Synthesis and Characterization of PPV Monomer for Subsequent Electropolymerization

Research ArticleSynthesis and Characterization of PPV Monomer forSubsequent Electropolymerization

Aacutelvaro Fontana1 Faacutebio Santana dos Santos1 Flaacutevia Aparecida Fonseca2

Adonilson Dos Reis Freitas1 Andersson Barison2 and Jarem Raul Garcia1

1Department of Chemistry State University of Ponta Grossa Uvaranas General Carlos Cavalcanti Avenue 474884030-900 Ponta Grossa PR Brazil2Department of Chemistry Federal University of Parana Polytechnic Center Garden of the AmericasCoronel Francisco Heraclito dos Santos Street 100 PO Box 19032 81531-980 Curitiba PR Brazil

Correspondence should be addressed to Alvaro Fontana alvarofontgmailcom

Received 6 February 2015 Revised 12 April 2015 Accepted 16 April 2015

Academic Editor Ewa Schab-Balcerzak

Copyright copy 2015 Alvaro Fontana et alThis is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Organic synthesis of the monomer of poly(p-phenylenevinylene) was performed starting by the 25-dimethylphenol compoundAn iodine atom was added to one end of the aromatic ring and then the iodine atom was substituted by a cyano group Oppositeto the cyano group was added a chain of six carbon atoms and the end of the carbon chain has an added bromine atom Thecharacterizations of the obtained compounds were made by FTIR GC-MS 1H and 13C NMR and showed that almost all of theproposed monomers were obtained in their totality

1 Introduction

One of the ways used to change the electronic properties ofconjugated polymers is to add side chain substituents donorsandor electron acceptors in the polymer chain as it is knownthat when substituted benzenes undergo electrophilic attackthe substituent groups already present in the ring affect therate of reaction and the attack siteThe substituent groups canbe divided into two classes according to their influence on thereactivity of the ring [1ndash4]

Those which make ring more reactive than benzene areactivator groups and those which make the ring less reactivethan benzene are called deactivator groups The activatinggroups on the aromatic ring influence electrophilic reactionsin order to guide the attack electrophiles in a position orthoor para to the substituent of the ring which may also becalled guiding ortho-para In other classes of substituentsthe deactivator tends to direct electrophilic substitution atthe meta position so we call this groups of guiding meta Inthe case of the monomer to be prepared in this study thestarting material 25-dimethylphenol has a hydroxyl groupand this group directs all reactions carried out in the ortho

and para positions being an activator group or makes themmore reactive aromatic ring due to partial increase of negativecharges in the ortho and para positions [4]

Two effects are responsible for the orientations of thearomatic electrophilic substitutions inductive effect and theresonance effect The resonance effect that is the effectrealized by hydroxyl present in the 25-dimethylphenol isfound by substituents which have one or more pairs ofnonbonding electrons and refers to the ability to increaseor decrease the stability of intermediate ion by resonance[4ndash7] The substituent group can for example cause one ofthe contributions to the resonance hybrid As for activatinggroups they are those that increase the stability of the ringby injecting electrons into the aromatic ring The effect isillustrated in Scheme 1

By carefully choosing the deactivator or activating groupor altering the side chain functionalities one should be ableto fabricate polymeric films to be applied as an active layer ofelectrochemical sensors for example humidity sensors [3]

In this paper we propose the synthesis of a derivativemonomer PPV that has in its structure a cyano group and 120587-acceptor connected directly to the ring since it is known that

Hindawi Publishing CorporationJournal of ChemistryVolume 2015 Article ID 620938 8 pageshttpdxdoiorg1011552015620938

2 Journal of Chemistry

OH

EE

E

O

E E E

Ortho position attack

Relatively stable intermediate ion

∙ ∙

∙ ∙

OH∙ ∙

∙ ∙ OH∙ ∙

∙ ∙

OH∙ ∙

∙ ∙

OH∙ ∙

∙ ∙

HO

HO

E

E

E E E E


Para position attack

∙ ∙

∙ ∙

HO∙ ∙

∙ ∙

HO∙ ∙

∙ ∙HO

∙ ∙

∙ ∙

HO∙ ∙

∙ ∙

Scheme 1 Resonance structures of ortho and para attacks in electrophilic substitutionswith activator group where ldquoErdquo can be any electrophile

NaINaClO

I

OH OH

Scheme 2 Synthesis of 4-iodo-25-dimethylphenol

this group stabilizes the HOMO and LUMO levels being ableto control their relatives positions [8] In the para position tothe cyano group we introduce a six carbon atoms chain andat the end of the carbon chain there is a bromine atom

2 Materials and Methods

21 Synthesis of 4-Iodo-25-dimethylphenol In this organicsynthesis Scheme 2 we used 002 moles of 25-dimethylphe-nol and equivalent amounts of sodium iodide and sodiumhydroxide were dissolved in 50mL of methanol present ina three-necked flask The solution was cooled in an ice bathand sodium chloride solution until the temperature reached0∘C for temperature control coupled to a thermometer in oneof the necked flasks In another necked flask adapted to anaddition funnel containing 375mL of a sodium hypochlorite

solution at 4wwThis solution was slowly dripped into thesolution contained in the flask in a way that the temperaturedid not exceed 4∘C

The mixture was stirred with the aid of magnetic stirringand after the addition of all the solution from the funnel themixture was left under stirring for another two hours at atemperature between 0 and 2∘C [9] For product purificationthe obtained solution was treated with 40mL of an aqueoussolution of sodium thiosulfate (Na

2S2O3) to 10 and then

the pH was adjusted to 70 using a 10 hydrochloric acidsolution In some cases the product was crystallized at thispoint and can thus be filtered By having no crystallizationoccurred 50mL of chloroform was added and the phaseswere separated by separatory funnel So it was added to thecalcium carbonate anhydrous in the organic phase (dryingagent) and the solution was then filtered and the solvent was

Journal of Chemistry 3

OH OH

I

CuCN

NC

Scheme 3 Synthesis of 4-hydroxy-25-dimethylbenzonitrile

subjected to fractional distillation under reduced pressurebp about 40∘C400mmHg [10] The product 4-iodo-25-dimethylphenol had a yield of 75 and the melting point ofthe crystals was approximately 90∘C

22 Synthesis of 4-Hydroxy-25-dimethylbenzonitrile In thesynthesis of Scheme 3 002 moles of 4-iodo-25-dimethyl-phenol obtained above was also employed and was dissolvedin 20mL of N N-dimethylformamide (DMF) and the mix-ture brought to an addition funnel An equivalent amount inmoles plus 10 copper cyanide was also dissolved in 20mLof DMF and added to a three-way flask [8 9]

The system has been mounted in which a flask inputsreceived the dropping funnel the other was connected toa condenser and the third way is closed With the aid ofmagnetic stirrer and heater it started heating With thebeginning of reflux the entire solution was dripped slowly inthe dropping funnel After complete addition the solutionwas refluxed continuously for another 6 hours [9] Aftertime of reflux the solution was allowed to reach roomtemperature and was added to 40mL of a saturated solutionof ethylenediaminetetraacetic EDTA which was allowed tostir for 24 hours

After this stage the solution was cooled down to obtainbetter crystals and then filtered For purification the productwas performed chemically active with an extraction solventwhere it is first dissolved in chloroform and we transferredthe entire contents to a separating funnel which underwentfive washes with 5 sodium hydroxide When obtaining anaqueous extract it was adjusted to pH 70 with drops ofconcentrated hydrochloric acid to obtain a precipitate whichis filtered and dried in a vacuum desiccator [9 11] Theproduct was obtained in a yield of 35 and its melting pointwas 121∘C

23 Synthesis of 4-[(6-Hydroxyhexyl)oxy]-25-dimetilbenzoni-trile The synthesis of Scheme 4 followed the methoddescribed byChang et al [10] where compoundwas preparedby alkylation of 4-hydroxy-25-dimethylbenzonitrile with 6-chlorohexan-1-ol A solution of 001moles of 4-hydroxy-25-dimethylbenzonitrile 0015 moles of potassium hydroxideand 000105moles of tetrabutylammoniumbromide in 20mLof distilled water was stirred at room temperature for 15minutes Subsequently we slowly added 001moles of 6-clorohexan-1-ol [10]

The reaction proceeded with stirring and reflux for 22hours After complete reaction the product was extractedwith 30mL of chloroform This organic phase was washedwith a sodium hydroxide solution of 10 and boiling watersuccessively Dry the resulting organic layer with anhydrous

magnesium sulphate for 24 hours and then we filtered andcarried out a fractionated distillation of the solvent underreduced pressure bp about 40∘C400mmHg to give 4-[(6-hydroxyhexyl)oxy]-25-dimethylbenzonitrile a light brownoil [10 12] From the obtained mass the volume was cal-culated using the approximate density of the compound133 gsdotmLminus1 and had a yield of about 30

24 Synthesis of 4-[(6-Bromohexyl)oxy]-25-dimetilbenzoni-trile For this synthesis Scheme 5 was adapted from thehydrobromic acidrsquos method described by [13] where theprocedure was applied for the preparation of 4-[(6-bro-mohexyl)oxy]-25-dimetilbenzonitrile from 4-[(6-hydroxy-hexyl)oxy]-25-dimetilbenzonitrile In a 25mL flask 050mLof concentrated sulphuric acid was slowly dissolved in080mL of 48 hydrobromic acid under stirring and exter-nal cooling 15mL of 4-[(6-hydroxyhexyl)oxy]-25-dimetil-benzonitrile was added then portion wise we added over035mL of concentrated sulphuric acid [12]

The system was allowed to warm to 30∘C for 2 hours andformed two phases We moved the cooled reaction mixtureto a separatory funnel separated the organic phase washedit with 20mL 10 hydrochloric acid 20mL of distilledwater and 10mL of an aqueous solution of 5 sodiumhydroxide and finally we washed it again with 20mL ofdistilled water The dry organic phase was extracted withanhydrous magnesium sulphate during a time of 24 hours

With filtration of the dried product directly to a 25mLflask and held fractional distillation under reduced pressurebp about 40∘C400mmHg the yield was approximately85

In addition to the techniques FTIR and NMR thisreaction was characterized by GC-MS to verify the change ofthe hydroxyl group by bromine

The solid obtained was dissolved in appropriated solventat room temperature An appropriate solution volume wasinjected into the chromatographer with a microsyringeGC-MS was performed in a Shimadzu gas chromatographcoupled with a mass selective detector model QP2000A

A 60m long and 025mm diameter SE-30 GC capillarycolumn coatedwith poly(dimethyl siloxane)was used and theappropriate solution was injected at 80∘C Column tempera-ture was programmed to remain at 40∘C for 6min and thenraised to 150∘C at a heating rate of 10∘Cminminus1 Helium wasused as a carrier gas at a flow rate of 30mLminminus1

3 Results and Discussion

31 Characterization of 4-Iodo-25-dimethylphenol In thereaction described for obtaining 4-iodo-25-dimethylphenolit is necessary basic medium to occur NaOH because thepresence of the base has the function to remove a proton fromthe hydroxyl group present in the compound 25-dimethyl-phenol thereby forming an activating group ortho-paramorereactive than phenol which makes entry iodine atom in thepara position favorable with respect to the hydroxyl groupAs to attack of the electrophilic compound it is generated insitu in the reaction medium by the reaction of sodium iodide


OHOH

NCNC

OHO(CH2)6ClKOHTBAB

Scheme 4 Synthesis of 4-[(6-hydroxyhexyl)oxy]-25-dimetilbenzonitrile

NCNC

O OOH + HBr H2SO4 Br

Scheme 5 Synthesis of 4-[(6-bromohexyl)oxy]-25-dimetilbenzonitrile

772

602

2857

1543

445

113412501406

1488

2360

2914

Tran

smitt

ance

()

3340

4000 3500 3000 2500 2000 1500 1000 5000

20

40

60

80

100

Wavenumber (cmminus1)

Figure 1 FTIR spectrum of 4-iodo-25-dimethylphenol

with sodium hypochlorite which causes the 3IminusI3

minus complexto remain in its oxidized form I

3

minusTo precipitate the crystals the pHwas adjusted to 7 for the

product to acquire the characteristic of the organic salt andthus lose the water solubility We carried out measurementof the melting point and this was 90∘C while the theoreticalmelting point of this compound is between 94 and 95∘CCompared to the melting point of 25-dimethylphenol 75∘Cit appears that the increase in temperature recorded isconsistent given that the addition of an iodine atom increasesthe molecular weight of the compound thereby increasing itsmelting point

The compound was characterized by infrared spec-troscopy FTIR and nuclear magnetic resonance 1H NMRand such characterizations are shown in Figures 1 and 2respectively

In Table 1 some major bands found in the infraredspectrum obtained in KBr tablet are shown

The characterization by 1H NMR to ascertain mainreason is that the connection of the ring formed with iodineis carried out in carbon position to the radical present in thephenol ring

752 164467

669

217

(ppm)

725

232

8 7 6 5 4 3 2 1 0

Figure 2 1H NMR spectrum of 4-iodo-25-dimethylphenol

Table 1 Major bands found in the FTIR spectrum of 4-iodo-25-dimethylphenol

Chemical bond Stretch Absorption band (cmminus1)O-H Axial deformation 3340C-H Csp3 methyl Axial deformation 2914ndash2857C=C aromatic ring Axial deformation 1543 1406 and 1250C-O Axial deformation 1134C-I Vibration 602

The 1H NMR spectrum of Figure 2 was obtained inCDCl

3solvent peak at 725 ppm The peaks found in 120575 sim

467 ppm and 120575 sim163 ppm can be hydrogen from hydroxylgroup and water dissolved in chloroform respectively in thesample because in solvent we used traces of water that maybe contaminating the sample show peaks in these values [1314] Another possibility is that the hydrogen atom behaviorof hydroxyl phenols resembles the hydrogen atom of thehydroxyl alcohols The corresponding signal is usually asharp singlet (fast change without coupling) and the regionthat appears depends on the compound concentration of


1190

1413

2922

2224 1611 691

507

3232

Tran

smitt

ance

()

4000 3500 3000 2500 2000 1500 1000 500


minus20

0

20

40

60

80

100

Figure 3 FTIR spectrum of 4-hydroxy-25-dimethylbenzonitrile

the solvent and temperature being generally in the left (120575 sim75 to 120575 sim40 ppm) of hydrogen atom sign of hydroxyl ofalcohol Signals at 669 and 752 ppm correspond to protonsof aromatic ring and signals at 232 and 217 ppm correspondto methyls groups to the aromatic ring [15]

The result showed that the product obtainedwas really the4-iodo-25-dimethylphenol The yield of synthesis was about70 One possible alternative for increasing the yield of thisreactionwas dripped sodiumhypochloritemore slowly to thereaction mixture or to control the temperature so that it doesnot exceed 2∘C [16]

32 Characterization of 4-Hydroxy-25-dimethylbenzonitrileThe inclusion of the cyanide group 120587-acceptor group ofelectrons stabilizes energy levels HOMO and LUMO bychanging the electronic distribution of the molecule But theentry of cyanide group in the aromatic ring does not occureasily as the halogens Therefore it was necessary to havea good leaving group in the ring for the later entrance ofthe cyanide group Then first iodine atom was added in 25-dimethylphenol compound being a good leaving group forlater reaction with cyanide group

The theoretical melting point of this compound is 110∘CThe melting point of the compound is consistent whencomparing it with the 25-dimethylphenol 75∘C and the 4-iodo-25-dimethylphenol 90∘C since the addition of a CNgroup increases the number of hydrogen bonds by increasingthe intermolecular force system which causes the meltingpoint to be also higher To verify the formation of CN-Ccoupling was performed and FTIR spectroscopy obtainingthe spectrum of Figure 3

The assignment of the bands observed in this spectrumcan follow the same system used in the allocation of spectrumbands of 4-hydroxy-25-dimethylbenzonitrile However onemust consider the disappearance of the band at 602 cmminus1shown in Figure 1 related to the axial vibration of the C-Ibond and the appearance of the band at 2224 cmminus1 in Figure 3which can be attributed to the presence of the CN group

Table 2 Major bands found in the FTIR spectrum of 4-hydroxy-25-dimethylbenzonitrile

Chemical bond Stretch Absorption band (cmminus1)O-H Axial deformation 3332C-H Csp3 methyl Axial deformation 2922ndash2857CN Axial deformation 2224C=C aromatic ring Axial deformation 1543 1406 and 1250C-O Axial deformation 1134

(ppm)

733725669

363

243218

115

8 7 6 5 4 3 2 1 0

Figure 4 1H NMR spectrum of 4-hydroxy-25-dimethylbenzoni-trile


The 1H NMR spectrum in Figure 4 was obtained usingCDCl

3solvent peak at 725 ppm and showed other peaks

In the spectrum of Figure 4 a peak was also observed at363 ppm which can be hydrogen of hydroxyl group and at115 ppm which can indicate that the sample is possibly con-taminated with traces of water while making the purificationprocess as described in [17] Shifting the two signals seen inFigure 4 (363 and 115 ppm) in relation to Figure 3 may beattributed to the electronic effects of the CN group in themolecule [1 4 9 11]

Peaks found in the 1H NMR showed the chemical shiftsexpected for the hydrogen atoms present in the molecule 4-hydroxy-25-dimethylbenzonitrile With the results obtainedby the characterizations we confirmed the formation of theexpected product in this organic synthesis

33 Characterization of 4-[(6-Hydroxyhexyl)oxy]-25-dimeth-ylbenzonitrile This reaction aims to form a compound con-taining six carbon atoms between the aromatic ring and anOH grouping at end of chain This structure is interestingto act as a strong flexible drive to the proton conductionfunction in the compound after the polymerization [14]

According to the spectrum shown in Figure 5 thebands found correspond to the compound 4-[(6-hydroxy-hexyl)oxy]-25-dimetilbenzonitrile It was confirmed that


22202940

3400

Tran

smitt

ance

()

1600 1500 125010802853

4000 3500 3000 2500 2000 1500 1000 500


000

002

004

006

008

Figure 5 FTIR spectrum of 4-[(6-hydroxyhexyl)oxy]-25-dimeth-ylbenzonitrile

Table 3 Major bands found in the spectrum FTIR of 4-[(6-hydrox-yhexyl)oxy]-25-dimethylbenzonitrile

Chemical bond Stretch Absorption band(cmminus1)

O-H Axial deformation 3400C-H Csp3 methyl Axial deformation 2940

C-H Csp3 (-CH2-)Axial deformation(asymmetric and

symmetric)2853

CN Axial deformation 2220C=C aromatic ring Axial deformation 1600 1500

C-O(alkyl-aryl-ether)

Axial deformation(asymmetric and

symmetric)1250

C-O alcohol Axial deformation 1080

the existence of the spectrum CN group of methyl bound tothe aromatic ring of the side chain methylene present in thecompound and that the presence of the alcoholic OH groupand ether was attached to the aromatic ring

The values of the bands of each connection are shownin Table 3 To confirm obtaining the compound 1H NMRanalyses Figure 6 were performed in order to compareproduct formation by the existence of a CN group boundto the aromatic ring and the existence of the chain sidecontaining six carbon atoms having the OH group at the endof the carbon chain

The spectrum of Figure 6 was obtained in CDCl3solvent

peak at 725 and shows two singlets relating to the chemicalshift region of hydrogen atom attached to the aromatic ring in730 and 665 ppmThese peaks indicate that only two singletsof the aromatic ring carbons are not substituted and hydrogenatoms are not close to each other The region between thepeaks of 145 and 182 ppm are indicative of protons belongingto the side chainThe peak in 397 ppm can be traces of water

(ppm)8 7 6 5 4 3 2 1 0

145182

215247

365

397

665730

725

161

Figure 6 1H NMR Spectrum of 4-[(6-hydroxyhexyl)oxy]-25-dimethylbenzonitrile

0

20

40

60

80

100Tr

ansm

ittan

ce (

)

516

670

2220

3400

2940

2853

40004500 3500 3000 2500 2000 1500 1000 500


Figure 7 FTIR spectrum of 4-[(6-bromohexyl)oxy]-25-dimeth-ylbenzonitrile

and the peak in 365 ppm is signal with respect to protonlinked to ether group in molecule

It can be said then that the aromatic ring is connectedto not only the methyl group in positions 2 and 5 becauseof the signs in 247 and 215 ppm but also the cyano groupand the side chain composed of 6 carbon atoms attached tothe aromatic ring and a hydroxyl group at the end of carbonchain

34 Characterization of 4-[(6-Bromohexyl)oxy]-25-dymethyl-benzonitrile According to Figure 7 it is not possible to saywith certainty whether there was formation of compound4-[(6-bromohexyl)oxy]-25-dimethylbenzonitrile since thedifference between the this compound and 4-[(6-hydrox-yhexyl)oxy]-25-dimethylbenzonitrile is the carbon-brominebond in the end of the side chain where the hydroxyl groupwas replaced by a bromine atom The bromine compound


(ppm)8 7 6 5 4 3 2 1 0

142160

181

215246

341

365397

529

665729

725

Figure 8 1HNMRspectrumof4-[(6-bromohexyl)oxy]-25-dimeth-ylbenzonitrile

absorbs in the regions of 690 and 515 cmminus1 and in Figure 7there are two very close bands with these theoretical valuesfor the bromination reaction of halogenated organic com-pounds signs but they have lower intensity than expected

It is also possible to see that there was a decrease ofthe band at 3470 cmminus1 when compared to the spectrumof Figure 5 which corresponds to compound 4-[(6-hydrox-yhexyl)oxy]-25-dimethylbenzonitrile in that region indi-cating the presence of hydroxyl group at the end of thechain It might be supposed that there is substitution of thehydroxyl group by a bromine atom at the end of the sidechain however bands corresponding to bromine absorptionare small To confirm the structure of the compound 1HNMRanalysis was done as it can be seen in Figure 8

Figure 8 shows that the 1H NMR spectrum of the com-pound 4-[(6-bromohexyl)oxy]-25-dimethylbenzonitrile wasobtained in CDCl

3solvent which is the difference in molec-

ular structure compared to the compound 4-[(6-hydrox-yhexyl)oxy]-25-dimethylbenzonitrile of Figure 6 which isbromine-carbon bond at one end of the side chain in placeof the hydroxyl group

In Figure 8 a signal appears at 365 ppm it is signal withrespect to proton linked to ether group in molecule andhas a triplet at 341 but with lower intensity The regionbetween the peaks of 142 and 181 ppm is indicative of protonsbelonging to the side chain The remainder of the observedsignals is quite similar for both compounds To confirmif they were actually replacing the hydroxyl group by abromine atom in the compound 4-[(6-hydroxyhexyl)oxy]-25-dimetilbenzonitrile 13C NMR analysis was made asshown in Figure 9

The chemical shifts of the signal expected for the carbon-bromine bond are at 3380 ppm whereas carbon-hydroxylbond happens at 6270 ppmThere is a chemical shift signal at3279 ppm and a small signal at 3360 ppmThese values couldbe evidence that the compound 4-[(6-bromohexyl)oxy]-25-dimethylbenzonitrile was obtained but in the same spectrum

(ppm)

3360

3279

6293

6823

0030060090012001500

Figure 9 13C NMR spectrum of 4-[(6-bromohexyl)oxy]-25-dimethylbenzonitrile

there is a signal at 6293 ppm These values lead us to believethat the compound was obtained but is present in a mixturewith the 4-[(6-hydroxyhexyl)oxy]-25-dimethylbenzonitrilecompound

In Figure 10 the multiple peaks in the GC-MS chro-matogram reveal that several products are formed during asynthesis process Freitas et al [17] used this technique inavailable degradation process of polychloroprene He mea-sured the appearing new peaks in CG-MS as functioning asdegradation reaction Curti et al [18] study of similar systemarrived at same conclusion This technique permits availingthe appearing or disappearing such as the identification ofsubstance in a chemical process In this sense the GC-MSwas used In this spectrum it is possible to see the presenceof duplicate signal of the molecular ion bromine isotope in119898119911 = 30898 and the peak signal based on119898119911 = 147 whichis expected to sign the most stable fragment C

9H8ON

Due to large extension of the target molecule an enor-mous fragment was waited in chromatogram Peak with119898119911 = 310 was found C

15H20BrON These peaks found in

the chromatogram are according to data from NMR andFTIR spectroscopy and this permits us to conclude that targetmolecule was obtained

4 Conclusion

In this work organic synthesis of the monomers precursorsof class of the poly-p-phenylenevinylene for possible laterelectropolymerization was made whose infrared spectra are1H and 13C NMR data confirmed obtaining the compounds4-iodo-25-dimethylphenol 4-hydroxy-25-dimethylbenzo-nitrile and 4-[(6-hydroxyhexyl)oxy]-25-dimethylbenzoni-trile wherein the compound 4-[(6-bromohexyl)oxy]-25-dimethylbenzoni-trile was obtained but contains impuritiesin its structure or associated to a mixture of compounds thisresult is also confirmed by Figure 10 GC-MS technique andFigure 9 13C NMR spectrum


3000

102030405060708090

100

Rela

tive a

bund

ance

14700

8296

1480113197

3089824705164969097 224867697 312012480918094 27983

50 100 150 200 250 350

mz

34495

Figure 10 Mass spectra of 4-[(6-bromohexyl)oxy]-25-dimethylbenzonitrile

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

References

[1] L Akcelrud ldquoElectroluminescent polymersrdquo Progress in Poly-mer Science vol 28 no 6 pp 875ndash962 2003

[2] K Norrman N B Larsen and F C Krebs ldquoLifetimes of organicphotovoltaics combining chemical and physical characterisa-tion techniques to study degradationmechanismsrdquo Solar EnergyMaterials and Solar Cells vol 90 no 17 pp 2793ndash2814 2006

[3] N Grossiord J M Kroon R Andriessen and P W M BlomldquoDegradation mechanisms in organic photovoltaic devicesrdquoOrganic Electronics Physics Materials Applications vol 13 no3 pp 432ndash456 2012

[4] T W G Solomons and C B Fryhle Organic Chemistry LTCRio de Janeiro Brasil 10th edition 2012

[5] S Yoon H-J Choi J-K Yang and H-H Park ldquoComparativestudy between poly(p-phenylenevinylene) (PPV) and PPVSiO2nano-composite for interface with aluminum electroderdquo

Applied Surface Science vol 237 no 1ndash4 pp 450ndash455 2004[6] J F Lee S L C Hsu P I Lee H Y Chuang J S Chen and W

Y Chou ldquoA new narrow bandgap polyfluorene copolymer con-taining 26-bis-(3-hexyl-thiophen-2-yl)-anthraquinone unit forsolar cell applicationsrdquo Solar EnergyMaterials amp Solar Cells vol96 no 1 pp 218ndash225 2012

[7] J L Bredas and A J Heeger ldquoInfluence of donor and acceptorsubstituents on the electronic characteristics of poly(paraphen-ylene vinylene) and poly(paraphenylene)rdquo Chemical PhysicsLetters vol 217 pp 507ndash512 1994

[8] H Firouzabadi N Iranpoor and M Jafarpour ldquoA simpleefficient and highly selective method for the iodination ofalcohols using ZrCl

4NaIrdquo Tetrahedron Letters vol 45 no 40

pp 7451ndash7454 2004[9] H Ryu L R Subramanian and M Hanack ldquoPhoto- and elec-

troluminescent properties of cyano-substituted styryl deriva-tives and synthesis of CN-PPV model compounds containingan alkoxy spacer for OLEDsrdquo Tetrahedron vol 62 no 26 pp6236ndash6247 2006

[10] H-T Chang H-T Lee and M-Y Yeh ldquoSynthesis and char-acterization of the soluble luminescent poly[2-decyloxy-5-(41015840-ethoxyphenyl)-14-phenylenevinylene]rdquo Polymer Bulletin vol57 no 6 pp 921ndash932 2006

[11] M R Pinto B Hu F E Karasz and L Akcelrud ldquoLight-emitting copolymers of cyano-containing PPV-based chro-mophores and a flexible spacerrdquoPolymer vol 41 no 7 pp 2603ndash2611 2000

[12] T Raju K Kulangiappar M Anbu Kulandainathan and AMuthukumaran ldquoA simple and regioselective 120572-bromination ofalkyl aromatic compounds by two-phase electrolysisrdquo Tetrahe-dron Letters vol 46 no 41 pp 7047ndash7050 2005

[13] B G Soares N A Souza and D X Pires Quımica OrganicamdashTeoria e Tecnica de Preparacao Purificacao e Identificacao deCompostos Organicos Guanabara SA Rio de Janeiro Brazil 1stedition 1988

[14] H Wendt M Linardi and E M Arico ldquoCelulas a Combustıvelde Baixa Potencia para Aplicacoes Estacionariasrdquo QuımicaNova vol 3 pp 470ndash476 2002

[15] R M Silverstein G C Bassler and T C Morrill SpectrometricIdentification of Organic Componds John Wiley amp Sons Singa-pore 5th edition 1991

[16] F Wudl and S Shi ldquoSynthesis and characterization of a water-soluble poly(p-phenylenevinylene) derivativerdquoMacromoleculesvol 23 no 8 pp 2119ndash2124 1990

[17] A R Freitas G J Vidotti A F Rubira and E C Muniz ldquoPoly-chloroprene degradation by a Photo-Fenton processrdquo PolymerDegradation and Stability vol 87 no 3 pp 425ndash432 2005

[18] P S Curti G J Vidotti A F Rubira and E C Muniz ldquoSomekinetic parameters of the degradation of natural rubber inducedby chloranil and iron (III) chloride in solutionrdquo PolymerDegradation and Stability vol 79 no 2 pp 325ndash331 2003

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CatalystsJournal of


OH

EE

E

O

E E E

Ortho position attack


∙ ∙

∙ ∙

OH∙ ∙

∙ ∙ OH∙ ∙

∙ ∙

OH∙ ∙

∙ ∙

OH∙ ∙

∙ ∙

HO

HO

E

E

E E E E


Para position attack

∙ ∙

∙ ∙

HO∙ ∙

∙ ∙

HO∙ ∙

∙ ∙HO

∙ ∙

∙ ∙

HO∙ ∙

∙ ∙

Scheme 1 Resonance structures of ortho and para attacks in electrophilic substitutionswith activator group where ldquoErdquo can be any electrophile

NaINaClO

I

OH OH

Scheme 2 Synthesis of 4-iodo-25-dimethylphenol

this group stabilizes the HOMO and LUMO levels being ableto control their relatives positions [8] In the para position tothe cyano group we introduce a six carbon atoms chain andat the end of the carbon chain there is a bromine atom

2 Materials and Methods

21 Synthesis of 4-Iodo-25-dimethylphenol In this organicsynthesis Scheme 2 we used 002 moles of 25-dimethylphe-nol and equivalent amounts of sodium iodide and sodiumhydroxide were dissolved in 50mL of methanol present ina three-necked flask The solution was cooled in an ice bathand sodium chloride solution until the temperature reached0∘C for temperature control coupled to a thermometer in oneof the necked flasks In another necked flask adapted to anaddition funnel containing 375mL of a sodium hypochlorite

solution at 4wwThis solution was slowly dripped into thesolution contained in the flask in a way that the temperaturedid not exceed 4∘C

The mixture was stirred with the aid of magnetic stirringand after the addition of all the solution from the funnel themixture was left under stirring for another two hours at atemperature between 0 and 2∘C [9] For product purificationthe obtained solution was treated with 40mL of an aqueoussolution of sodium thiosulfate (Na

2S2O3) to 10 and then

the pH was adjusted to 70 using a 10 hydrochloric acidsolution In some cases the product was crystallized at thispoint and can thus be filtered By having no crystallizationoccurred 50mL of chloroform was added and the phaseswere separated by separatory funnel So it was added to thecalcium carbonate anhydrous in the organic phase (dryingagent) and the solution was then filtered and the solvent was


OH OH

I

CuCN

NC


















OHOH

NCNC

OHO(CH2)6ClKOHTBAB


NCNC



772

602

2857

1543

445

113412501406

1488

2360

2914

Tran

smitt

ance

()

3340

4000 3500 3000 2500 2000 1500 1000 5000

20

40

60

80

100





3






752 164467

669

217

(ppm)

725

232

8 7 6 5 4 3 2 1 0








1190

1413

2922

2224 1611 691

507

3232

Tran

smitt

ance

()

4000 3500 3000 2500 2000 1500 1000 500


minus20

0

20

40

60

80

100









(ppm)

733725669

363

243218

115

8 7 6 5 4 3 2 1 0










22202940

3400

Tran

smitt

ance

()

1600 1500 125010802853

4000 3500 3000 2500 2000 1500 1000 500


000

002

004

006

008






symmetric)2853




symmetric)1250






(ppm)8 7 6 5 4 3 2 1 0

145182

215247

365

397

665730

725

161


0

20

40

60

80

100Tr

ansm

ittan

ce (

)

516

670

2220

3400

2940

2853

40004500 3500 3000 2500 2000 1500 1000 500







(ppm)8 7 6 5 4 3 2 1 0

142160

181

215246

341

365397

529

665729

725









(ppm)

3360

3279

6293

6823

0030060090012001500




9H8ON




4 Conclusion



3000

102030405060708090

100

Rela

tive a

bund

ance

14700

8296

1480113197

3089824705164969097 224867697 312012480918094 27983

50 100 150 200 250 350

mz

34495




References































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


OH OH

I

CuCN

NC


















OHOH

NCNC

OHO(CH2)6ClKOHTBAB


NCNC



772

602

2857

1543

445

113412501406

1488

2360

2914

Tran

smitt

ance

()

3340

4000 3500 3000 2500 2000 1500 1000 5000

20

40

60

80

100





3






752 164467

669

217

(ppm)

725

232

8 7 6 5 4 3 2 1 0








1190

1413

2922

2224 1611 691

507

3232

Tran

smitt

ance

()

4000 3500 3000 2500 2000 1500 1000 500


minus20

0

20

40

60

80

100









(ppm)

733725669

363

243218

115

8 7 6 5 4 3 2 1 0










22202940

3400

Tran

smitt

ance

()

1600 1500 125010802853

4000 3500 3000 2500 2000 1500 1000 500


000

002

004

006

008






symmetric)2853




symmetric)1250






(ppm)8 7 6 5 4 3 2 1 0

145182

215247

365

397

665730

725

161


0

20

40

60

80

100Tr

ansm

ittan

ce (

)

516

670

2220

3400

2940

2853

40004500 3500 3000 2500 2000 1500 1000 500







(ppm)8 7 6 5 4 3 2 1 0

142160

181

215246

341

365397

529

665729

725









(ppm)

3360

3279

6293

6823

0030060090012001500




9H8ON




4 Conclusion



3000

102030405060708090

100

Rela

tive a

bund

ance

14700

8296

1480113197

3089824705164969097 224867697 312012480918094 27983

50 100 150 200 250 350

mz

34495




References































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


OHOH

NCNC

OHO(CH2)6ClKOHTBAB


NCNC



772

602

2857

1543

445

113412501406

1488

2360

2914

Tran

smitt

ance

()

3340

4000 3500 3000 2500 2000 1500 1000 5000

20

40

60

80

100





3






752 164467

669

217

(ppm)

725

232

8 7 6 5 4 3 2 1 0








1190

1413

2922

2224 1611 691

507

3232

Tran

smitt

ance

()

4000 3500 3000 2500 2000 1500 1000 500


minus20

0

20

40

60

80

100









(ppm)

733725669

363

243218

115

8 7 6 5 4 3 2 1 0










22202940

3400

Tran

smitt

ance

()

1600 1500 125010802853

4000 3500 3000 2500 2000 1500 1000 500


000

002

004

006

008






symmetric)2853




symmetric)1250






(ppm)8 7 6 5 4 3 2 1 0

145182

215247

365

397

665730

725

161


0

20

40

60

80

100Tr

ansm

ittan

ce (

)

516

670

2220

3400

2940

2853

40004500 3500 3000 2500 2000 1500 1000 500







(ppm)8 7 6 5 4 3 2 1 0

142160

181

215246

341

365397

529

665729

725









(ppm)

3360

3279

6293

6823

0030060090012001500




9H8ON




4 Conclusion



3000

102030405060708090

100

Rela

tive a

bund

ance

14700

8296

1480113197

3089824705164969097 224867697 312012480918094 27983

50 100 150 200 250 350

mz

34495




References































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


1190

1413

2922

2224 1611 691

507

3232

Tran

smitt

ance

()

4000 3500 3000 2500 2000 1500 1000 500


minus20

0

20

40

60

80

100









(ppm)

733725669

363

243218

115

8 7 6 5 4 3 2 1 0










22202940

3400

Tran

smitt

ance

()

1600 1500 125010802853

4000 3500 3000 2500 2000 1500 1000 500


000

002

004

006

008






symmetric)2853




symmetric)1250






(ppm)8 7 6 5 4 3 2 1 0

145182

215247

365

397

665730

725

161


0

20

40

60

80

100Tr

ansm

ittan

ce (

)

516

670

2220

3400

2940

2853

40004500 3500 3000 2500 2000 1500 1000 500







(ppm)8 7 6 5 4 3 2 1 0

142160

181

215246

341

365397

529

665729

725









(ppm)

3360

3279

6293

6823

0030060090012001500




9H8ON




4 Conclusion



3000

102030405060708090

100

Rela

tive a

bund

ance

14700

8296

1480113197

3089824705164969097 224867697 312012480918094 27983

50 100 150 200 250 350

mz

34495




References































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


22202940

3400

Tran

smitt

ance

()

1600 1500 125010802853

4000 3500 3000 2500 2000 1500 1000 500


000

002

004

006

008






symmetric)2853




symmetric)1250






(ppm)8 7 6 5 4 3 2 1 0

145182

215247

365

397

665730

725

161


0

20

40

60

80

100Tr

ansm

ittan

ce (

)

516

670

2220

3400

2940

2853

40004500 3500 3000 2500 2000 1500 1000 500







(ppm)8 7 6 5 4 3 2 1 0

142160

181

215246

341

365397

529

665729

725









(ppm)

3360

3279

6293

6823

0030060090012001500




9H8ON




4 Conclusion



3000

102030405060708090

100

Rela

tive a

bund

ance

14700

8296

1480113197

3089824705164969097 224867697 312012480918094 27983

50 100 150 200 250 350

mz

34495




References































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


(ppm)8 7 6 5 4 3 2 1 0

142160

181

215246

341

365397

529

665729

725









(ppm)

3360

3279

6293

6823

0030060090012001500




9H8ON




4 Conclusion



3000

102030405060708090

100

Rela

tive a

bund

ance

14700

8296

1480113197

3089824705164969097 224867697 312012480918094 27983

50 100 150 200 250 350

mz

34495




References































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


3000

102030405060708090

100

Rela

tive a

bund

ance

14700

8296

1480113197

3089824705164969097 224867697 312012480918094 27983

50 100 150 200 250 350

mz

34495




References































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

Synthesis and Characterization of PPV Monomer for Subsequent Electropolymerization

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Transcript of Synthesis and Characterization of PPV Monomer for Subsequent Electropolymerization