2-Dialkylamino-5-hydroxy-1, 3-dithian-2-ylium perchlorates (2) could be synthesized by reaction of 2-alkyl-1-chloro-2, 3-epoxypropane derivertives (4) with aqueous dialkylammonium N, N-dialkyldithiocarbamates (5), followed by treatment with NaCIO4 in methanol. Reaction of 2 with bases gave 2, 3-epithiopropyl N, N-dialkylthiolcarbamates (8). In these cases, the reaction pathway involving intramolecular rearrrangement of 2 via formation of intermediate, heterobridged bicyclo compound, was proposed.