Advertisement

Chemistry of Heterocyclic Compounds

, Volume 10, Issue 9, pp 1053–1059 | Cite as

Lactam acetals

XII. Investigation of the internal rotation in cyclic enamines by PMR spectroscopy
  • N. P. Kostyuchenko
  • V. G. Granik
  • A. M. Zhidkova
  • R. G. Glushkov
  • Yu. N. Sheinker
Article

Abstract

The cis-trans isomerization in a number of enamines — 1-methyl-2-(2'-R-2'-R'-methylene)pyrrolidines,-piperidines, and -hexahydroazepines — depends substantially on the nature of the 2'-substituent and the ring size. The energy barrier to this process decreases as the ability of the substituents to delocalize the anionic center in the transition state increases. The free energy of activation of rotation about the C=C bond is appreciably lower for six-membered enamines than for the corresponding seven- and five-membered analogs.

Keywords

Acetal Free Energy Organic Chemistry Transition State Energy Barrier 
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.

Literature cited

  1. 1.
    A. M. Zhidkova, V. Granik, N. S. Kuryatov, V. P. Pakhomov, O. S. Anisimova, and R. G. Glushkov, Khim. Geterotsikl. Soedin., 1089 (1974).Google Scholar
  2. 2.
    J. Shvo and H. Shanan-Atidi, J. Amer. Chem. Soc., 91, 6684 (1969).Google Scholar
  3. 3.
    J. Shvo and H. Shanan-Atidi, J. Amer. Chem. Soc., 91, 6689 (1969).Google Scholar
  4. 4.
    V. G. Granik, I. V. Persianova, N. P. Kostyuchenko, R. G. Glushkov, and Yu. N. Sheinker, Zh. Organ. Khim., 8, 181 (1972).Google Scholar
  5. 5.
    H. S. Gutowsky and C. H. Holm, J. Chem. Phys., 25, 1228 (1956).Google Scholar
  6. 6.
    R. Huisgen, H. Brade, and H. Wals, and J. Glogger, Ber., 90, 1437 (1957).Google Scholar
  7. 7.
    R. W. Taft, Jr., in: Steric Effects in Organic Chemistry, Wiley, New York (1956).Google Scholar
  8. 8.
    N. S. Zefirov and V. I. Sokolov, Usp. Khim., 36, 243 (1967).Google Scholar
  9. 9.
    V. G. Granik and R. G. Glushkov, Zh. Organ. Khim., 7, 1146 (1971).Google Scholar
  10. 10.
    H. Bredereck and K. Bredereck, Ber., 94, 2278 (1961).Google Scholar

Copyright information

© Plenum Publishing Corporation 1976

Authors and Affiliations

  • N. P. Kostyuchenko
    • 1
  • V. G. Granik
    • 1
  • A. M. Zhidkova
    • 1
  • R. G. Glushkov
    • 1
  • Yu. N. Sheinker
    • 1
  1. 1.S. Ordzhonikidze All-Union Scientific-Research Institute of Pharmaceutical ChemistryMoscow

Personalised recommendations