Intermediate stages of the sulfohaloform reaction. Preparation of α-halosulfoxides and sulfinyl chlorides. Oxygen-transfer reactions

Abstract

Details are provided of synthetic routes from dialkyl sulfides to both α-halosulfoxides and sulfinyl chlorides. In the case of the former, oxidation of α-halosulfides to the sulfoxide stage is achieved by chlorine in acetic acid containing controlled amounts of water. Sulfinyl chlorides are prepared by chlorination of α-polyhalosulfoxides in methylene chloride. During investigations into the details of the sulfohaloform reaction, a number of novel redox reactions involving oxygen transfer between sulfur species have been observed and these are presented. They include a reduction of a sulfoxide with thionyl chloride.