90609-83-9

Upstream product

• 6343-54-0 N-benzylformamide 
• 67-68-5 dimethyl sulfoxide 
• 65263-72-1 N-benzyl O-methyl thiocarbamate 
• 67-56-1 methanol 
• 868-84-8 S,S-dimethyl dithiocarbonate 
• 100-46-9 benzylamine 
• 54985-63-6 N-(Benzyl)imidodithiokohlensaeure-S,S'-dimethylester 

Downstream Products

• 39896-97-4 benzyl-carbamic acid benzyl ester 
• 124068-98-0 4-chlorophenyl benzylcarbamate 
• 350602-62-9 hexadecyl benzylcarbamate 
• 132906-00-4 4-bromophenyl benzylcarbamate 
• 41891-25-2 benzylaminocarbonyl chloride 
• 14117-22-7 N-benzyl-N′-butylurea 
• 538-32-9 benzylurea 

Relevant academic research and scientific papers

One-Pot Synthesis of Thiocarbamates

An efficient isocyanide-based synthesis of S-thiocarbamates was discovered and thoroughly investigated. The new reaction protocol is a one-pot procedure and allows the direct conversion of N-formamides into thiocarbamates by initial dehydration with p-toluene sulfonyl chloride to the respective isocyanide and subsequent addition of a sulfoxide component. Contrary to recent literature, which also uses isocyanides as starting material, but with other sulfur reagents than sulfoxides, in this protocol, no isolation and purification of the isocyanide component is necessary, thus significantly decreasing the environmental impact and increasing the efficiency of the synthesis. The new protocol was applied to synthesize a library of sixteen thiocarbamates, applying four N-formamides and four commercially available sulfoxides. Furthermore, experiments were conducted to investigate the reaction mechanism. Finally, four norbornene-based thiocarbamate monomers were prepared and applied in controlled ring-opening metathesis polymerization (ROMP) reactions. The polymers were characterized by size-exclusion chromatography (SEC) and their properties were investigated utilizing differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).

O,S-Dimethyl carbonodithioate as a phosgene substitute for the preparation of S-methyl alkylcarbamothioates and dialkylcarbamothioates

O,S-Dimethyl carbonodithioate is proposed as a suitable and safely handled reagent that can be used as a replacement for phosgene in the synthesis of S-methyl alkyl- and dialkylcarbamothioates. The former were obtained by a two-step procedure, which can also be carried out in a one-pot fashion without isolating the intermediates O-methyl alkylcarbamothioates; the overall yields of the pure S-methyl alkylcarbamothioates were 94-98%. Optimal conditions for the synthesis of S-methyl dialkylcarbamothioates involved a one-step procedure in a solvent-free system in the presence of triethyl(methyl)ammonium methyl carbonate as a catalyst; yields of the pure products were 85-98%. A mechanism is proposed for the carbamothioate-formation reaction. Georg Thieme Verlag Stuttgart.

One-pot, three-step preparation of alkyl and aryl alkylcarbamates from S-methyl N-alkylthiocarbamates

A general procedure for the synthesis of alkyl and aryl alkylcarbamates starting from the corresponding 5-methyl N-alkylthiocarbamates is described. This procedure consists of three steps that are carried out in a one-pot fashion, without isolating the intermediate N-alkylcarbamoyl chlorides or alkyl isocyanates. All the target products were obtained in high yields (16 examples, average yield 91%). To be noted is the recovery of a co-product of industrial interest, dimethyl disulfide, in a half mole amount for each mole of thiocarbamate, with complete exploitation of the reagent. The alkyl isocyanates, if required, can also be isolated in high yields. Georg Thieme Verlag Stuttgart.

An easy and efficient one-step procedure for the preparation of alkyl and aryl alkylcarbamates from S-methyl N-alkylthiocarbamates

A general, one-step procedure for the synthesis of alkyl and aryl alkylcarbamates, by the direct reaction of S-methyl N-alkylthiocarbamates with alcohols or phenols in toluene at reflux in the presence of triethylamine, is reported. All the target products were obtained in high yield (15 examples, average yield 94%) and very high purity (>99.2%). The recovery of a co-product of industrial interest, methanethiol, in an amount of one mole for each mole of thiocarbamate, with complete exploitation of the reagent, should also be noted. Georg Thieme Verlag Stuttgart.

A general, facile, and safe procedure for the preparation of S-methyl N-alkylthiocarbamates by methylthiocarbonylation of primary aliphatic amines with S,S-dimethyl dithiocarbonate

A general procedure is reported for the selective preparation of S-methyl N-alkylthiocarbamates by methylthiocarbonylation of primary aliphatic amines, employing S,S-dimethyl dithiocarbonate as a phosgene substitute. The reactions are carried out in water at room temperature (20-25°C), with S,S-dimethyl dithiocarbonate/amine ratios varying between 1:1.2 and 1:2, and with quantitative recovery of the excess amine. The target products are obtained in exceptionally high yields (generally >95%) and with very high purity (generally >99.5%). Also to be noted is the complete chemoselectivity of the reactions, which can be carried out in the presence of hydroxy or aminophenyl groups. Georg Thieme Verlag Stuttgart.

Preparation of mono-, di-, and trisubstituted ureas by carbonylation of aliphatic amines with S,S-dimethyl dithiocarbonate

General procedures are reported to prepare N-alkylureas, N,N′-dialkylureas (both symmetrical and unsymmetrical), and N,N,N′-trialkylureas by carbonylation of aliphatic amines, employing S,S-dimethyl dithiocarbonate (DMDTC) as a phosgene substitute. All reactions were carried out in water. Symmetrical disubstituted ureas were prepared directly working at 60°C with a molar ratio of DMDTC:amine = 1:2, preferably under nitrogen. Unsymmetrical ureas were prepared in two steps via S-methyl N-alkyl-thiocarbamate intermediates, which are formed selectively in the first step at room temperature. These intermediates react in the second step with ammonia or various aliphatic amines, both primary and secondary, at temperatures varying between 50 and 70°C. All the target ureas were obtained in high yields (28 examples, average yield 94%) and with very high purity (generally >99.2%). Also to be noted is the recovery of a co-product of industrial interest, methanethiol, in an amount of two moles for each mole of DMDTC, with complete exploitation of the reagent. Georg Thieme Verlag Stuttgart.

Process to prepare alkyl-ureas from O,S-dimethyl dithiocarbonate

The present invention relates to the preparation of alkyl-ureas, starting from O,S-dimethyl dithiocarbonate, which provides the following steps: A) causing the O,S-dimethyl dithiocarbonate to react with a primary amine of general formula R1NH2in order to obtain an O-methyl thiocarbamate; B) isomerising the O-methyl thiocarbamate in order to obtain an S-methyl thiocarbamate; C) causing the S-methyl thiocarbamate with a compound of general formula R′R″NH, wherein R′ and R″ may be equal or different one in respect of the other and of R1and may be H, R2or R3, in order to obtain one of the alkyl-ureas of formula (4), (5) or (6).

Process to prepare alkyl-ureas from O,S-dimethyl dithiocarbonate

The present invention relates to the preparation of alkyl-ureas, starting from O,S-dimethyl dithiocarbonate, which provides the following steps:A) causing the O,S-dimethyl dithiocarbonate to react with a primary amine of general formula R1NH2 in order to obtain an O-methyl thiocarbamate;B) isomerising the O-methyl thiocarbamate in order to obtain an S-methyl thiocarbamate;C) causing the S-methyl thiocarbamate with a compound of general formula R'R"NH, wherein R' and R" may be equal or different one in respect of the other and of R1 and may be H, R2 or R3, in order to obtain one of the alkyl-ureas of formula (4), (5) or (6).

Conversion of carbonimidodithioates to carbamates

Carbonimidodithioates derived from primary amines or α-amino acid esters have been converted to N-benzyloxycarbonyl derivatives under mild conditions by treatment first with sodium benzyl alcoholate and then with water. N-Benzyloxycarbonyl α-amino acids have been generated from the methyl esters by alkaline hydrolysis or from the allyl esters by Pd0-catalysed de-allylation.