Facile One-Pot Synthesis of S-Alkyl Thiocarbamates

Abstract

We report a novel one-pot two-step synthesis of a variety of S-alkyl thiocarbamates. This method offers a two-directional approach making use of trichloroacetyl chloride, requires no complex starting material, incorporates a variety of substituents, and proceeds in high yields.

Superparamagnetic Fe3O4 Nanoparticles in a Deep Eutectic Solvent: An Efficient and Recyclable Catalytic System for the Synthesis of Primary Carbamates and Monosubstituted Ureas

“…During the past few years, great efforts have been made to explore environmentally benign routes that employ other carbonyl sources, including 1,1,1‐trichloromethyl formate (diphosgene), trichloroacetyl chloride, 1,1‐carbonyldiimidazole (CDI), carbonate esters, N ‐acylbenzotriazoles, isocyanates or cyanate salts, isocyanides, dialkylazodicarboxylate, azides, amides, CO 2 , and CO, instead of COCl 2 for carbamate production. Despite the development of carbonyl sources, these processes utilize strong bases, toxic metal‐based catalysts, expensive ligands, multistep procedures, and harsh reaction conditions.…”

One-pot synthesis of carbamates and thiocarbamates from Boc-protected amines

“…The traditional method involves the use of toxic phosgene or triphosgene and transition metal species such as palladium, 4 nickel, 5 and rhodium. 4b, 6 Recently, more environmentally benign procedures also have been developed. For example, carbonates, 7 N-N'-carbonyldiimidazole, 8 1,1′-carbonylbisbenzotriazole, 9 S,S-dimethylthiocarbonate, 10 and Smethylthiocarbamate 11 have been used for the synthesis of carbamates and thiocarbamates.…”

A new route to allyl thiols and allyl thiocarbamates from Baylis‐Hillman adducts

“…Generally, thiols have been synthesized mainly from alkyl halides with thioacetate ion followed by deacetylation with base [15], disulfides via reduction [16], alkenes via anti‐Markovnikov addition of thiolacetic acid, followed by deacetylation with strong base [17], alcohols via refluxing with hydrobromic acid and thiourea, followed by hydrolysis with strong base [18], thiocyanates via reduction [19], and thiocarbamates via hydrolysis [20]. The most widely used method for the preparation of thiocarbamates makes use of gaseous carbonyl sulfides and an amine, followed by subsequent treatment with base and alkyl halide [12, 21], condensation of a thiol with an isocyanate [10], nucleophilic substitution of trichloroacetyl chloride with a thiol, followed by treatment of an amine [22], and the hydration of an organic thiocyanate [23, 24]. In view of their significance in organic synthesis, it is still necessary to extend the scope of the allyl thiol and thiocarbamate families and develop new and convenient synthetic routes.…”