Neighbouring group participation in reactions of sulphides with chloramine-t

F. Ruff, I. Kapovits, J. Rábai, Á Kucsman

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27 Citations (Scopus)

Abstract

Neighbouring group participation in reactions of chloramine-T with ortho-substituted aryl methyl sulphides and diaryl sulphides has been studied. The reaction is markedly hindered by the steric effect of the ortho substituent of the phenyl ring, but groups having a CO moiety show an anchimeric effect in the following order: o-CH2CO2Me ~ o-CH2CO2H < o-CH2CO2- < o-CO2Me ~ o-CO2H < o-CO2- ≪ 2o-CO2 in the rate-determining step may be ruled out on the basis of salt and isotope effect. Substituents with neighbouring group participation diminish the yield of sulphilimine in solvents containing water. The electrophilic chlorination of sulphides by TsNHCl may be assumed to be the rate-determining step with the positively charged sulphonium centre stabilized by the negatively polarized or charged carbonyl-oxygen in the transition state. This type of interaction hinders the nucleophilic attack of sulphonamidate ion at the sulphonium centre in the fast product-controlling steps, decreasing the yield of sulphilimine.

Original languageEnglish
Pages (from-to)2767-2774
Number of pages8
JournalTetrahedron
Volume34
Issue number18
DOIs
Publication statusPublished - 1978

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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