Advertisement

Chemistry of Heterocyclic Compounds

, Volume 29, Issue 3, pp 313–320 | Cite as

Structure and properties of 8-azasteroids synthesized by regio- and stereoselective annelation of 3,4-dihydroisoquinolines by asymmetric 2-acyl-1,3-cyclohexanediones

  • A. L. Mikhal'chuk
  • O. V. Gulyakevich
  • D. B. Rubinov
  • A. A. Akhrem
Article
  • 31 Downloads

Abstract

It was found that annelation of 3,4-dihydroisoquinolines by 2-acyl-1,3-cyclohexanediones takes place regio- and stereoselectively, leading to C(11)- and C(17)-substituted derivatives of the 8-aza-D-homogonane series with a trans-disposition of the substituents (Me, Br, Cl, COOMe) at the above positions relative to the angular substituent (H, Me) at C(9). It was shown that the C(17)-halogen and methoxycarbonyl derivatives exist in crystals in the form of one stereoisomer, while in solutions as a mixture of stereoisomers, caused by a keto-enol tautomerism of the C(17a)-carbonyl. In solutions of acids, these derivatives exist in N(8)- ... — C(17a) immonium-enol form, as one stereoisomer. It was found that the C(11)-methyl derivatives are obtained in the form of two restrained conformers with respect to ring C, which on boiling are reduced to one conformer. The assignment of the enol regiomers of 4-substituted 2-acetyldimedones has been carried out.

Keywords

Methyl Organic Chemistry Carbonyl Cyclohexanediones Halogen 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    M. von Strandtmann, M. P. Cohen, and J. Shavel, Jr., J. Org. Chem., 31, 797 (1966).Google Scholar
  2. 2.
    A. A. Akhrem, A. M. Moiseenkov, and V. A. Krivoruchnko, Izv. Akad. Nauk SSSR, Ser. Khim., No. 9, 2078 (1972).Google Scholar
  3. 3.
    A. A. Akhrem, A. M. Moiseenkov, and A. I. Poselenov, Dokl. Akad. Nauk SSSR, 203, 95 (1972).Google Scholar
  4. 4.
    A. A. Akhrem and Yu. A. Titov, Total Synthesis of Steroids [in Russian], Nauka, Moscow (1967).Google Scholar
  5. 5.
    A. A. Akhrem, B. B. Kuz'mitskii, F. A. Lakhvich, V. A. Khripach, and Yu. L. Zhuravkov, Chemistry and Biology of Immunoregulators [in Russian], Zinatne, Riga (1985), p. 265.Google Scholar
  6. 6.
    B. B. Kuz'mitskii, O. V. Stoma, L. M. Slepneva, A. E. Mashkovich, V. P. Nasek, O. V. Gulyakevich, and A. L. Mikhal'chuk, Farmakol. Toksikol., 52, 71 (1989).Google Scholar
  7. 7.
    A. A. Akhrem and A. L. Mikhal'chuk, Summaries of Lectures at the 7th Conference on the Chemistry of Dicarbonyl Compounds [in Russian], Riga (1991), p. 7.Google Scholar
  8. 8.
    A. A. Akhrem, A. M. Moiseenkov, and V. A. Krivoruchko, Izv. Akad. Nauk SSSR, Ser. Khim., No. 6, 1302 (1973).Google Scholar
  9. 9.
    A. A. Akhrem, F. A. Lakhvich, L. G. Lis, and V. N. Pshenichnyi, Dokl. Akad. Nauk Beloruss. SSR, 22, 431 (1978).Google Scholar
  10. 10.
    A. A. Akhrem, F. A. Lakhvich, V. N. Pshenichnyi, O. F. Lakhvich, and B. B. Kuz'mitskii, Dokl. Akad. Nauk SSSR, 240, 595 (1978).Google Scholar
  11. 11.
    W. M. Whaley and T. R. Govindachari, Organic Reactions [Russian translation], Vol. 6, Inostr. Lit., Moscow (1953), p. 98.Google Scholar
  12. 12.
    A. A. Akhrem, F. A. Lakhvich, S. I. Budai, T. S. Khlebanovich, and I. I. Petrusevich, Synthesis, No. 2, 925 (1978).Google Scholar
  13. 13.
    Japanese Patent 79 63,052; Chem. Abstr., 91, 192911w (1979).Google Scholar
  14. 14.
    L. De Buyck, D. Seynaeve, and N. De Kimpe, Bull. Soc. Chim. Belg., 94, 363 (1985).Google Scholar
  15. 15.
    E. V. Borisov and T. S. Khlebnikov, Dokl. Akad. Nauk Beloruss. SSR, 31, 539 (1987).Google Scholar
  16. 16.
    W. F. Rowe, Jr., R. W. Duerst, and E. B. Wilson, J. Am. Chem. Soc., 98, 4021 (1976).Google Scholar
  17. 17.
    A. J. Vila, C. M. Lagier, and A. C. Olivieri, J. Chem. Soc. Perkin Trans. 2, No. 16, 1615 (1990).Google Scholar
  18. 18.
    W. Winter, K.-P. Zeller, and S. Berger, Z. Naturforsch., 34b, 1606 (1979).Google Scholar
  19. 19.
    R. Bible, Interpretation of Nuclear Magnetic Resonance Spectra [Russian translation], Atomizdat, Moscow (1969).Google Scholar
  20. 20.
    V. G. Avakyan, V. V. Gromak, and V. Z. Kurbako, Izv. Akad. Nauk SSSR, Ser. Khim., No. 9, 2377 (1989).Google Scholar

Copyright information

© Plenum Publishing Corporation 1993

Authors and Affiliations

  • A. L. Mikhal'chuk
    • 1
  • O. V. Gulyakevich
    • 1
  • D. B. Rubinov
    • 1
  • A. A. Akhrem
    • 1
  1. 1.Institute of Bioorganic ChemistryAcademy of Sciences of BelarusMinsk

Personalised recommendations