Rearrangement of radicals with migration of the chlorine atom from sulfur to carbon during the reaction of thiols with vinylsulfonyl chloride

Abstract

1. A study was made of the reaction of n-butanethiol and thiophenol with vinylsulfonyl chloride at ∼20° in an argon atmosphere. The reaction products are, respectively,β-chloroethyl butyl sulfide andβ-chloroethyl phenyl sulfide (8–12% yields), and SO2 is liberated. The other reaction products are, respectively, the dibutyl and diphenyl disulfides (60–70% yields), HCl, and H2O. 2. Apparently, the formation ofβ-chloroethyl butyl sulfide andβ-chloroethyl phenyl sulfide is associated with the addition of the thiyl radical to the double bond of vinylsulfonyl chloride and subsequent rearrangement of the RSCH2CHSO2Cl radicals, with the migration of chlorine from sulfur to the adjacent carbon atom.