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Synthesis 2009(5): 801-808  
DOI: 10.1055/s-0028-1083340
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Preparation of N,N-Dimethyl-N′-Arylureas Using S,S-Dimethyl Dithio­carbonate as a Carbonylating Reagent

Iacopo Degani, Rita Fochi*, Claudio Magistris, Mara Migliaccio
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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Publication History

Received 8 October 2008
Publication Date:
27 January 2009 (online)

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Abstract

A new, general method for the preparation of N,N-di­methyl-N′-arylureas using S,S-dimethyl dithiocarbonate as a phosgene substitute is reported. The method has been set up according to four procedures, all including three steps: (1) reaction of S,S-di­methyl dithiocarbonate with dimethylamine to give S-methyl N,N-dimethylthiocarbamate; (2) halogenation with various halogenating reagents (chlorine, methanesulfenyl chloride, bromine, and methanesulfenyl bromide) to give N,N-dimethylcarbamoyl chloride or bromide; (3) in situ reaction with primary arylamines. All the target products were obtained in high yields (85-98%; 16 reactions, average yield 93%) and with high purity. Also noteworthy is the recovery of byproducts of industrial interest, namely methanethiol and dimethyl disulfide, with complete exploitation of the reagent S,S-dimethyl dithiocarbonate.

Key words

ureas - S,S-dimethyl dithiocarbonate - halodemethylthio­lations - halogenations - carbonylations

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1

Professor Emeritus, University of Turin, Italy.

16

Oxon Italia S.p.A., 20016 Pero (Milano), Italy.

30

¹H NMR spectrum (500 MHz) of N,N-dimethylcarbamoyl bromide(6): in the gas phase at r.t.: δ = 3.01 (s); in the liquid phase: two singlets with a chemical shift difference of 46 Hz (data are not reported). [³¹]