Abstract
Synthesis was performed and structure studied of endo-4-cyanotetracyclo[6.2.1.13,6.02,7]dodec-9-ene prepared by reaction of a stereochemically uniform endo-5-cyanobicyclo[2.2.1]hept-2-ene with cyclopentadiene. By analysis of potential energy surface (PES) for reactions of endo-5-cyanobicyclo[2.2.1]hept-2-ene and the respective exo-stereoisomer with cyclopentadiene (in B3LYP/6-31G(d) approximation) the endo,exo-junction and anti-orientation of the methylene bridges in the bicyclic fragments of the adducts were shown to be preferable. Reduction of the tetracyclic nitrile with lithium aluminum hydride yielded endo-4-aminomethyltetracyclo-[6.2.1.13,6.02,7]dodec-9-ene whose geometry and conformational characteristics were studied by means of molecular mechanics method. Products were obtained from reactions of the tetracyclic amine with p-toluene-, p-chloro-benzene-, p-nitrobenzenesulfonyl chlorides, p-nitrobenzoyl chloride, succinic anhydride, mesityl and p-toluene-sulfonyl isocyanates, phenyl, p-toluenesulfonyl, and benzoyl isothiocyanates, p-nitrophenyloxirane, and N-(2,3-epoxypropyl)carbazole. A series of the amine derivatives was epoxidized with perphtahlic acid. The structure of compounds synthesized was confirmed by analysis of their IR spectra, 1H, 13C, and two-dimensional NMR spectra, and additionally by calculation of the chemical shifts in 1H and 13C NMR spectra by procedures GIAO and CSGT in PBE1PBE/6-31G## approximation.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
REFERENCES
Vereshchagin, A.N. and Arbuzov, B.A., Izv. Akad. Nauk SSSR, 1965, p. 35.
Japan Patent 74118902, 1974; Chem. Abstr., 1975, vol. 82, 141886v.
Patent 74123189, 1974; Chem. Abstr., 1975, vol. 82, 15750b; Patent 2249808, 1973; Chem. Abstr., 1973, vol. 79, 19679f.
Patent 57-16972, 1982; Ref. Zh. Khim., 1983, vol. 23, no. 96P; German Patent 221172, 1985; Ref. Zh. Khim., 1985, 24O68P.
Kas'yan, A.O., Golodaeva, E.A., Yuzlenko, O.V., Shishkina, C.V., Shishkin, O.V., and Kas'yan, L.I., Zh. Org. Khim., 2003, vol. 39, p. 1796.
Kas'yan, L.I., Okovityi, S.I., Kas'yan, A.O., Golodaeva, E.A., and Yuzlenko, O.V., Vi sn. Dni propetrovs' kogo un-tu., 2000, no. 3.
Molecular Mechanics, Burkert, U. and Allinger, N. L., Eds., Washington, DC: ACS, 1982.
Becke, A.D., J. Phys. Chem., 1973, vol. 98, p. 5648.
Fliege, W. and Huisgen, R.N., Liebigs, Ann. Chem., 1973, vol. 12, p. 2038; Onishchenko, A.S., Dienovyi sintez Moscow: Mir, 1963.
Wipff, G. and Morokuma, K., Tetrahedron Lett., 1980, vol. 21, p. 4445.
Kas'yan, A.O., Tarabara, I.N., Zlenko, E.T., Okovityi, S.I., and Kas'yan, L.I., Zh. Org. Khim., 1999, vol. 35, p. 1042.
Nakanisi, K., Infrared Absorption Spectroscopy. Practical, San Francisco: Holden-Day; Tokyo: Nankodo, 1962.; Bellamy, L.J., Advances in Infra-red Group Frequencies, London: Methuen, 1966. Translated under the title Novye dannye po IK spektram slozhnykh molekul, Moscow: Mir, 1971, p. 177.
Zefirov, N.S. and Sokolov, V.I., Usp. Khim., 1967, vol. 36, p. 243.
Kas'yan, L.I., Zlenko, O.T., Mamchur, V.I., Kas'yan, A.O., and Tarabara, I.M., Farmatsevtichnii Zhurn., 2001, vol. 2, p. 59.
Parker, R.E. and Isaacs, N.C., Chem. Rev., 1959, vol. 59, p. 737; Kirk, D.N., Chem. Ind., 1973, p. 109.
Kas'yan, L.I., Seferova, M.F., and Okovityi, S.I., Alitsiklicheskie epoxydnye soedineniya Metody sinteza (Alicyclic Epoxy Compounds. Methods of Synthesis), Dnipropetrovs'k.: Vidav. DDU, 1996, 192 p; Kas'yan, L.I., Kas'yan, A.O., Okovityi, S.I. and Tarabara, I.N., Alitsiklicheskie epoxydnye soedineniya. Reaktsionnaya sposobnost. (Alicyclic Epoxy Compounds. Reactivity), Dnipropetrovs'k: Vidav. DNU, 2003, 516 p; Kasyan, L.I., Sereda, S.V., Potekhin, K.A., and Kasyan, A.O., Heteroatom Chem., 1997, vol. 8, p. 177; Kasyan, L.I., Tarabara, I.N., Savel'eva, O.A., and Kasyan, A.O., Heteroatom Chem., 2001, vol. 12, p. 119; Kas'yan, L.I., Zh. Org. Khim., 1999, vol. 35, p. 661; Kas'yan, L.I., Krasnovskaya, O.Yu., and Kas'yan, A.O.,Zh. Org. Khim., 1996, vol. 32, p. 1106; Golodaeva, E.A., Kas'yan, A.O., Bakumov, V.A., and Kas'yan, L.I., Zh. Org. Khim., 2003, vol. 39, p. 297.
Zefirov, N.S., Kasyan, L.I., Gnedenkov, L.Yu., Shashkov, A.S., and Cherepanova, E.G., Tetrahedron Lett., 1979, vol. 11, p. 949; Kas'yan, L.I., Kas'yan, A.O., Gorb, L.G., and Klebanov, B.M., Zh. Org. Khim., 1995, vol. 31, p. 678.
Tori, K., Kitahonoki, K., Tanida, H., and Tsuji, T., Tetrahedron Lett., 1964, vol. 11, p. 559; Shashkov, A.S., Cherepanova, E.G., Kas'yan, L.I., Gnedenkov, L.Yu., and Bombushkar., M.F., Izv. Akad. Nauk SSSR, Ser. Khim., 1980, p. 564.
London, F.J., Phys. Radium., 1937, vol. 8, p. 397; Ditchfield, R., Mol. Phys., 1974, vol. 27, p. 789; Wolinski, K., Hinton, J.F., and Pulay, P.J., J. Am. Chem. Soc., 1990, vol. 112, p. 8251.
Keith, T.A. and Bader, R.H.W., Chem. Phys. Lett., 1992, vol. 194, p. 1.
Perdew, J.P., Burke, K., and Ernzerhof, M., Phys. Rev. Lett., 1996, vol. 77, p. 3865.
Rossikhin, V.V., Okovytyy, S.I., Kasyan, L.I., Voronkov, E.O., Umrikhina, L.K., and Leszczynski, J. J., Phys. Chem. A, 2002, vol. 106, p. 4176.
Alder, K., Heimbach, K., and Reubke, R., Chem. Ber., 1958, vol. 91, p. 1516.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Kas'yan, L.I., Golodaeva, E.A., Okovityi, S.I. et al. Synthesis, Structure, and Derivatives of endo-4-Aminomethyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene. Russian Journal of Organic Chemistry 40, 1080–1091 (2004). https://doi.org/10.1023/B:RUJO.0000045886.62849.a8
Issue Date:
DOI: https://doi.org/10.1023/B:RUJO.0000045886.62849.a8