl~ va;t,1,ra ab,OJr~a. no ;ia~PX':!!tt~l..o~i- A. ~econ.a a;~t,t~nipt ,at a.;t..;ltal:l.ne 11.y(i~:t.yid~t! .:Mv~ ~ $.~µl amo·µµt 4J:f a. ~1@~· :)'.'"~d conipoµ'Ad, -ItlifP.• lA,4:7:l41t, -1.nl3'lltf'ieit?n.t ,f-of ptJri:m tl<tr.d:;ioµ .ttJld. ,._4enUti()nti_oµ.;i Wher e:voluti<>:n of anntt.oni;a t?tts noted. ~~l.Y~-- ·in 5% fby V~1tl.ill~) 0$ aq~epµ1S sUl~lQ ~oi~l SEiiv~ a nm~ ai119unt q:t qompoutld, m.:p. :is:¼~158°,- 1l'lS~;f;t_t;ti·$:n;t. tor put-:~t.icat1bll, ~#ff . :Ldenti.tica.ti:011. In ariotb.e~ •~~el"'iment 1~·;9% ot th~ a t,e.r'G;ng ma t,ez-,-;.~i was, .. _reqove~q..

1.. tt.R.Rttssel a;:nd C .• A.VanderWert, J~ Ame;r. Chem •. Soc.,. §.2, 11 (1947) •

2. X.G.Jttli:nge:ti,. J •. Amer •. Ob.emo Soo., ~~. 4792. (1950). . .

z. E.E, van 'l!amelen, ;., _A.meli. Chem. Soc • ., ~, j44·4 (l.961) • ,'

4.. R.O ,Wate:t's, Fh~D, •. ~es:ts, Univ. of K&'n$eu.t, U.1.ry, l95fh1

5. H.a.Ollitwood an.cl. a.'.f.Preuz-e, l. Ame~. Ohom. •. soc$, 68, 680 ( 1946)•' ....... .

a. lll.L,Orut'penter; TJ.S •. Patent 2,4531 0e2, ~ff 4, 1946.

·7• S,bto, J, Pliarm. Soc. Japan, :a,,, 20~~0 (1~51). a. ,.m.:rsastbs.m;, S,delhDa.nent, a.nd l? .E,Beaub1&n;

Oa.n. 3 • Ollom., !2,11 575 ( 1951) • ·

!ih Q.O.Guss and lI.O.Mt;utner, J. Oi,g~ Chem., lJ, 887 (1951).

l.O.

11 •.

L.O.Xing, lf.W.Be11st, and F.N.Itayea, Soo., n,,. 3498 (1949) •

A.M.Eastbam and B.deB.J)arw'ent~ O,a;n. 585 (1951),,

12.. R.G.ltstdeseh, J. 4mer. Ohem. Soc., 681 46 (1946) • - ,

13. J.Ransson., svensk. Kem. Tid., eo, 183 (1948). -14. P.Ferroro, F.Berbe and L.R.Fl8.lllln$; Bull. SO(h

chime Belges, 56, 349 ( 1947) e

i:..smtth and. T.!11.lsecn., 1. p:rakt. Oh•m., 16~, 63 .(1943) • . .. -.

17, L.Smith. S~Ma,ttson :and s.Ande:rson, ~l• Jtstog~a:f .. , Sallskap-e Lund., _!!; Bo. 7, 1 (l946)J Chem. 4b$•~ ~- 6458 (1947).

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