Zum Mechanismus der Umlagerung von N-Aryl-S,S-dimethylsulfimiden zu o-Methylthiomethylanilinen - Methylthiomethylierung von Anilinen und Phenolen, 8. Mitt.

Abstract

N-Aryl-S,S-dimethyl sulfimides may be rearranged to yield o-methylthiomethyl anilines either in aprotic solvents in presence of bases (triethyl amine) or in protic solvents (alcohols, water) without addition of base. The rate of the rearrangement is determined by the rate of proton abstraction from one of the S-methyl groups as well as by the position of the equilibrium for protomation of the nitrogen atom, as indicated by kinetic isotope effects and the influence of p-substituents, respectively. The rearrangement of the intermediate S-ylide is faster than its reprotonation by protic solvents and represents a sigmatropic [2.3]-migration. © 1972 Springer-Verlag.