Thiocarbamyl chlorides, reactions

Thiophosgene reacts with alcohols and phenols to form chlorothionoformates or thiocarbonates. The most studied reactions of thiophosgene are with primary amines to give isothiocyanates and with secondary amines to give thiocarbamyl chlorides ... 

The submitters have prepared the following thiocarbamyl chlorides by the chlorination of the corresponding disulfides dimethylthiocarbamyl chloride, b.p. 90-95°/0.5 mm., m.p. 42.5-43.5°, carbon tetrachloride reaction medium diisopropylthio-carbamyl chloride, m.p. 69-71°, benzene reaction medium diiso-butylthiocarbamyl chloride, m.p. 46-48°, no solvent. 

A theoretical study of the reactions of carbamyl and thiocarbamyl chlorides and fluorides in the gas phase and in aqueous solution concluded that (i) FCONH2 reacted in the gas phase via a neutral TI formed via attack by NHj at the C=0 group with concurrent proton transfer, but CICONH2 proceeded via a concerted mechanism involving a tetrahedral TS, and (ii) FCONH2 reacted in aqueous solution via a stepwise mechanism involving a stable zwitterionic TI, but CICONH2 proceeded in a concerted manner, as in the gas phase. ... 

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