Silver ion-mediated desulfurization of N-aroyl-S- (disubstituted thiocarbamoyl) -thio-hydroxylamines (1) and disubstituted dithiocarbamic acid phenacyl esters (4) in aqueous solution gives the corresponding their carbamoyl derivatives. On the other hand, the reaction of 4 in acetic acid leads to formation of 2- (N, N-disubstituted amino) -5-phenyl-1, 3-oxathiolium salts in one pot.