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

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.