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Catalysis in β-elimination reactions. 6. Quantum-chemical calculations on intermediate compounds with correction for solvation in slightly polar solvents

  • Physical Chemistry
  • Published:
Bulletin of the Academy of Sciences of the USSR, Division of chemical science Aims and scope

Conclusions

  1. 1.

    Quantum-chemical calculations by the CNDO/BW and MINDO/2 methods have been carried out on certain modelβ-elimination reactions.

  2. 2.

    Study of various mechanisms involving ion solvation has shown that heterolytic C-H bond rupture is energetically favored over C-OR bond heterolysis, in solution but not in the gaseous phase.

  3. 3.

    In solutions with low dielectric constant (benzene, CH3COOH), ionic mechanisms can be realized only under the action of bases with PA's comparable to that of KOH.

  4. 4.

    Forβ-elimination reactions catalyzed by compounds such as CH3COOH and pyridine, we have proposed nonionic mechanisms based on proton transfer from theβ-carbon atom to the oxygen of the departing alcohol group.

  5. 5.

    It is proposed that the proton solvation energy in low-polarity solvents be calculated by making use of the electrostatic expression for the energy of solvation of the protonated solvent molecule.

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Authors and Affiliations

  1. N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow

    V. I. Faustov, I. N. Fundyler, I. A. Esikova & S. S. Yufit

Authors
  1. V. I. Faustov
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  2. I. N. Fundyler
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  3. I. A. Esikova
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  4. S. S. Yufit
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Additional information

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2694–2702, December, 1977.

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Faustov, V.I., Fundyler, I.N., Esikova, I.A. et al. Catalysis in β-elimination reactions. 6. Quantum-chemical calculations on intermediate compounds with correction for solvation in slightly polar solvents. Russ Chem Bull 26, 2490–2497 (1977). https://doi.org/10.1007/BF00924550

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  • DOI: https://doi.org/10.1007/BF00924550

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