Chemistry of Heterocyclic Compounds

, Volume 22, Issue 7, pp 713–722 | Cite as

Mechanism of the Fischer indole synthesis. Quantum-chemical interpretation of the rearrangement of substituted cyclohexanone arylhydrazones to tetrahydrocarbazoles

  • Yu. B. Vysotskii
  • N. M. Przheval'skii
  • B. P. Zemskii
  • I. I. Grandberg
  • L. Yu. Kostromina
Article

Abstract

Calculations of a number of model structures within the scheme of the Fishcer indole synthesis were made on the basis of a bonding variant of perturbation theory in the self-consistent-field (SCF) MO LCAO method. A quantum-chemical interpretation of the effect of substituents on the course of the thermal process is given. The kinetics of the thermal and acid-catalyzed indolization of substituted cyclohexanone arylhydrazones to tetrahydrocarbazoles were studied by spectrophotometry. It was shown that the experimental data are in satisfactory agreement with the calculated values. It was concluded that a concerted mechanism (a [3,3]-sigmatropic shift) for the step involving the formation of a carbon-carbon bond in the Fischer reaction is preferred.

Keywords

Experimental Data Organic Chemistry Perturbation Theory Indole Spectrophotometry 

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Copyright information

© Plenum Publishing Corporation 1987

Authors and Affiliations

  • Yu. B. Vysotskii
    • 1
  • N. M. Przheval'skii
    • 1
  • B. P. Zemskii
    • 1
  • I. I. Grandberg
    • 1
  • L. Yu. Kostromina
    • 1
  1. 1.K. A. Timiryazev Moscow Agricultural AcademyMoscow

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