The rearrangement of benzylic trichloromethane-sulfenates to sulfoxides and chlorides

S. Braverman, B. Sredni

Research output: Contribution to journalArticlepeer-review

21 Scopus citations


While benzyl trichloromethanesulfenate undergoes no rearrangement to sulfoxide even at high temperatures, the corresponding anisyl ester rearranges to p-anisyl trichloromethyl sulfoxide in hexane under mild conditions. Substitution of hexane by chloroform under similar conditions, lead to the formation of p-anisyl chloride and dichlorosulfine as main reaction products. This process is enhanced by the use of more polar solvents and higher temperatures. The conversion of trichloromethanesulfenate to chloride has also been observed with the benzyl and benzhydryl esters on heating in various solvents, though at very differing rates. Both rearrangements are suggested to take place by an ionization mechanism. Depending on the reaction conditions and nature of the substrate, the sulfenate anion can either recombine with the cation to give sulfoxide, or further dissociate to dichlorosulfine and chloride ion, which gives the benzyl chloride. The observation of an SN1 type mechanism for rearrangement of sulfenates appears to be unique.

Original languageEnglish
Pages (from-to)2379-2384
Number of pages6
Issue number15
StatePublished - 1974


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