55852-80-7Relevant academic research and scientific papers
O,S-Dimethyl carbonodithioate as a phosgene substitute for the preparation of S-methyl alkylcarbamothioates and dialkylcarbamothioates
Degani, Iacopo,Fochi, Rita,Magistris, Claudio
experimental part, p. 3807 - 3818 (2010/03/30)
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.
Solvent-free synthesis of urea derivatives from primary amines and sulfur under carbon monoxide and oxygen at atmospheric pressure
Mizuno, Takumi,Mihara, Masatoshi,Nakai, Takeo,Iwai, Toshiyuki,Ito, Takatoshi
, p. 3135 - 3140 (2008/04/03)
A solvent-free carbonylation and oxidation system aimed at green and sustainable chemistry was developed. With these reactions, an environmentally benign synthesis of urea derivatives could be carried out in good to excellent yields from primary amines and sulfur at ambient pressure of carbon monoxide and oxygen. For example, N,N′-dioctylurea was prepared in 99% yield from two equivalents octylamine and one equivalent sulfur in the presence of carbon monoxide (1 atm) at 80°C and oxygen (1 atm) at room temperature, in the complete absence of solvent. Georg Thieme Verlag Stuttgart.
Solvent-assisted thiocarboxylation of amines and alcohols with carbon monoxide and sulfur under mild conditions
Mizuno, Takumi,Iwai, Toshiyuki,Ishino, Yoshio
, p. 9157 - 9163 (2007/10/03)
DMSO or DMF as a solvent strongly accelerated the thiocarboxylation of amines and alcohols with carbon monoxide and sulfur. Under mild conditions (1 atm, 20°C), this thiocarboxylation of amines assisted by DMSO with carbon monoxide and sulfur has been developed into a practical and convenient synthetic method for S-alkyl thiocarbamates in good to excellent yields, including EPTC, thiobencarb, orbencarb, and molinate (herbicides). DMF also showed the similar solvent effect. NMP slightly decreased the effect for the thiocarboxylation of amines, and the yield of S-alkyl thiocarbamate was lowered in DMAc. Surprisingly, no formation of S-alkyl thiocarbamate was observed at the use of the other solvents, such as THF, hexane, toluene, AcOEt, MeCN, MeOH, and H 2O. The present solvent-assisted thiocarboxylation with carbon monoxide and sulfur could be also applied to a new synthesis of S-alkyl O-alkyl carbonothioates from alcohols under mild conditions (1 atm, 20°C) in DMF using DBU (1,8-diazabicyclo[5.4.0]undec-7-ene).
Facile S-alkyl thiocarbamate synthesis by a novel DBU-assisted carbonylation of amines with carbon monoxide and sulfur
Mizuno, Takumi,Takahashi, Junko,Ogawa, Akiya
, p. 1327 - 1331 (2007/10/03)
A novel DBU-assisted carbonylation of amines with carbon monoxide and sulfur has been developed for the synthesis of S-alkyl thiocarbamates. In the presence of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), S-alkyl thiocarbamates are synthesized in excellent yields from amines, carbon monoxide, sulfur, and alkyl halides under mild conditions (1 atm, 20°C). In the absence of DBU, however, no formation of S-alkyl thiocarbamate is observed. The present DBU-assisted carbonylation can also be applied to new synthetic methods for benthiocarb and orthobencarb (herbicides) and carbamoyl chlorides.
Reaction of Thiolates with Carbon Monoxide
Mizuno, Takumi,Daigaku, Takayuki,Nishiguchi, Ikuzo
, p. 1533 - 1536 (2007/10/02)
Thiolates generated from elemental sulfur with amines or lithium amides, easily reacted with carbon monoxide to form thiocarbamates in good yields.Furthermore, the reaction of diaminodisulfide with carbon monoxide in the presence of DBU proceeded similarl
Novel synthesis of S-alkyl thiocarbamates from amines, carbon monoxide, elemental sulfur, and alkyl halides in the presence of a selenium catalyst
Mizuno, Takumi,Nishiguchi, Ikuzo,Sonoda, Noboru
, p. 5669 - 5680 (2007/10/02)
Carbonyl selenide easily reacted with elemental sulfur at low temperature to form carbonyl sulfide in a good yield, and reaction of ammonium salts of selenocarbamates with elemental sulfur brought about ready transformation to those of thiocarbamates. On the basis of the high catalytic activity of selenium for carbonylation of amines with carbon monoxide in addition to these important findings, a convenient new method for synthesis of S-alkyl thiocarbamates was developed through the carbonylation of amines with carbon monoxide and elemental sulfur in the presence of a selenium catalyst under mild conditions followed by alkylation of ammonium salts of the thiocarbamates with alkyl halides.
REACTIONS OF UNSTABLE DIALKYLCARBAMOYL LITHIUMS WITH SULFUR COMPOUNDS
Mizuno, Takumi,Nishiguchi, Ikuzo,Hirashima, Tsuneaki
, p. 2403 - 2412 (2007/10/02)
Unstable dialkylcarbamoyl lithiums, generated from the reaction of lithium dialkylamides with carbon monoxide, were successfully trapped by sulfur compounds (elemental sulfur, disulfides, carbon disulfide, and carbonyl sulfide) at low temperature, through their potent affinity with a sulfur atom.These efficient reactions were also applied to development of a facile synthetic method for thiocarbamates, useful herbicides, and thiooxamates.
