Preparation of arenesulphonyl chlorides from Grignard reagents

Abstract

Reaction of phenylmagnesium bromide with excess of sulphuryl chloride in ether–hexane at 0° gives benzenesulphonyl chloride and bromide in a combined yield of at least 58%. Substituted sulphonyl halides, YC₆H₄·SO₂X (Y =o-Me, m-Me, m-Cl, and m-CF₃), are produced similarly in comparable yields. Diphenylmagnesium, diphenylcadmium, or phenyl-lithium under similar conditions give somewhat smaller yields of benzenesulphonyl halides. Use of arylmagnesium chlorides, ArMgCl (Ar = Ph, o-MeO·C₆H₄, p-Me₃Si·C₆H₄, and C₆Cl₅), in tetrahydrofuran–hexane at 0° gives pure arenesulphonyl chlorides in yields of 53–64%. Reactions of phenylethynylmagnesium chloride and of some benzylmagnesium chlorides with sulphuryl chloride in ether–hexane have also been studied.