Formation of acyldisulfide ions from the reaction of sulfur with thiocarboxylate ions, and reactivity towards acyl chlorides in N,N-dimethylacetamide

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Julie Robert, Meriem Anouti and Jacky Paris


Abstract

The reactivity of sulfur towards thiocarboxylate ions RC(O)S- a (R = Ph 1, Me 2, But 3) has been studied by spectroelectrochemistry in N,N-dimethylacetamide. For 2a–3a, two parallel and partial reactions, for which equilibrium constants have been determined, led to: (i) [RC(O)]2S2- b species and S3·-/S82- polysulfide ions and (ii) RC(O)S2 ions c; only traces of 1c were detected by voltammetry. As previously observed with thiolate ions, our results are consistent with an initial monoelectronic transfer between RC(O)S- ions and S2 molecules in equilibrium with S8, followed by concurrent couplings of RC(O)S˙ and S2·- radicals. On a preparative scale, when sulfur was added to RC(O)S- ions 1a,3a the enhanced reactivity of RC(O)S2- ions towards acyl chlorides RC(O)Cl (R = C6H5 and But, respectively) only yielded diacyl disulfides 1b,3b.


References

  1. G. Bosser, M. Anouti and J. Paris, J. Chem. Soc., Perkin Trans. 2, 1966, 1993 Search PubMed.
  2. (a) A. J. Parker and N. Kharasch, Chem. Rev., 1959, 59, 583 CrossRef CAS; (b) A. J. Parker and N. Kharasch, J. Am. Chem. Soc., 1960, 82, 3071 CrossRef CAS.
  3. S. Oae, Organic Sulfur Chemistry: Structure and Mechanism, CRC Press, Ann Arbor, 1991, pp. 119–134 and references cited therein Search PubMed.
  4. G. Bosser and J. Paris, New J. Chem., 1995, 19, 391 Search PubMed and references cited therein.
  5. C. Degrand and H. Lund, Acta Chem. Scand., Ser. B, 1979, 33, 512 Search PubMed.
  6. J. Courtot-Coupez and M. Le Démézet, Bull. Soc. Chim. Fr., 1969, 3, 1033.
  7. L. Eberson and J. H. P. Utley, in Organic Electrochemistry, eds. M. M. Baizer and H. Lund, Marcel Dekker, New York and Basel, 1983, pp. 435–462 and references cited therein Search PubMed.
  8. (a) B. Svenmark, in Organic Electrochemistry, eds. M. M. Baizer and H. Lund, Marcel Dekker, New York and Basel, 1993, pp. 523–524 Search PubMed; (b) Y. Hirabayashi and T. Mazume, Bull. Chem. Soc. Jpn., 1966, 39, 1971 CAS.
  9. J. Paris and V. Plichon, Electrochimica Acta, 1981, 26, 1823 CrossRef CAS.
  10. M. Benaïchouche, G. Bosser, J. Paris, J. Auger and V. Plichon, J. Chem. Soc., Perkin Trans. 2, 1990, 31 RSC.
  11. J. M. Savéant and K. B. Su, J. Electroanal. Chem., 1984, 171, 341 CrossRef CAS.
  12. M. V. Rao, C. B. Reese and Z. Zhengyun, Tetrahedron Lett., 1992, 33, 4839 CrossRef CAS.
  13. M. Benaïchouche, G. Bosser, J. Paris and V. Plichon, J. Chem. Soc., Perkin Trans. 2, 1990, 1421 RSC.
  14. J. Voss, in Comprehensive Organic Synthesis, ed. B. M. Trost, Pergamon Press, Oxford, New York, Seoul, Tokyo, 1991, vol. 6, pp. 435–445 and references cited therein Search PubMed.
  15. G. Bosser and J. Paris, J. Chem. Soc., Perkin Trans. 2, 1992, 2057 RSC.
  16. S. Kawamura, T. Horii and J. Tsurugi, J. Org. Chem., 1971, 36, 3677 CrossRef.
  17. (a) J. Edwards and R. Pearson, J. Am. Chem. Soc., 1962, 84, 16 CrossRef CAS; (b) J. Dixon and T. Bruice, J. Am. Chem. Soc., 1972, 94, 2052 CrossRef.
  18. M. Mikolajczyk, P. Kielbasinski and H. M. Schiebel, J. Chem. Soc., Perkin Trans. 1, 1976, 564 RSC.
  19. C. Christophersen and P. Carlsen, Tetrahedron, 1976, 32, 745 CrossRef CAS.
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