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Synthesis 2009(22): 3807-3818  
DOI: 10.1055/s-0029-1218117
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

O,S-Dimethyl Carbonodithioate as a Phosgene Substitute for the Preparation of S-Methyl Alkylcarbamothioates and Dialkylcarbamothioates

Iacopo Degani, Rita Fochi*, Claudio Magistris
Dipartimento di Chimica Generale e Chimica Organica, Università degli Studi di Torino, C.so M. D’Azeglio 48, 10125 Torino, Italy
e-Mail: rita.fochi@unito.it;
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Publikationsverlauf

Received 18 June 2009
Publikationsdatum:
23. September 2009 (online)

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Erratum zu diesem Artikel:

O,S-Dimethyl Carbonodithioate as a Phosgene Substitute for the Preparation of S-Methyl Alkylcarbamothioates and DialkylcarbamothioatesSynthesis 2010; 2010(02): 364-364
DOI: 10.1055/s-0029-1218617

Abstract

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 dialkylcarbamo-thioates. 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.

Key words

O,S-dimethyl carbonodithioate - carbamothioates - carbonylation - isomerization - S,S-dimethyl carbonodithioate

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1

Professor Emeritus, University of Turin, Italy.

9

For syntheses and applications of S-alkyl carbamothioates, particularly S-methyl carbamothioates, see Ref. 6 and references cited therein.

12

Degani, I.; Fochi, R.; Magistris, C. unpublished results.

13

Oxon Italia SpA., 20016 Pero (Milano), Italy.