Abstract
Knoevenagel condensation of phenylacetonitrile with 4-diphenylaminophenylacetonitrile in the presence of piperidine was carried out to obtain a novel conjugated compound. In addition to the expected compound 2-(phenyl)-3-(4-diphenylaminophenyl)acrylonitrile (I), the 3-((4-diphenylamino)phenyl)-2,4-diphenylpentanedinitrile (II) was also obtained with a good yield. Compound II was obtained as a result of the Michael addition of phenylacetonitrile with 2-(phenyl)-3-(4-diphenylaminophenyl)acrylonitrile (I). Conversely, when the same reaction was performed in the presence of KOH as catalyst, only the α,β-unsaturated nitrile (I) was afforded with a 92 % yield. The structures were confirmed with IR, EI-MS and NMR spectroscopy. Single crystals I and II were formed and their structures were determined by X-ray single-crystal diffraction analysis. Crystal I belongs to the monoclinic system with space group P21/n having unit cell parameters of a = 16.8589(5) Å, b = 6.68223(17) Å, c = 19.8289(7) Å, β = 111.133(4)○ and Z = 4. Crystal II belongs to the same monoclinic system with space group P21/c, having unit cell parameters of a = 10.8597(4) Å, b = 24.7533(10) Å, c = 9.7832(4) Å, β = 91.297(3)○ and Z = 4. In addition to the structural data analysis, some theoretical calculations that reveal the nature of relevant structure-property relationships are also reported.
[1] Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G., & Taylor, R. (1987). Tables of bond lengths determined by X-ray and neutron diffraction. Part 1. Bond lengths in organic compounds. Journal of the Chemical Society, Perkin Transactions 2, 1987, S1–S19. DOI: 10.1039/p298700000s1. 10.1039/p298700000s1Search in Google Scholar
[2] Augé, J., Lubin, N., & Lubineau, A. (1994). Acceleration in water of the Baylis-Hillman reaction. Tetrahedron Letters, 35, 7947–7948. DOI: 10.1016/0040-4039(94)80018-9. 10.1016/0040-4039(94)80018-9Search in Google Scholar
[3] Becke, A. D. (1993). Density-functional thermochemistry. III. The role of exact exchange. The Journal of Chemical Physics, 98, 5648–5652. DOI: 10.1063/1.464913. http://dx.doi.org/10.1063/1.46491310.1063/1.464913Search in Google Scholar
[4] Bellamy, L. J. (1975). The infra-red spectra of complex molecules. New York, NY, USA: Wiley. http://dx.doi.org/10.1007/978-94-011-6017-910.1007/978-94-011-6017-9Search in Google Scholar
[5] Ditchfield, R., Hehre, W. J., & Pople, J. A. (1971). Self-consistent molecular-orbital methods. IX. An extended Gaussian-type basis for molecular-orbital studies of organic molecules. The Journal of Chemical Physics, 54, 724–728. DOI: 10.1063/1.1674902. http://dx.doi.org/10.1063/1.167490210.1063/1.1674902Search in Google Scholar
[6] D’Sa, B. A., Kisanga, P., & Verkade, J. G. (1998). Direct synthesis of α,β-unsaturated nitriles catalyzed by nonionic superbases. The Journal of Organic Chemistry, 63, 3961–3967. DOI: 10.1021/jo972343u. http://dx.doi.org/10.1021/jo972343u10.1021/jo972343uSearch in Google Scholar
[7] Fraysse, M. J. (1980). Nitriles: their application in perfumery. Perfumer & Flavorist, 4, 11–12. Search in Google Scholar
[8] Fringuelli, F., Pani, G., Piermatti, O., & Pizzo, F. (1994). Condensation reactions in water of active methylene compounds with arylaldehydes. One-pot synthesis of flavonols. Tetrahedron, 50, 11499–11508. DOI: 10.1016/s0040-4020(01)89287-5. 10.1016/S0040-4020(01)89287-5Search in Google Scholar
[9] Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G. A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H. P., Izmaylov, A. F., Bloino, J., Zheng, G., Sonnenberg, J. L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J. A., Jr., Peralta, J. E., Ogliaro, F., Bearpark, M., Heyd, J. J., Brothers, E., Kudin, K. N., Staroverov, V. N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J. C., Iyengar, S. S., Tomasi, J., Cossi, M., Rega, N., Millam, N. J., Klene, M., Knox, J. E., Cross, J. B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R. E., Yazyev, O., Austin, A. J., Cammi, R., Pomelli, C., Ochterski, J. W., Martin, R. L., Morokuma, K., Zakrzewski, V. G., Voth, G. A., Salvador, P., Dannenberg, J. J., Dapprich, S., Daniels, A. D., Farkas, Ö., Foresman, J. B., Ortiz, J. V., Cioslowski, J., & Fox, D. J. (2009). Gaussian 09 Revision A.1 [computer software]. Wallingford, CT, USA: Gaussian. Search in Google Scholar
[10] Frost, H. V. (1889). Ueber die Condensation von Benzylcyanid und seinen Substitutionsproducten mit Aldehyden und mit Amylnitrit. Justus Liebigs Annalen der Chemie, 250, 156–166. DOI: 10.1002/jlac.18892500106. (in German) http://dx.doi.org/10.1002/jlac.1889250010610.1002/jlac.18892500106Search in Google Scholar
[11] Guillemin, J. C., Breneman, C. M., Joseph, J. C., & Ferris, J. P. (1998). Regioselectivity of the photochemical addition of ammonia, phosphine, and silane to olefinic and acetylenic nitriles. Chemistry — A European Journal, 4, 1074–1082. DOI: 10.1002/(sici)1521-3765(19980615)4:6〈1074::aid-chem1074〉3.0.co;2-b. http://dx.doi.org/10.1002/(SICI)1521-3765(19980615)4:6<1074::AID-CHEM1074>3.0.CO;2-B10.1002/(SICI)1521-3765(19980615)4:6<1074::AID-CHEM1074>3.0.CO;2-BSearch in Google Scholar
[12] Guillot, R., Loupy, A., Meddour, A., Pellet, M., & Petit, A. (2005). Solvent-free condensation of arylacetonitrile with aldehydes. Tetrahedron, 61, 10129–10137. DOI: 10.1016/j.tet.2005.07.040. http://dx.doi.org/10.1016/j.tet.2005.07.04010.1016/j.tet.2005.07.040Search in Google Scholar
[13] Improta, R., & Santoro, F. (2005). Excited-state behavior of trans and cis isomers of stilbene and stiff stilbene: A TD-DFT study. The Journal of Physical Chemistry A, 109, 10058–10067. DOI: 10.1021/jp054250j. http://dx.doi.org/10.1021/jp054250j10.1021/jp054250jSearch in Google Scholar
[14] Jenner, G. (1996). Comparative study of physical and chemical activation modes. The case of the synthesis of β-amino derivatives. Tetrahedron, 52, 13557–13568. DOI: 10.1016/0040-4020(96)00831-9. 10.1016/0040-4020(96)00831-9Search in Google Scholar
[15] Knoevenagel, E. (1896). Ueber eine Darstellungsweise des Benzylidenacetessigesters. Berichte der Deutschen Chemischen Gesellschaft, 29, 172–174. DOI: 10.1002/cber.18960290133. (in German) http://dx.doi.org/10.1002/cber.1896029013310.1002/cber.18960290133Search in Google Scholar
[16] Lin, R., Horng, H. C., Lin, H.M., Lin, S. Y., Hon, Y. S., & Chow, T. J. (2010). 2-Amino-3-naphthylacrylonitrile derivatives as green luminance dyes. Journal of the Chinese Chemical Society, 57, 805–810. http://dx.doi.org/10.1002/jccs.20100002710.1002/jccs.201000027Search in Google Scholar
[17] Lorente, A., Galan, C., Fonseca, I., & Sanz-Aparicio, J. (1995). 1-Aminocyclohexene-2,4-dicarbonitrile derivatives. Syntheses and structural study. Canadian Journal of Chemistry, 73, 1546–1555. DOI: 10.1139/v95-192. 10.1139/v95-192Search in Google Scholar
[18] Loupy, A., Pellet, M., Petit, A., & Vo-Thanh, G. (2005). Solvent-free condensation of phenylacetonitrile and nonanenitrile with 4-methoxybenzaldehyde: Optimization and mechanistic studies. Organic & Biomolecular Chemistry, 3, 1534–1540. DOI: 10.1039/b418156e. http://dx.doi.org/10.1039/b418156e10.1039/b418156eSearch in Google Scholar
[19] Lubineau, A., & Augé, J. (1999). Water as solvent in organic synthesis. In P. Knochel (Ed.), Modern solvents in organic synthesis (pp. 1–39). Berlin, Germany: Springer. DOI: 10.1007/3-540-48664-x 1. http://dx.doi.org/10.1007/3-540-48664-X_110.1007/3-540-48664-XSearch in Google Scholar
[20] Mabrouk, A., Azazi, A., & Alimi, K. (2010). On the properties of new benzothiazole derivatives for organic light emitting diodes (OLEDs): A comprehensive theoretical study. Journal of Physics and Chemistry of Solids, 71, 1225–1235. DOI: 10.1016/j.jpcs.2010.04.020. http://dx.doi.org/10.1016/j.jpcs.2010.04.02010.1016/j.jpcs.2010.04.020Search in Google Scholar
[21] Michel, F., Mecklein, L., Crastes de Paulet, A., Doré, J. C., Gilbert, J., & Miquel, J. F. (1984). The effect of various acrylonitriles and related compounds on prostaglandin biosynthesis. Prostaglandins, 27, 69–84. DOI: 10.1016/0090-6980(84)90221-1. http://dx.doi.org/10.1016/0090-6980(84)90221-110.1016/0090-6980(84)90221-1Search in Google Scholar
[22] Mori, K. (1976). Synthetic chemistry of insect pheromones and juvenile hormones (Recent developments in the chemistry of natural carbon compounds). Budapest, Hungary: Akadémiai Kiadó. Search in Google Scholar
[23] Nakanishi, K., & Solomon, P. H. (1977). Infrared absorption spectroscopy. Oakland, CA, USA: Holden-Day. Search in Google Scholar
[24] Peat, J. R., Minchin, F. R., Jeffcoat, B., & Summerfield, R. J. (1981). Young reproductive structures promote nitrogen fixation in soya bean. Annals of Botany, 48, 177–182. 10.1093/oxfordjournals.aob.a086111Search in Google Scholar
[25] Percino, M. J., Chapela, V. M., Montiel, L. F., Pérez-Gutiérrez, E., & Maldonado, J. L. (2010). Spectroscopic characterization of halogen- and cyano-substituted pyridinevinylenes synthesized without catalyst or solvent. Chemical Papers, 64, 360–367. DOI: 10.2478/s11696-010-0012-z. http://dx.doi.org/10.2478/s11696-010-0012-z10.2478/s11696-010-0012-zSearch in Google Scholar
[26] Percino, M. J., Chapela, V. M., Pérez-Gutiérrez, E., Cerón, M., & Soriano, G. (2011). Synthesis, optical and spectroscopic characterisation of substituted 3-phenyl-2-arylacrylonitriles Chemical Papers, 65, 42–51. DOI: 10.2478/s11696-010-0075-x. http://dx.doi.org/10.2478/s11696-010-0075-x10.2478/s11696-010-0075-xSearch in Google Scholar
[27] Percino, M. J., Chapela, V. M., Cerón, M., Castro, M. E., Soriano-Moro, G., Pérez-Gutiérrez, E., & Meléndez-Bustamante, F. (2012). Synthesis and characterization of conjugated pyridine-(N-diphenylamino) acrylonitrile derivatives: Photophysical properties. Journal of Materials Science Research, 1, 181–192. DOI: 10.5539/jmsr.v1n2p181. http://dx.doi.org/10.5539/jmsr.v1n2p18110.5539/jmsr.v1n2p181Search in Google Scholar
[28] Pérez-Gutiérrez, E., Percino, M. J., Chapela, V. M., Cerón, M., Maldonado, J. L., & Ramos-Ortiz, G. (2011). Synthesis, characterization and photophysical properties of pyridinecarbazole acrylonitrile derivatives. Materials, 4, 562–574. DOI: 10.3390/ma4030562. http://dx.doi.org/10.3390/ma403056210.3390/ma4030562Search in Google Scholar PubMed PubMed Central
[29] Saidalimu, I., Fang, X., Lv, W. W., Yang, X. Y., He, X. P., Zhang, J. Y., Wu, F. H., & Pizzo, F. (2013). Organocatalytic asymmetric Michael addition/carbon-carbon bond cleavage of trifluoromethyl α-fluorinated gem-diols to nitroolefins. Advanced Synthesis & Catalysis, 355, 857–863. DOI: 10.1002/adsc.201200757. http://dx.doi.org/10.1002/adsc.20120075710.1002/adsc.201200757Search in Google Scholar
[30] Sağirli, A., Dürüst, Y., Kariuki, B., & Knight, D. W. (2013). A practical isocyanide-based multicomponent synthesis of polysubstituted cyclopentenes. Tetrahedron, 69, 69–72. DOI: 10.1016/j.tet.2012.10.065. http://dx.doi.org/10.1016/j.tet.2012.10.06510.1016/j.tet.2012.10.065Search in Google Scholar
[31] Sheldrick, G. M. (1998). SHELXL 97 [computer software]. Göttingen, Germany: University of Göttingen. Search in Google Scholar
[32] The Cambridge Crystallographic Data Centre (2012). Mercury 3.0 [computer software]. Cambridge, UK: The Cambridge Crystallographic Data Centre. Search in Google Scholar
[33] Williams, D. H., & Fleming, I. (1980). Spectroscopic methods in organic chemistry (3rd ed.). London, UK: MacGraw-Hill. Search in Google Scholar
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