Thioacetic acid (TAA) has been subjected to dichlorovinylation with trichloroethene (TCE) under free-radical conditions to form 1-acetylthio-2,2-dichloroethene 1 (yield 70%) which reacts with TAA at room temperature under phase-transfer catalysis conditions to afford a mixture of E- and Z-isomers of 1,2-bis(acetylthio)-2-chloroethene 2 (total yield 71%); ethylthio(chloro)ethyne with sodium thioacetate gives acetylthio(ethylthio)ethyne 3.