Inorganic chemistry,thiocarbamates (thiourethanes) are a family oforganosulfur compounds. As the prefixthio- suggests, they aresulfur analogues ofcarbamates. There are twoisomeric forms of thiocarbamates:O-thiocarbamates,ROC(=S)NR₂ (esters), andS-thiocarbamates,RSC(=O)NR₂ (thioesters).

Thiocarbamates can be synthesised by the reaction of water or alcohols uponthiocyanates (Riemschneider thiocarbamate synthesis):^[1][2]

RSCN + H₂O → RSC(=O)NH₂

RSCN + R'OH → RSC(=O)NR'H

Similar reactions are seen between alcohols and thiocarbamoyl chlorides such asdimethylthiocarbamoyl chloride; as well as betweenthiols andcyanates.^[2] The herbicide Cycloate is produced in this way:

C₆H₁₁(C₂H₅)NCOCl + C₂H₅SH → C₆H₁₁(C₂H₅)NCOSC₂H₅ + HCl

Other related thiocarbamate herbicides include vernolate(C₃H₇)₂NCOSC₃H₇ and triallate ((i−C₃H₇)₂NCOSCH₂CCl=CCl₂.^[3]

Salts of thiocarbamate arise by the reaction of amines withcarbonyl sulfide:

2 R₂NH + COS → [R₂NH+2][R₂N−COS⁻]

In theNewman-Kwart rearrangementO-thiocarbamates canisomerise toS-thiocarbamates.^[4] This reaction, which generally requires high temperatures, is an important method for the synthesis ofthiophenols.

Goitrin is a cyclic thiocarbamate found in some vegetables.^[5]

Thiocarbamate based herbicides (e.g.prosulfocarb) were introduced in 1957 and in 2017 was a $200,000,000 market.^[6] Other thiocarbamate herbicides arepebulate,molinate,EPTC,butylate,triallate,vernolate andcycloate.^[7]

• Dithiocarbamate
• Carbamate
• Tolnaftate, a thiocarbamate used as an antifungal agent

• Thiocarbamates
• Functional groups

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• Short description matches Wikidata