Chlorosulfination of Aromatic Methyl Ethers with Thionyl Chloride

Abstract

Aromatic sulfinyl chlorides have been prepared in high yield by direct chlorosulfination of some aromatic ethers (1,3-dimethoxybenzene, 2- methyl- and 4-chloro-1,3-dimethoxybenzene, 1,2,3-trimethoxybenzene, 1- and 2-methoxynaphthalene, 1,5-, 1,7-, 2,6- and 2,7- dimethoxynaphthalene ) with thionyl chloride alone at or below room temperature. Under the same conditions, 1,4-dimethoxynaphthalene and 1,3-dimethoxy-5-methylbenzene yield chlorinated starting materials and sulfides. 1,3,5-Trimethoxybenzene yields chlorinated starting material, sulfide, and a chlorinated disulfide. Some other ethers (e.g. anisole, 1,2- and 1,4-dimethoxybenzene, 5-chloro-1,3-dimethoxybenzene) are unreactive under these conditions.