THE REACTION OF SULFONYLIMIDO INTERMEDIATES WITH AROMATIC COMPOUNDS

Abstract

Thermolysis of methanesulfonyl azide in aromatic solvents gives methanesulfonamide and the isomeric methanesulfonanilides. The orientation of the latter and the relative reactivities of the aromatic substrate towards attack by the methylsulfonylimido intermediate have been studied quantitatively. The high reactivity and also great selectivity of the attacking species are interpreted in terms of a rate-determining addition process to give a sulfonylaziridine derivative followed by a product-determining ring opening and rearrangement to the substituted anilides. Partial rate factors are discussed, as are possible mechanisms for the formation of the methanesulfonamide. The methanesulfonylimido intermediate must be abstracting two hydrogen atoms synchronously from the aromatic substrate.