Nucleophilic substitution of acyl chlorides by electrogenerated polysulfide ions in N,N-dimethylacetamide

Abstract

The reactions between acyl chlorides RC(O)Cl (a) [R = Me (1), Prⁱ (2), Bu^t (3), Ph(4)] and electrogenerated S₃^˙- (⇌ S₆^2- ) ions have been investigated in N,N-dimethylacetamide by spectroelectrochemistry. With R = alkyl, thiocarboxylate ions and sulfur resulting from the fast initial substitutions cause partial formation of both acyl disulfide ions and diacyl disulfides (b) at a y ratio [RC(O)Cl]/[S₃^˙-] of 0.5; the second step stoichiometrically (y = 1) affords diacyl disulfides 1b–4b as the presumed products. The formation of these species only is confirmed on a preparative scale from two sets of experiments: (i) direction addition of acyl chlorides (1a–4a) to chemically generated S ^⅓- solutions; (ii) electrolysis of sulfur in the presence of acyl chlorides 2a–4a.

References

1. (a) J. Paris and V. Plichon, Nouv. J. Chim., 1984, 8, 733; (b) M. Benaïchouche, G. Bosser, J. Paris and V. Plichon, J. Chem. Soc., Perkin Trans. 2, 1991, 817; (c) G. Bosser and J. Paris, J. Chem. Soc., Perkin Trans. 2, 1992, 2057; (d) G. Bosser, M. Benaïchouche, R. Coudert and J. Paris, New J. Chem., 1994, 18, 511.
2. G. Bosser, M. Anouti and J. Paris, J. Chem. Soc., Perkin Trans. 2, 1996, 1993.
3. M. Benaïchouche, G. Bosser, J. Paris, J. Auger and V. Plichon, J. Chem. Soc., Perkin Trans. 2, 1990, 31.
4. G. Bosser and J. Paris, New J. Chem., 1995, 19, 391 and references cited therein.
5. D. T. Sawyer and M. J. Gibian, Tetrahedron, 1979, 35, 1471 and references cited therein.
6. M. Gareil, J. Pinson and J. M. Savéant, Nouv. J. Chim., 1981, 5, 311 and references cited therein.
7. C. Degrand and H. Lund, Acta Chem. Scand., Ser. B, 1979, 33, 512.
8. J. Robert, M. Anouti and J. Paris, J. Chem. Soc., Perkin Trans. 2, 1997, 473.
9. (a) R. Johnson, Tetrahedron Lett., 1976, 5, 331; (b) D. T. Sawyer, J. J. Stamp and K. A. Menton, J. Org. Chem., 1983, 48, 337.
10. (a) J. P. Stanley, J. Org. Chem., 1980, 45, 1413; (b) A. Le Berre and Y. Berguer, Bull. Soc. Chim. Fr., 1966, 7, 2368.
11. M. Bréant and J. Georges, J. Electroanal. Chem., 1976, 68, 165.
12. J. Paris and V. Plichon, Electrochim. Acta, 1982, 10, 1501.
13. M. Delamar and J. C. Marchon, J. Electroanal. Chem., 1975, 63, 351.
14. R. L. Franck and J. R. Blegen, Org. Synth. Coll., vol. III, 1955, 116.
15. Y. Hirabayashi and T. Mazume, Bull. Chem. Soc. Jpn., 1966, 39, 1971.
16. J. A. Gladysz, V. K. Wong and B. S. Jick, Tetrahedron, 1979, 35, 2329.
17. (a) M. Kodomari, M. Fukuda and S. Yoshitomi, Synthesis, 1981, 8, 637; (b) J. X. Wang, W. Cui, Y. Hu and K. Zhao, Synth. Commun., 1995, 25, 889.
18. M. T. Gibian, D. T. Sawyer, T. Ungermann, R. Tangpoonpholvivat and M. M. Morrison, J. Am. Chem. Soc., 1979, 101, 640.
19. F. Magno and G. Bontempelli, J. Electroanal. Chem., 1976, 68, 337.
20. J. San Filippo Jr., L. J. Romano, C. I. Chern and J. S. Valentine, J. Org. Chem., 1976, 41, 586.
21. K. U. Ingold, Acc. Chem. Res., 1969, 2, 1.
22. (a) R. Dietz, A. G. Forno, B. E. Larcombe and M. E. Peover, J. Chem. Soc. (B), 1970, 816; (b) K. Daasbjerg and H. Lund, Acta Chem. Scand., Ser. B, 1993, 47, 597 and references cited therein.
23. J. Dixon and J. Bruice, J. Am. Chem. Soc., 1972, 94, 2052 and references cited therein.
24. M. Benaïchouche, G. Bosser, J. Paris and V. Plichon, J. Chem. Soc., Perkin Trans. 2, 1990, 1421.
25. F. Magno, G. Bontempelli and M. M. Andreuzzi Sedea, J. Electroanal. Chem., 1979, 97, 85.
26. J. Paris and V. Plichon, Electrochim. Acta, 1981, 26, 1823.
27. C. Christophersen and P. Carlsen, Tetrahedron, 1976, 32, 745.