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

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Chemistry of Heterocyclic Compounds Aims and scope

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.

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Authors and Affiliations

  1. K. A. Timiryazev Moscow Agricultural Academy, 127550, Moscow

    Yu. B. Vysotskii, N. M. Przheval'skii, B. P. Zemskii, I. I. Grandberg & L. Yu. Kostromina

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  1. Yu. B. Vysotskii
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  2. N. M. Przheval'skii
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  3. B. P. Zemskii
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  4. I. I. Grandberg
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  5. L. Yu. Kostromina
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Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 898–907, July, 1986.

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Vysotskii, Y.B., Przheval'skii, N.M., Zemskii, B.P. et al. Mechanism of the Fischer indole synthesis. Quantum-chemical interpretation of the rearrangement of substituted cyclohexanone arylhydrazones to tetrahydrocarbazoles. Chem Heterocycl Compd 22, 713–722 (1986). https://doi.org/10.1007/BF00522729

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  • DOI: https://doi.org/10.1007/BF00522729

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