Thiocarbamate

In organic chemistry, thiocarbamates are a family of organosulfur compounds. As the prefix thio- suggests, they are sulfur analogues of carbamates. There are two isomeric forms of thiocarbamates: O-thiocarbamates,, and S-thiocarbamates, .

Synthesis

Thiocarbamates can be synthesised by the reaction of water or alcohols upon thiocyanates :
Similar reactions are seen between alcohols and thiocarbamoyl chlorides such as dimethylthiocarbamoyl chloride; as well as between thiols and cyanates. The herbicide Cycloate is produced in this way:
Other related thiocarbamate herbicides include vernolate and triallate (.
Salts of thiocarbamate arise by the reaction of amines with carbonyl sulfide:

Reactions

In the Newman-Kwart rearrangement O-thiocarbamates can isomerise to S-thiocarbamates. This reaction, which generally requires high temperatures, is an important method for the synthesis of thiophenols.

Occurrence

Goitrin is a cyclic thiocarbamate found in some vegetables.

Uses

Thiocarbamate based herbicides were introduced in 1957 and in 2017 was a $200,000,000 market. Other thiocarbamate herbicides are pebulate, molinate, EPTC, butylate, triallate, vernolate and cycloate.