PDF herunterladen
Synthesis 2008(10): 1612-1618  
DOI: 10.1055/s-2008-1072573
PAPER
© Georg Thieme Verlag Stuttgart · New York

One-Pot, Three-Step Preparation of Alkyl and Aryl Alkylcarbamates from S-Methyl N-Alkylthiocarbamates

Emma Artuso, 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
Fax: +39(011)6707642; e-Mail: rita.fochi@unito.it;
Weitere Informationen

Publikationsverlauf

Received 30 January 2008
Publikationsdatum:
27. März 2008 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

A general procedure for the synthesis of alkyl and aryl alkylcarbamates starting from the corresponding S-methyl N-alkyl­thiocarbamates is described. This procedure consists of three steps that are carried out in a one-pot fashion, without isolating the intermediate N-alkylcarbamoyl chlorides or alkyl isocyanates. All the target products were obtained in high yields (16 examples, average yield 91%). To be noted is the recovery of a co-product of industrial interest, dimethyl disulfide, in a half mole amount for each mole of thiocarbamate, with complete exploitation of the reagent. The alkyl isocyanates, if required, can also be isolated in high yields.

Key words

carbamates - amines - dithiocarbonates - thiocarbamates - isocyanates

    References

  • 2 Artuso E. Degani I. Fochi R. Magistris C. Synthesis  2007,  3497 
    Thieme Connect
  • 3 Artuso E. Carvoli G. Degani I. Fochi R. Magistris C. Synthesis  2007,  1096 
    Thieme Connect
  • 4a Carvoli G, Degani I, Pallucca E, Fochi R, Gazzetto S, Artuso E, Lazzaroni M, and Cadamuro S. inventors; Oxon Italia S.p.A., Italy, patent request No. MI 2005  001284. 
  • 4b Carvoli G, Degani I, Pallucca E, Fochi R, Serri AM, Cadamuro S, Gazzetto S, and Migliaccio M. inventors; Oxon Italia S.p.A., Italy, patent request No. MI 2004  002402. 
  • For reviews on carbamates, see:
  • 5a Chaturvedi D. Ray S. Chem. Rev.  2006,  137:  127 
    CrossrefSuche in Google Scholar
  • 5b Rossi L. In Science of Synthesis   Vol. 18:  Knight JG. Thieme Verlag; Stuttgart: 2005.  p.461-598  
    CrossrefSuche in Google Scholar
  • 5c Belli Dell’Amico D. Calderazzo F. Labella L. Marchetti F. Pampaloni G. Chem. Rev.  2003,  103:  3857 
    CrossrefSuche in Google Scholar
  • 5d Petersen U. In Houben-Weyl   4th ed., Vol. E4:  Hagemann H. Thieme; Stuttgart: 1983.  p.142-238  
    CrossrefSuche in Google Scholar
  • 5e Melnikov NN. In Chemistry of Pesticides   Gunther FA. Gunther JD. Springer-Verlag; Berlin: 1971.  p.206-222  
    Crossref
  • 5f Adams P. Baron FA. Chem. Rev.  1965,  65:  567 
    CrossrefSuche in Google Scholar
  • 6 For plentiful literature on the syntheses and applications of carbamates, see: Feroci M. Casadei MA. Palombi L. Inesi A. J. Org. Chem.  2003,  68:  1548 ; and references cited therein
    CrossrefPubMedSuche in Google Scholar
  • 7 For plentiful literature on the syntheses of carbamates using carbon dioxide, see: Feroci M. Orsini M. Sotgiu G. Rossi L. Inesi A. J. Org. Chem.  2007,  72:  200 ; and references cited therein
    CrossrefPubMedSuche in Google Scholar
  • For example, for toxicity of phosgene, see:
  • 8a Cotarca L. Eckert H. In Phosgenations - A Handbook   Wiley-VCH; Weinheim: 2003.  p.9 
  • 8b Senet J.-P. (Groups SNPE) In The Recent Advance in Phosgene Chemistry   Vol. 1:  GPA; Nanterre: 1997.  p.10-11  
    Suche in Google Scholar
  • 8c Sax NI. In Dangerous Properties of Industrial Materials   Van Nostrand Reinhold Company; New York: 1984.  p.2210-2211  
  • For some recent references on carbamates (after 2005), see:
  • 9a Gogoi P. Konwar D. Tetrahedron Lett.  2007,  48:  531 
    CrossrefSuche in Google Scholar
  • 9b Singh OV. Han H. J. Am. Chem. Soc.  2007,  129:  774 
    CrossrefSuche in Google Scholar
  • 9c Meudt A, Böhm C, and Schweitzer K. inventors; Archimica GmbH Germany, WO  2007006465.  ; Chem. Abstr. 2007, 146, 162924
    Crossref
  • 9d Singh KN. Synth. Commun.  2007,  37:  2651 
    CrossrefSuche in Google Scholar
  • 9e Srinivas D, Srivastava R, and Ratnasamy P. inventors; US  20070270605.  ; Chem. Abstr. 2007, 148, 12984
    Crossref
  • 9f Han C. Porco JA. Org. Lett.  2007,  9:  1517 
    CrossrefSuche in Google Scholar
  • 9g Zheng S. Li F. Liu J. Xia C. Tetrahedron Lett.  2007,  48:  5883 
    CrossrefSuche in Google Scholar
  • 9h Orito K. Miyazawa M. Nakamura T. Horibata A. Ushito H. Nagasaki H. Yuguchi M. Yamashita S. Yamazaki T. Tokuda M. J. Org. Chem.  2006,  71:  5951 
    CrossrefSuche in Google Scholar
  • 9i Distaso M. Quaranta E. Appl. Catal. B  2006,  66:  72 
    CrossrefSuche in Google Scholar
  • 9j Litwnowicz M. Kijenski J. Kwiatkowski J. Pasinska-Grochowy D. Przem. Chem.  2006,  85:  114 ; Chem. Abstr. 2006, 145, 358699
    CrossrefSuche in Google Scholar
  • 9k Gupte SP, Chaudari RV, Anandkumar BS, and Mulla SA. inventors; Council of Scientific & Industrial Research India, WO  2005063698.  ; Chem. Abstr. 2005, 143, 77708
    Crossref
  • 9l Gupte SP, Chaudari RV, Anandkumar BS, and Mulla SA. inventors; Council of Scientific & Industrial Research India, US  2005222450.  ; Chem. Abstr. 2005, 143, 115358
    Crossref
  • 9m Srivastava R. Srinivas D. Ratnasamy P. Appl. Catal.  2005,  289:  128 
    CrossrefSuche in Google Scholar
  • 9n Chaturvedi D. Ray S. Lett. Org. Chem.  2005,  2:  742 ; Chem. Abstr. 2006, 144, 488108
    CrossrefSuche in Google Scholar
  • 9o Lebel H. Leogane O. Org. Lett.  2005,  7:  4107 
    CrossrefSuche in Google Scholar
  • 9p Hiegel GA. Hogenauer TJ. Synth. Commun.  2005,  35:  2091 
    CrossrefSuche in Google Scholar
  • 9q Spino C. Joly M.-A. Godbout C. Arbour M. J. Org. Chem.  2005,  70:  6118 
    CrossrefSuche in Google Scholar
  • 9r Grzyb JA. Shen M. Yoshina-Ishii C. Chi W. Brown RS. Tetrahedron  2005,  61:  7153 
    CrossrefSuche in Google Scholar
  • 9s Ramesh R. Bhat RG. Chandrasekaran S. J. Org. Chem.  2005,  70:  837 
    CrossrefSuche in Google Scholar
  • 9t Raje VP. Bhat RP. Samant SD. Tetrahedron. Lett.  2005,  46:  835 
    CrossrefSuche in Google Scholar
  • 10 Minato H. Takeda K. Miura T. Kobayashi M. Chem. Lett.  1977,  1095 
    Crossref
  • 11a Cotarca L. Eckert H. In Phosgenations - A Handbook   Wiley-VCH; Weinheim: 2003.  p.208-210 and 270-273  
    Crossref
  • 11b Bigi F. Sartori G. Green Chem.  2000,  2:  140 
    CrossrefSuche in Google Scholar
  • 13 Degani I. Fochi R. Regondi V. Synthesis  1981,  149 
    Thieme Connect
  • 14 D’Silva TDJ. Lopes A. Jones RL. Singhawangcha S. Chan JK. J. Org. Chem.  1986,  51:  3781 
    Suche in Google Scholar
  • 15 Dictionary of Organic Compounds on CD-ROM   Chapman & Hall, Electronic Publishing Division; London: 2007. Version 15.2 [CD ROM]
  • 18 Kolbezen MJ. Metcalf RL. Fukuto TR. J. Agric. Food Chem.  1954,  2:  864 
    CrossrefSuche in Google Scholar
  • 19 Heiss R, Bocker E, and Morschel H. inventors; Bayer AG, DE  1165577.  ; Chem. Abstr. 1964, 61, 1797a
  • 20 Al-Rawi H. Williams A. J. Am. Chem. Soc.  1977,  99:  2671 
    CrossrefSuche in Google Scholar
  • 21 Pianka M. Polton DJ. J. Chem. Soc.  1960,  983 
  • 22 Yu QS. Schoenenberger B. Brossi A. Heterocycles  1987,  26:  1271 
    CrossrefSuche in Google Scholar
  • 23 Wallace GC. Zerba EN. Pestic. Sci.  1989,  215 
    Crossref
  • 24 Ben-Ishai D. Katchalski E. J. Org. Chem.  1951,  16:  1025 
    CrossrefSuche in Google Scholar
  • 25 Pelah Z. inventors; Makhteshim Chem Works LTD, DE  1910296.  ; Chem. Abstr. 1970, 72, 43298e
  • 26 Berntsson P. Brandstrom A. Junggren U. Palmer L. Sjostrandi SE. Sundell G. Acta Pharm. Suec.  1977,  14:  229 ; Chem. Abstr. 1978, 89, 59754
    Suche in Google Scholar
  • 27 Schalk W, and Schmied-Kowarzik V. inventors; Union Carbide Corp., DE  1138277.  ; Chem. Abstr. 1961, 55, 2591b
  • 28 Ramesh R. Chandrasekaran Y. Legha R. Chandrasekaran S. Tetrahedron  2007,  63:  9153 
    CrossrefSuche in Google Scholar
  • 29 Pierce AC. Joullie MM. J. Org. Chem.  1963,  28:  658 
    CrossrefSuche in Google Scholar
  • 30 McGhee W. Riley D. Christ K. Pan Y. Parnas B.
    J. Org. Chem.  1995,  60:  2820 
    CrossrefSuche in Google Scholar
  • 31 Fraley RW. inventors; PPG Industries Inc., US  3734945.  ; Chem. Abstr. 1971, 79, 18453
  • 32 Patonay T. Patonay-Peli E. Mogyorodi F. Synth. Commun.  1990,  20:  2865 
    CrossrefSuche in Google Scholar
  • 33 Thompson RD. Baumgarten HE. Org. Synth. Coll. Vol. V   John Wiley & Sons; London: 1973.  p.709 
1

Professor Emeritus, University of Turin (Italy).

12

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

16

Spectral Data Base for Organic Compounds SDBS (National Institute of Advanced Industrial Science and Technology). SDBS Web: http://riodb.ibase.aist.go.jp/index.html.

17

Details are reported in reference 4a.