Abstract
A number of previously unknown N-isopropenyl-substituted pyrroles, indoles, and di- and -triazoles were synthesized in 20-86% yield by reaction of the corresponding azole with an equilibrium mixture of propyne with allene or pure propyne and allene in the system KOH-DMSO (105-145°C, 5-15 h, atmospheric or elevated pressure). The reaction is regioselective. The electronic and steric structure and the degree of conjugation between the exocyclic double bond and the azole ring are discussed on the basis of the 1H and 13C NMR spectra. Almost complete absence of p-π conjugation in α,α'-disubstituted N-isopropenylazoles have been found.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
REFERENCES
Tarasova, O.A., Mal'kina, A.G., Mikhaleva, A.I., Brandsma, L., and Trofimov, B.A., Synth. Commun., 1994, vol. 24, p. 2035.
Trofimov, B.A., Pyrroles. Part Two: The Synthesis, Reactivity, and Physical Properties of Substituted Pyrroles, Jones, A., Ed., New York: Wiley, 1992, p. 131.
Mikhaleva, A.I., Trofimov, B.A., Korostova, S.E., Vasil'ev, A.N., and Balabanova, L.N., Izv. Sib. Otd. Akad. Nauk SSSR, Ser. Khim., 1979, issue 4, p. 105.
Trofimov, B.A., Mikhaleva, A.I., Korostova, S.E., Vasil'ev, A.N., and Balabanova, L.N., Khim. Geterotsikl. Soedin., 1977, p. 213.
Shostakovskii, M.F., Skvortsova, G.G., Glazkova, N.P., and Domnina, E.S., Khim. Geterotsikl. Soedin., 1969, p. 1070.
Skvortsova, G.G., Domnina, E.S., Shestova, L.A., Voronov, V.K., and Keiko, V.V., Khim. Geterotsikl. Soedin., 1976, p. 1247.
Domnina, E.S., Skvortsova, G.G., Glazkova, N.P., and Shostakovskii, M.F., Khim. Geterotsikl. Soedin., 1966, p. 390.
Ermakova, T.G., Tatarova, L.A., and Kuznetsova, N.P., Russ. J. Gen. Chem., 1997, vol. 67, p. 805.
Voropaev, V.N., Domnina, E.S., Glazkova, N.P., and Skvortsova, G.G., Zh. Prikl. Khim., 1983, vol. 56, p. 2289.
Russian Patent no. 2 030 406, 1995; Chem. Abstr., 1996, vol. 124, no. 117 324 d.
Wattanasin, S. and Kathawala, F.G., Synth. Commun., 1989, vol. 19, p. 2659.
Katritzky, A.R., Li, J., and Malhotra, N., Justus Liebigs Ann. Chem., 1992, p. 843.
Hopff, H., Wyss, U., and Lussi, H., Helv. Chim. Acta, 1960, vol. 43, p. 1967.
Ogata, M., Matsumoto, H., Kida, S., and Shimizu, S., Tetrahedron Lett., 1979, p. 5011.
Taber, A.M., Mushina, E.A., and Krentsel', B.A., Allenovye uglevodorody (Allene Hydrocarbons), Moscow: Nauka, 1987.
Trofimov, B.A., Tarasova, O.A., Mikhaleva, A.I., Kalinina, N.A., Sinegovskaya, L.M., and Henkelmann, J., Synthesis, 2000, p. 1585.
Tarasova, O.A., Shmidt, E.Yu., Albanov, A.I., Mikhaleva, A.I., Brandsma, L., and Trofimov, B.A., Russ. J. Org. Chem., 1999, vol. 35, p. 1499.
Tarasova, O.A., Amosova, S.V., and Trofimov, B.A., Zh. Org. Khim., 1982, vol. 18, p. 2042.
Trofimov, B.A., Korostova, S.E., Shevchenko, S.G., Polubentsev, E.A., and Mikhaleva, A.I., Zh. Org. Khim., 1990, vol. 26, p. 1110.
Ionin, B.I., Ershov, B.A., and Kol'tsov, A.I., YaMR spektroskopiya v organicheskoi khimii (NMR Spectroscopy in Organic Chemistry), Leningrad: Khimiya, 1983, p. 159.
Brandsma, L. and Verkruijsse, H., Studies in Organic Chemistry. 8. Synthesis of Acetylenes, Allenes and Cumulenes, Amsterdam: Elsevier, 1981, p. 143.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Trofimov, B.A., Tarasova, O.A., Shemetova, M.A. et al. N-Isopropenylazoles: I. Direct N-Isopropenylation of Azoles with Propyne and Allene. Russian Journal of Organic Chemistry 39, 408–414 (2003). https://doi.org/10.1023/A:1025502016921
Issue Date:
DOI: https://doi.org/10.1023/A:1025502016921