An Easy and Efficient One-Step Procedure for the Preparation of Alkyl and Aryl Alkylcarbamates from S-Methyl N-Alkylthiocarbamates

Abstract

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.

Key words

carbamates - thiocarbamates - S,S-dimethyl dithiocarbonate - green chemistry

References

• For reviews on carbamates, see:
• 2a Chaturvedi D. Ray S. Chem. Rev.  2006,  137:  127 
• 2b Rossi L. In Science of Synthesis   Vol. 18:  Knight JG. Thieme Verlag; Stuttgart: 2005.  p.461-598  
• 2c Belli Dell’Amico D. Calderazzo F. Labella L. Marchetti F. Pampaloni G. Chem. Rev.  2003,  103:  3857 
• 2d Petersen U. In Houben-Weyl   4th ed., Vol. E4:  Hagemann H. Thieme Verlag; Stuttgart: 1983.  p.142-238  
• 2e Melnikov NN. In Chemistry of Pesticides   Gunther FA. Gunther JD. Springer-Verlag; Berlin: 1971.  p.206-222  
• 2f Adams P. Baron FA. Chem. Rev.  1965,  65:  567 
• For plentiful literature on the syntheses and applications of carbamates, see:
• 3a Feroci M. Casadei MA. Palombi L. Inesi A. J. Org. Chem.  2003,  68:  1548 ; and references cited therein
• 3b Feroci M. Orsini M. Sotgiu G. Rossi L. Inesi A. J. Org. Chem.  2007,  72:  200 ; and references cited therein
• 4 Artuso E. Degani I. Fochi R. Magistris C. Synthesis  2008,  1612 
• 5 Artuso E. Carvoli G. Degani I. Fochi R. Magistris C. Synthesis  2007,  1096 
• 6 Tandel SK. Rajappa S. Pansare SV. Tetrahedron  1993,  49:  7479 
• 7 Fujita T. Kamoshita K. Nishioka T. Nakajima M. Agric. Biol. Chem.  1974,  38:  1521 
• 8 Dictionary of Organic Compounds on CD-ROM   version 16.1 [CD ROM]:  Chapman & Hall, Electronic Publishing Division; London: 2008. 
• 9 Curry HM. Mason JP. J. Am. Chem. Soc.  1953,  75:  6357 
• 11 Lin G. Lai C.-Y. Liao W.-C. Bioorg. Med. Chem.  1999,  7:  2683 
• 12 Salvatore RN. Shin SI. Nagle AS. Jung KW. J. Org. Chem.  2001,  66:  1035 
• 13 Falcone SJ, and McCoy JJ. inventors; Atlantic Richfield Co. USA, FR  2481699.  ; Chem. Abstr. 1982, 96, 103895
• 14 Ben-Ishai D. Berger A. J. Org. Chem.  1952,  17:  1564 
• 15 Patonay T. Patonay-Peli E. Mogyorodi F. Synth. Commun.  1990,  20:  2865 
• 16 Degani I. Fochi R. Regondi V. Synthesis  1981,  149 
• 18 Yamagani C. Talcao N. Nishioka T. Fujita T. Takeuchi Y. Org. Magn. Reson.  1984,  22:  439 
• 19 Distaso M. Quaranta E. Tetrahedron  2004,  60:  1531 
• 20 McGhee W. Riley D. Christ K. Pan Y. Parnas B. J. Org. Chem.  1995,  60:  2820 
• 21 Salvatore RN. Chu F. Nagle AS. Kapxhiu EA. Cross RM. Jung KW. Tetrahedron  2002,  58:  3329 

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Professor Emeritus, University of Turin (Italy).

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For details, see IT patent application pending: Carvoli, G.; Degani, I.; Pallucca, E.; Fochi, R.; Gazzetto, S.; Artuso, E.; Lazzaroni, M.; Cadamuro, S. Oxon Italia S.p.A. Italy, patent request No. MI 2005 001284, 2005.

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