Thiocarbamate

In organic chemistry, thiocarbamates (thiourethanes) are a family of organosulfur compounds.

There are two isomeric forms of thiocarbamates: O-thiocarbamates, ROC(=S)NR2 (esters), and S-thiocarbamates, RSC(=O)NR2 (thioesters).

Thiocarbamates can be synthesised by the reaction of water or alcohols upon thiocyanates (Riemschneider thiocarbamate synthesis):[1][2] Similar reactions are seen between alcohols and thiocarbamoyl chlorides such as dimethylthiocarbamoyl chloride; as well as between thiols and cyanates.

[3] Salts of thiocarbamate arise by the reaction of amines with carbonyl sulfide: In the Newman-Kwart rearrangement O-thiocarbamates can isomerise to S-thiocarbamates.

[4] This reaction, which generally requires high temperatures, is an important method for the synthesis of thiophenols.