Application of mercaptide anions to the dechlorination of an α-polychlorosulfonyl substrate has provided the key step in a successful synthesis of the title compound. 5-Phenyl-2, 4, 5- trithiapentane-2, 2-dioxide undergoes chlorinolysis in an aqueous medium to yield products consistent with the view that α-sulfonyl oxodichlorosulfonium chlorides and α-sulfonyl dichlorosulfonium chlorides may undergo unusually facile Pummerer rearrangements.