Thiocarbamates can be synthesised by the reaction of water or alcohols upon thiocyanates (Riemschneider thiocarbamate synthesis):
:RSCN + HO → RSC(=O)NH
:RSCN + ROH → RSC(=O)NRH
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: