Theoretica chimica acta

, Volume 59, Issue 4, pp 357–364 | Cite as

Cycloreversion reactions for five to seven membered rings

  • Karl Jug
  • C. P. D. Dwivedi
Original Investigations

Abstract

The cycloreversion of the following ring systems was studied: (1) Cyclopentyl anion → allyl anion + ethylene, (2) Cyclohexene → butadiene + ethylene, (3) Cyclohept-4-enyl cation → butadiene + allyl cation. The potential energy surfaces of these reactions were investigated by the semiempirical MO method SINDO1 under inclusion of a 4 × 4 CI. All internal coordinates were varied. We found major differences in the nature and geometry of transition states and intermediates of these reactions. Diradical character is involved only in the fragmentation of the six membered ring.

Key words

Cycloreversion of rings 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Dewar, M. J. S., Griffin, A. C., Kirschner, S.: J. Am. Chem. Soc.96, 6225 (1974)CrossRefGoogle Scholar
  2. 2.
    Townshend, L. R. E., Rammuni, G., Segal, G. A., Hehre, W. J., Salem, L.: J. Am. Chem. Soc.98, 2190 (1976)CrossRefGoogle Scholar
  3. 3.
    Burke, L. A., Leroy, G., Sana, M.: Theoret. Chim. Acta (Berl.)40, 313 (1975);44, 219 (1977)CrossRefGoogle Scholar
  4. 4.
    Jug, K., Krüger, H. W.: Theoret. Chim. Acta (Berl.)52, 19 (1979)CrossRefGoogle Scholar
  5. 5.
    Dewar, M. J. S., Olivella, S., Rzepa, H. S.: J. Am. Chem. Soc.100, 5650 (1978)CrossRefGoogle Scholar
  6. 6.
    Nanda, D. N., Jug, K.: Theoret. Chim. Acta (Berl.),57, 95, 107 (1980)CrossRefGoogle Scholar
  7. 7.
    Hoffmann, H. M. R.: Angew. Chem. Int. Ed. Engl.12, 819 (1973)CrossRefGoogle Scholar
  8. 8.
    Willcott, M. R., Cargill, R. L., Sears, A. B.: Progress in physical organic chemistry, Vol. 9, p. 25, Streitwieser, A., Taft, R. W., Eds. New York: Wiley-Interscience 1972Google Scholar
  9. 9.
    Stang, P. J., Rappoport, Z., Hanack, M., Subramanian, L. R.: Vinyl cations. New York: Academic Press 1979Google Scholar

Copyright information

© Springer-Verlag 1981

Authors and Affiliations

  • Karl Jug
    • 1
  • C. P. D. Dwivedi
    • 1
  1. 1.Theoretische ChemieUniversität HannoverHannover 1Federal Republic of Germany

Personalised recommendations