The chemistry of trisulphenamides [N(SR)3]. Part I. Preparation, thermal decomposition, and reactions of tribenzenesulphenamide [N(SPh)3]

Abstract

Treatment of the sodium salt of dibenzenesulphenamide with acetic anhydride gave tribenzenesulphenamide [N(SPh)₃]. Decomposition of this substance at ca. 80° gave nitrogen and diphenyl disulphide in quantitative yields. Phenols react with tribenzenesulphenamide to give quinone phenylthioimines. Where both ortho- and para-positions in the phenol are available for substitution, ortho-substitution predominates. The mechanism of this reaction involves initial H· abstraction from the phenol by the ·N(SPh)₂ radical to give e.g. species (XVI). Subsequent decomposition of such intermediates gives the isolated product. Amines give less specific reactions compared with phenols.