Thiocarbamates

Thiocarbamates are a family of organosulfur compounds. As the name suggests, they are sulphur analogues of carbamates. There are two isomeric forms of thiocarbamate esters: O-thiocarbamates, ROC(=S)NR2, and S-thiocarbamates, RSC(=O)NR2. Thiocarbamates are a family of organosulfur compounds. As the name suggests, they are sulphur analogues of carbamates. There are two isomeric forms of thiocarbamate esters: O-thiocarbamates, ROC(=S)NR2, and S-thiocarbamates, RSC(=O)NR2. Thiocarbamates can be synthesised by the reaction of water or alcohols upon thiocyanates (Riemschneider thiocarbamate synthesis): Similar reactions are seen between alcohols and thiocarbamoyl chlorides such as dimethylthiocarbamoyl chloride; as well as between thiols and cyanates. Alternatively, they arise by the reaction of amines with carbonyl sulfide. In the Newman-Kwart rearrangement O-thiocarbamates can isomerise to S-thiocarbamates. This is generally performed by heating to high temperatures and is an important method for synthesising thiophenols. Dithiocarbamates are related to thiocarbamates by the replacement of O by S. Despite this structural similarity their synthesis and chemistry is quite different. Dithiocarbamates and their derivatives are widely used in the vulcanization of rubber.