Mallakpour, Shadpour E

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Indian Journal of ChemistryVol. 36B, Apri11997, pp. 354-356One pot synthesis of 1,4-dicarboxymethyl-2,3-diphenylnaphthaleneShadpour E MallakpourOrganic Polymer Chemistry Research Laboratory, College ofChemistry, Isfahan University of Technology, Isfahan, 84156,I.R. IranReceived 24 July 1996; accepted 19 November 1996Benzene 2 from aprotic diazotization of anthranilicacid 1 with isoamylnitrite and subsequent thermal de-composition of the resulted benzenediazonium-2-car-boxylate (in situ), has been reacted with 2,5-dicarbome-thoxy- 3,4-diphenylcyclopentadienone 3 in 1,2-dichlor-oethane as a solvent at the refluxing temperature. Thisreaction furnishes 1,4-dicarboxymethyl- 2,3-diphenylnaphthalene 5 after loss of carbon monoxide in quanti-tative yield. It has been converted into its dicarbohydra-zine derivatives. These naphthalene derivatives havebeen studied by high field IH-NMR and 13C-NMRspectroscopy.Difunctional carboxylic acids. and their derivativesare very valuable compounds for the synthesis ofcommercial polyesters and polyamides 1• Simplearomatic or aliphatic dicarboxylic acids are usuallyprepared by oxidation of the corresponding diolsor dialkyl derivatives. More complicated dicarbox-ylic acids however, need several steps for theirpreparation. Recently we reported/ the synthesisof some alkyl and phenyl substituted naphthalenesin one step.The purpose of this work was to synthesis 1,4-dicarboxymethyl-2,3-diphenylnaphthalene 5 in onestep and study its high field NMR. Although thereare a variety of methods for the generation of thereactive intermediate benzene':" 2 but one of thebest methods is through the aprotic diazotizationof anthraniic acid 1 and subsequent thermal de-composition of diazonium salt. This techniques togenerate benzene 2 avoids the isolation and handl-ing of the hazardous and explosive benzenediazo-nium-2-carboxylate and serves as a convenientpreparative source for benzyne.2,5- Dicarbomethoxy- 3,4-diphenylcyclopentadie-none 3 was prepared from base-catalyzed conden-sation of dimethyl acetonedicarboxylate with ben-zil and subsequent acid-catalyzed dehydration ofthe resulted enol". Benzyne 2 was generated fromanthranilic acid 1 in 1,2-dichloroethane at 85°Cunder aprotic condition with isoamylnitrite andNoteoIIO(-OHI --~NH2oIIE = COMe 3I SOLVENT+~©ItD• -coD-BuOHScheme Iwas reacted with 3 via [4 + 2] Diels-Alder cycload-dition reaction. The resulted adduct 4 was notstable at the reaction temperature, as it lostcarbon monoxide and gave 5 in 100% yield~SchemeI).The high field 1H NMR spectrum of 5 showeda. singlet at 3.54 ppm due to the two methyl pro-tons. The peaks at 7.05-7.25 ppm were assigned,to the ten protons of the phenyl group". Thepeaks at 7.54-7.57 ppm (distorted doublet of dou-blet) and 7.86-7.89 ppm (distorted doublet ofdoublet) were assigned to the four protons of thenaphthalene ring. The protons on position 5 and 8of the naphthalene ring (HA and HA') are chemicalshift equivalent to each other and the protons onposition 6 and 7 of the naphthalene ring (Hx andHx') are also chemical shift equivalent to eachother. lAX and lAX' are the same and equal to 6.41Hz. lAX and lAX' are also the same but smallerand are equal to 3.20 Hz. Since HA and HA' cou-~le differently to another specific proton, they arenot magnetically equivalent. Thus, it resembles anAA'XX' pattern of two distorted doublet of dou-blet.The compound 5 has 26 carbon atoms in itsskeleton. Since this compound has a plane ofsymmetry, therefore its i3C NMR signal reduces tofewer peaks. Thus 11 signals were observed onl3C NMR spectrum which are completely assignedto the corresponding carbon atoms (Table I).The compound 5 was allowed to react with hy-drazine monohydrate in refluxing n-butanol andthe compound 6 was obtained in high yield. Thehigh field 1H NMR spectrum of 6 showed anAAXX' pattern similar to 5. It does not showpeak between 3.00-4.00 ppm which indicates theabsence of any diesters. The l3C NMR spectrumof 6 showed peaks at 125.30, .125.56, 126.60,126.78, 128.18, 130.58, 132.59, 139.28, 140.63 and172.70 ppm which was in agreement with assignedstructure 6.Conclusions1,4-Dicarboxymethyl- 2,3-diphenyl naphtha-lene 5 can be easily synthesized in one pot reac-tion as a crystalline solid in quantitative of yield.This compound is readily converted to its dihyd-razine 6 derivative. The compounds 5 and 6 arevery interesting difuctional monomers and havepotential to be used in poly condensation reactionsfor making novel polymers. Work in this area isunder investigation.Experimental Section •General. Infrared spectra (KBr) were recordedon a Shimadzu 435 infrared spectrophotometer(vmax in cm-l) and IH NMR (500 MHz) and i3CNMR (125 MHz) spectra were obtained on a Var-ian XL-500 and Bruker AM400 spectrometer.All' melting points were taken on a Gallenhampmelting point apparatus and are uncorrected. Ele-mental analysis was performed by the ResearchInstitute of Petroleum Industry, Tehran, IR Iran.Reagents were [purchased from Aldrich ChemicalCO., Fluka Chemical CO. and Riedel-dehaen AG.2,5- Dicarbomethoxy- 3,4-diphenylcyclopentadie-none 3Base catalyzed condensation reaction of benzilwith dimethyl-1,3-acetonedicarboxylate gave 2,5-dicarbomethoxy-t-hydroxyl- 3,4-diphenylcydopent-2-en-1-one in 83% yield, m.p. 134-36° (Lit.16 m.p.136-40°). It was not recrystallized and used assuch for further reaction. Acid catalyzed dehydra-tion of this compound in acetic anhydride gave 3as orange crystals (99.6%), m.p. 166-68° (Lit.16m.p. 162-164° after recrystallization from aceticacid).NOTES 355type of ppm type of ppmcarbon carbona 52.07 g 129.91b 12~<.24 h 133.33c 127.03 137.14d 127.38 j 138.10 .e 127.63 k 169.09f 128.70Reaction of benzyne 2 with 3: Formation of 5\In a 100 mL three-necked round-bottomed flask,equipped with a magnetic stirring bar, a watercooled condenser and two constant pressuredropping funnels were placed 0,30 g (8.612 x 10-4mole) of 3 and 20 mL of 1,2-dichloroethane. Asolution of 0.118 g (8.612 x 10-4 mole) of anthra-nilic acid in 15 mL of 1,2-dichloroethane was tak-en in one of the dropping funnels. The other fun-nel was charged with a solution of 0.20 g (0.23mL, 1.722 x 10-3 mole) of isoamylnitrite in 15 mLof 1,2-dichloroethane. The flask was heated on aheating mantle while stirring. Solutions fromdropping funnels were added dropwise simultane-ously to the refluxing mixture over a period of 35min. and then continued for 60 min. The orangesolution turned to pale yellow color. The solventwas removed by simple distillation. The residuewas triturated with 10 mL of methanol. The whitesolid formed as filtered and dried 0.34 g, (100%).Recrystallization from hot n-hexane gave whitecrystals, m.p. 148-50°; IR (KBr): 3050(w),2950(w), 1720(s), 1600(w), 1570(w), 1'500(m),1440(s), 1370(s), 13lO(s), 1250(m), 1230(s),1200(s), 1140(s), 1100(w), 1070(m), 1040(s),1020(s), 950(m), 918(m), 840(m), 800(m), 760(s),700(s), 600(m), 560(m); IH NMR (500 MHz,CDCI3, int. ref. CDd3): 0 3.54 (s, 6H), 7.05-7.25(m, 10H), 7.54.7.57 (tld, 2H, JAX = JAX' = 6.41 Hz,JAX,=JAX' = 3.20 r)' 7.86-7.89 (dd, 2H,JAx=JAx,=6.41 Hz, iJAX,=JAX=3.20 Hz) (Found:C, 78.10; H, 5.20. C26H2004 requires C, 78.77; H,5.09%).1,4- Dicarbohydrazine- 2,3-diphenyl naphthalene6, 1,4-Dicarboxymethyl- 2,3-diphenyl naphthalene356 INDIAN J. CHEM. SEe. B, APRIL 1997(5; 1.13 g, 2.851 x 10-3 mole), 28 mL of hydra-zine monohydrate and 40 mL of n-butanol wereplaced into a 250 mL round-bottomed flask. Theflask was equipped with a water cooled condenserand a magnetic stirrer. The mixture was refluxedfor 24 hr while stirring. The solvent and excesshydrazine were removed to give 1.13 g (100%) ofwhite solid which was recrystallized from isoprop-anol, m.p. 320-22°; IR (KBr): 3350(m), 3200-2400(s, br) 1600(s, sh), 1590-1480(s, br), 1430(w),1410(s), 1330(m), 1280(m), 1l00(m), 1090(w),1070(w), 950(w), 850(w), 81O(m), 760(m), 700(s),590{m); 1H NMR (400 MHz, DMSO-dn, into ref.DMSO-dn): & 6.00-7.30(s, br, NHs) 7.00-7.08 (m,lOH), 7.42-7.44 (dd, 2H, JAX=JA'X:=6.46 Hz,JAX' = JAX' = 3.32 Hz), 7.93-7.96 (dd, 2H,JAX = JAX' = 6.46 Hz, lAX' =1J>;X = 3.32 Hz).AcknowledgementFinancial support for this work by the researchaffair, Isfahan university of Technology, Isfahan IRIran, IS gratefully acknowledged. I thank Dr OjvindDavidson, Department of Organic Chemistry, Uni-versity of Gotenborg for his kind help in recording500 MHz NMR spectra and to prof. R Stadler,Institute of Organic Chemistry, Johannes Guten-berg University of Mianz, Germany, for the 400MHz NMR spectra.References1 Stevens M P, Polymer chemistry, 2nd Ed (Oxford Univers-ity Press), 1990.2 Mallakpour S E, J Sci I R Iran, 4,1993,112.3 Wittig G & Pohmer L, Angew Chern, 67, 1955,348.4 Rabjohn N, Org Synth Call, 4, 1963,965.5 Leguldo F M, J Arn Chern Sac, 85,1963,1549.6 Friedman L & Loguldo F M, J Org Chern, 34, 1969,3089.7 GoffEL,J Am rhernSoc, 84, 1962, 3786.8 Beringer F M & Huang S J, J Org Chern, 29, 1964,445.9 Verbit L, Levy J S, Rabitz H & Kwalwasser W, Tetrahe-dron Lett, 1966, 1053.10 Stevens T E, J Org Chern, 32, 1965,855.11 Wittig G, Angew Chern int Ed Eng~ 4,1965,731.12 McNelies E, J Org Chern, 28, 1963,3188.13 ,Embree H D, Chern E"6 New, 49,1971,3.14 Wittig G & Hoffmann R W, Chern Ber, 95, 1962,2718.15 Campbell C D & Rees C W, Proc Chern Sac, 1964,296.16 White D M, J Org Chern, 39,1974, 1951.

One pot synthesis of 1,4-dicarboxymethyl-2,3-diphenylnaphthalene

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One pot synthesis of 1,4-dicarboxymethyl-2,3-diphenylnaphthalene

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