Abstract
Diels-Alder reactions of 1,2,3,4-tetrachloro-, 1,2,3,4-tetrachloro-5,5-dimethoxy-, and hexachlorocyclopentadienes with vinyl-and allylacetylene dienophiles were studied. Kinetic parameters of these reactions were determined, and the cycloaddition processes were assigned to the “neutral” type involving symmetric arrangement of the highest occupied and lowest unoccupied molecular orbitals of the diene and dienophile. Vinylacetylene derivatives were found to be more reactive than allylacetylenes. Increase in the number of chlorine atoms in the bicycloheptene fragment of the adduct favors its acetylene-allene isomerization.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
REFERENCES
Jeffery, T., Tetrahedron Lett., 1989, vol. 30, p. 2225.
Wong, T., Romero, F., and Fallis, A.G., J. Org. Chem., 1994, vol. 59, p. 5527.
Veliev, M.G., Shatirova, M.I., Chalabiev, Ch.A., Mamedov, I.M., and Mustafaev, A.M., Russ. J. Org. Chem., 1995, vol. 31, p. 52.
Mignani, G., Chevalier, C., Grass, P., Allmang, G., and Mord, D., Tetrahedron Lett., 1990, vol. 31, p. 5161.
Shostakovskii, M.F., Komarov, N.V., and Misyunas, V.K., Dokl. Akad. Nauk SSSr, 1967, vol. 173, p. 843.
Belyaev, N.M., Stadnichuk, M.D., and Boronaeva, T.R., Zh. Obshch. Khim., 1976, vol. 46, p. 1545.
Veliev, M.G., Guseinov, M.M., Yanovskaya, L.A., and Burstein, K.Ya., Tetrahedron, 1985, vol. 41, p. 749.
Veliev, M.G., Guseinov, M.M., Yanovskaya, L.A., Mamedov, E.Sh., and Bairamov, A.A., Izv. Akad. Nauk SSSR, Ser. Khim., 1980, p. 1358.
Veliev, M.G., Guseinov, M.M., Yanovskaya, L.A., and Gakhramanov, R.F., Izv. Akad. Nauk SSSR, Ser. Khim., 1981, p. 144.
Guseinov, M.M., Akhmedov, I.M., Ismailzade, I.G., Veliev, M.G., and Mamedov, I.M., Zh. Org. Khim., 1972, vol. 8, p. 1428.
Veliev, M.G., Chalabieva, A.Z., Gakhramanov, R.F., and Shatirova, M.I., Zh. Org. Khim., 1993, vol. 29, p. 1798.
Veliev, M.G., Chalabieva, A.Z., Gakhramanov, R.F., and Mustafaev, A.M., Zh. Org. Khim., 1994, vol. 30, p. 40.
Veliev, M.G., Chalabieva, A.Z., Shatirova, M.I., Mamedov, E.Sh., and Mamedov, I.M., Russ. J. Org. Chem., 2001, vol. 37, p. 223.
Marchand, P. and Rose, E., J. Am. Chem. Soc., 1968, vol. 90, p. 3724.
Franzus, B., Beurel, C., Chamberlain, F., Hines, T., and Snyder, I., J. Am. Chem. Soc., 1968, vol. 90, p. 3721.
Gordon, A.J. and Ford, R.A., The Chemist's Companion, New York: Wiley, 1972.
Singleton, D.A., Merrigan, S., and Thomas, A.A., Tetrahedron Lett., 1999, vol. 40, p. 639.
Onishchenko, A.S., Dienovyi sintez(Diels-Alder Reaction), Moscow: Akad. Nauk SSSR, 1963.
Zefirov, N.S., Shestakova, T.G., and Kirpichenok, M.A., Khimiya geksakhlortsiklopentadiena i rodstvennykh soedinenii(Chemistry of Hexachlorocyclopentadiene and Related Compounds), Moscow: Mosk. Gos. Univ., 1985.
Konovalov, A.I., Zh. Org. Khim., 1969, vol. 5, p. 1713.
Bazilevskii, M.V., Metod molekulyarnykh orbit i reaktsionnaya sposobnost' organicheskikh molekul(Molecular Orbital Theory and Reactivity of Organic Molecules), Moscow: Khimiya, 1969.
Burshtein, K.Ya. and Shorygin, P.P., Kvantovo-khimi-cheskie raschety v organicheskoi khimii i molekulyarnoi spektroskopii(Quantum-Chemical Calculations in Organic Chemistry and Molecular Spectroscopy), Moscow: Nauka, 1989.
Emanuel', N.M. and Knorre, D.G., Kurs khimicheskoi kinetiki(Lectures on Chemical Kinetics), Moscow: Vysshaya Shkola, 1969.
Mamedov, M.A., Akhmedov, I.M., and Ismailov, N.M., Khimiya atsetilena. Trudy III Vsesoyuznoi konferentsii(Chemistry of Acetylene. Proc. IIIrd All-Union Conf.), Moscow: Nauka, 1972, p. 188.
Rights and permissions
About this article
Cite this article
Veliev, M.G., Chalabieva, A.Z., Shatirova, M.I. et al. Diels-Alder Reaction of Polychlorocyclopentadienes with Vinyl-and Allylacetylene Dienophiles. Russian Journal of Organic Chemistry 40, 946–952 (2004). https://doi.org/10.1023/B:RUJO.0000045182.48103.82
Issue Date:
DOI: https://doi.org/10.1023/B:RUJO.0000045182.48103.82