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Electrochemical Production and Examination of Redox Conversions of 2,4-Diphenyl-6H-cyclopenta[b]thiopyran and 2,4-Diphenylcyclopenta[b]thiopyrilium Perchlorate

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Abstract

The mechanism governing the formation of 2,4-diphenyl-6H-cyclopenta[b]thiopyran and corresponding thiopyrilium perchlorate from 1,3-diphenyl-3-(2-oxocyclopentyl)-1-propanon in conditions of oxidative activation of hydrogen sulfide is considered. The process of oxidation of 2,4-diphenyl-6H-cyclopenta[b]thiopyran in a nonaqueous environment is shown to proceed stepwise through the intermediate formation of a radical cation, radical, and anhydrobase, to aromatic system 2,4-diphenylcyclopentadieno[b]thiopyranilidene. A similar product is obtained when oxidizing the 2,4-diphenylcyclopenta[b]thiopyrilium cation. Reduction of thiopyrilium perchlorate was observed to lead to the formation of a 2,4-diphenylcyclopenta[b]thiopyranyl radical, which is confirmed by an ESR method. The mechanism of redox conversions of thiopyran and thiopyrilium salt is substantiated by a quantum-chemical calculation.

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Authors and Affiliations

  1. Astrakhan State Technical University, ul. Tatishcheva 16, Astrakhan, 414025, Russia

    N. T. Berberova, E. V. Shinkar', O. N. Akimova & K. P. Pashchenko

  2. Saratov Veterinary Academy, Saratov, Russia

    S. K. Klimenko & D. R. Sharafutdinov

Authors
  1. N. T. Berberova
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  2. S. K. Klimenko
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  3. E. V. Shinkar'
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  4. O. N. Akimova
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  5. D. R. Sharafutdinov
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  6. K. P. Pashchenko
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Correspondence to N. T. Berberova.

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Berberova, N.T., Klimenko, S.K., Shinkar', E.V. et al. Electrochemical Production and Examination of Redox Conversions of 2,4-Diphenyl-6H-cyclopenta[b]thiopyran and 2,4-Diphenylcyclopenta[b]thiopyrilium Perchlorate. Russian Journal of Electrochemistry 39, 1287–1293 (2003). https://doi.org/10.1023/B:RUEL.0000009094.85140.f2

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  • DOI: https://doi.org/10.1023/B:RUEL.0000009094.85140.f2

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