Nucleophilic Substitutions of Unactivated Vinyl Halides with Alkanethiolate Anions in Hexamethylphophoramide

Article abstract of DOI:10.1021/jo00173a003

The reactions of unactivated vinyl halides with the sodium salts of alkanethiols in HMPA gave vinyl alkyl sufides in high yields.These reactions occur with complete retention of configuration.With di-, tri-, and tetrachloroethylenes all the chlorine atoms are substituted by alkylthio groups.By treatment with alkanethiolates the vinyl sulfides are dealkylated to give the sodium salts of the ene thiols.By reaction with sodium all the alkylthiogroups present in the molecule suffer fragmentation to give the sodium salts of the corresponding mercaptoethylenes.