Reaction of (Organylthio)chloroacetylenes With Aliphatic 1,2-Dithiols: A Route to Functionalized 1,3-Dithiolanes

Abstract

Organylthio)chloroacetylenes react with aliphatic 1,2-dithiols in dimethyl sulfoxide at 20-25 • C in the presence of a two-fold molar excess of alkali to form 2-[(alkylthio)methyliden]-1,3-dithiolanes in up to 66% yield.Earlier, we reported the reactions of (organylthio)chloroacetylenes 1 with S-centered nucleophiles (sodium sulfide, 1 thiols, 2 thioacetic acid 3 ), which followed the addition and/or substitution schemes. (Organylthio)chloroacetylenes reacted with bidentate nucleophiles giving either functionally substituted acetylenic sulfides or organylthio substituted heterocyclic compounds. 2,4−6 Thus, 2-{[2-(alkylthio)ethynyl]thio}ethan-1-ammonium 5 and S-(alkylthioethynyl) isothiuronium 4 chlorides were prepared by the reaction of (alkylthio)-chloroacetylenes with 2-aminoethan-1-thiol and thiourea respectively. Under similar conditions, the reaction of (phenylthio)chloroacetylene with thiourea gave quantitatively 4-(phenylthio)-1,3-thiazol-2(3H)-imine hydrochloride. 4 (Organylthio)chloroacetylenes readily reacted with 2-mercaptoethan-1-ol (KOH-DMSO, 20-22 • C) to afford Financial support from the Ministry of Industry, Science and Technologies of Russian Federation (grants no. NSH-

Reaction of Alkylsulfanylchloroacetylenes with 1,1-Dimethylhydrazine

“…Depending on the nucleophile nature and conditions, these reactions could produce not only normal nucleophilic substitution products but also sulfanyl-substituted heterocyclic compounds [1][2][3][4][5][6][7]. Reactions of compounds I with 1,1-dimethylhydrazine (which is a large-scale product of chemical industry) have not been studied so far.…”