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Synthesis 2007(7): 1096-1102  
DOI: 10.1055/s-2007-965943
PAPER
© Georg Thieme Verlag Stuttgart · New York

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

Emma Artusoa, Gianni Carvolib, Iacopo Degani, Rita Fochi*a, Claudio Magistrisa
a Dipartimento di Chimica Generale ed Organica Applicata, Università Torino, C.so M. D’Azeglio 48, 10125 Torino, Italy
e-Mail: rita.fochi@unito.it;
b Oxon Italia S.p.A., Via Sempione 195, 20016 Pero (Milano), Italy
Further Information

Publication History

Received 12 December 2006
Publication Date:
20 February 2007 (online)

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Abstract

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.

Key words

thiocarbamates - thiocarbonylation - dithiocarbonates - amines - chemoselectivity

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1

Professor Emeritus, University of Turin (Italy).

17

Oxon Italia S.p.A. (Italy).