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;
Further Information

Publication History

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

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.

    References

  • 2 Kirk-Othmer: Encyclopedia of Chemical Technology   3rd ed., Vol. 12:  Grayson M. Eckroth D. John Wiley & Sons; New York: 1980.  p.319-324  
  • For reviews on the synthesis and applications of substituted ureas, see:
  • 3a Petersen U. In Houben-Weyl   4th ed., Vol. E4:  Hagemann H. Thieme; Stuttgart: 1983.  p.334-367  ; and references cited therein
  • 3b Vishnyakova TP. Golubeva IA. Glebova EV. Russ. Chem. Rev.  1985,  54:  249 
  • 3c Petersen H. In Ullmann’s Encyclopedia of Industrial Chemistry   5th ed., Vol. A27:  Elvers B. Hawkins S. VCH; Weinheim: 1996.  p.355-365  
  • 3d Tafesh AM. Weiguny J. Chem. Rev.  1996,  96:  2035 
  • 3e Bigi F. Maggi R. Sartori G. Green Chem.  2000,  2:  140 
  • 3f Sartori G. Maggi R. In Science of Synthesis   Vol. 18:  Knight JG. Thieme; Stuttgart: 2005.  p.665-758  
  • 4 For recent references on synthesis and applications of substituted ureas, see: Artuso E. Degani I. Fochi R. Magistris C. Synthesis  2007,  3497 ; and references cited therein
  • 5a Todd CWEI. inventors; US  2655445.  , (du Pont de Nemours & Co., USA); ; Chem. Abstr. 1954, 48, 5057
  • 5b Searle NEEI. inventors; US  2764478.  , (du Pont de Nemours & Co., USA); ; Chem. Abstr. 1957, 51, 7203
  • 6a Scherer O, Hörlein G, and Schönowsky H. inventors; US  3937726.  , (Hoechst Aktiengesellschaft Germany); ; Chem. Abstr. 1976, 85, 192415
  • 6b Spatz DM, and Cross B. inventors; US  4289903.  , (American Cyanamid Co., USA); ; Chem. Abstr. 1982, 96, 6442
  • 6c inventors; JP  56156253. Sumitomo Chemical Co., Ltd., Japan; ; Chem. Abstr. 1982, 96, 122456
  • 6d Koenig KH, Schwendemann V, Schirmer U, Liesner M, and Wuerzer B. inventors; DE  3213375.  , (BASF AG, Germany); ; Chem. Abstr. 1984, 100, 51297
  • 6e Haeberle N, Oeltze H, and Brader L. inventors; DE  3638753.  , (Dow Chemical Co., USA); ; Chem. Abstr. 1988, 109, 149091
  • 6f Haug M, Santel HJ, Schmidt RR, and Strang H. inventors; DE  3800269.  , (Bayer AG, Germany); ; Chem. Abstr. 1990, 112, 193779
  • 7a inventors; GB  1407587.  Ciba Geigy AG, Switzerland; ; Chem. Abstr. 1976, 84, 4711
  • 7b Lamuela J. inventors; ES  505400.  , (Kemichrom S. L., Spain); ; Chem. Abstr. 1983, 98, 71722
  • 7c inventors; JP  57169454. Asahi Chemical Industry Co., Ltd., Japan; ; Chem. Abstr. 1983, 98, 53444
  • 7d Sales Barquets R, Perez Esteban L, Martin Recio R, and Hervas Gayo A. inventors; ES  520096.  , (Industria Espanola de Productos Organicos S. A., Spain); ; Chem. Abstr. 1987, 107, 236251
  • 7e Wang X, Mei J, and Lu S. inventors; CN  1597663.  , (Faming Zhuanli Shenqing Gongkai Shuomingshu); ; Chem. Abstr. 2006, 144, 191981
  • 8a Schroth W. Andersch J. Schaedler H.-D. Spitzner R. Chem.-Ztg.  1989,  113:  261 ; Chem. Abstr. 1990, 112, 157600
  • 8b inventors; WO  9706134. Ucb S. A., Belgium; ; Chem. Abstr. 1997, 126, 211920
  • 9a Goldhamer DL. Onyszkewycz M. Wilson A. Tetrahedron Lett.  1968,  38:  4077 
  • 9b inventors; GB  1152892. CIBA Ltd.; ; Chem. Abstr. 1969, 71, 123898
  • 9c inventors; JP  56053645.  Ihara Chemical Industry Co., Ltd., Kumiai Chemical Industry Co., Ltd., Japan; ; Chem. Abstr. 1981, 95, 115096
  • 9d Seckinger K. inventors; DE  3300154.  , (Sandoz GmbH, Germany); ; Chem. Abstr. 1983, 99, 158051
  • 9e Takematsu T, Fukuoka D, Takahashi K, and Hashimoto I. inventors; WO  8700840.  , (Mitsui Petrochemical Industries Ltd., Japan); ; Chem. Abstr. 1987, 107, 236509
  • 9f Camps Anaya M, and Riba Garcia MJ. inventors; ES  2027074.  , (Valles Industrias Organicas S. A., Spain); ; Chem. Abstr. 1993, 118, 21952
  • 9g Igarashi S, Futagawa M, Tanaka N, Kawamura Y, and Morimoto K. inventors; WO  9839289.  , (Nissan Chemical Industries Ltd., Japan); ; Chem. Abstr. 1998, 129, 216611
  • 10a Jones RL. inventors; US  2768971.  , (Imperial Chemical Industries Limited, UK); ; Chem. Abstr. 1957, 51, 39387
  • 10b Wu Z, Guo D, and Zou Z. inventors; CN  1063279.  , (Faming Zhuanli Shenqing Gongkai Shuomingshu, China); ; Chem. Abstr. 1993, 119, 159904
  • 11 Werther RH, Korntner H, Auer E, and Thonhofer K. inventors; Patent Application EP  427963.  , (Agrolinz Agrarchemikalien GmbH, Austria); ; Chem. Abstr. 1991, 115, 70946
  • 12a Yang Y. Lu S. Org. Prep. Proced. Int.  1999,  31:  559 
  • 12b Yang Y, and Lu S. inventors; CN  1276368.  , (Faming Zhuanli Shenqing Gongkai Shuomingshu); ; Chem. Abstr. 2001, 135, 107150
  • 12c Wang X. Li P. Yuan X. Lu S. J. Mol. Catal. A: Chem.  2006,  253:  261 
  • 13a Tietz H, Schwetlick K, Schoebel HJ, Herbig H, and Lankau HJ. inventors; DD  227700.  , (VEB Synthesewerk Schwarzheide); ; Chem. Abstr. 1986, 104, 224726
  • 13b Goodall BL, and Terlouw W. inventors; Patent Application EP  319111.  , (Shell Internationale Research Maatschappij B. V., NL); ; Chem. Abstr. 1989, 111, 214245
  • 13c Yang Y, and Lu S. inventors; CN  1294122.  , (Faming Zhuanli Shenqing Gongkai Shuomingshu); ; Chem. Abstr. 2001, 136, 19950
  • 13d Mei J. Yang Y. Xue Y. Lu S. J. Mol. Catal. A: Chem.  2003,  191:  135 
  • 13e Mei J, Lu S, Yuan X, and Yang Y. inventors; CN  1415601.  , (Faming Zhuanli Shenqing Gongkai Shuomingshu); ; Chem. Abstr. 2005, 143, 132848
  • 13f Mei J, and Lu S. inventors; CN  1491938.  , (Faming Zhuanli Shenqing Gongkai Shuomingshu); ; Chem. Abstr. 2005, 143, 77962
  • On the toxicity of phosgene, see for example:
  • 14a Sax NI. In Dangerous Properties of Industrial Materials   Sax N. I. Van Nostrand Reinhold; New York: 1984.  p.2210-2211  
  • 14b Senet J.-P. (Groupe SNPE); In The Recent Advances in Phosgene Chemistry   Vol. 1:  Groupe SNPE, GPA; Nanterre: 1997.  p.10-11  
  • 14c Cotarca L. Eckert H. Phosgenations - A Handbook   Wiley-VCH; Weinheim: 2003.  p.9 
  • 15 Degani I. Fochi R. Regondi V. Synthesis  1981,  149 
  • 17a Degani I, Fochi R, and Regondi V. inventors; Patent Application EP  63327.  , (CNR, Italy); ; Chem. Abstr. 1983, 98, 160238
  • 17b Degani I. Fochi R. Regondi V. Synthesis  1983,  630 
  • 17c Degani I. Fochi R. Regondi V. Synthesis  1986,  1070 
  • 17d Cadamuro S. Degani I. Fochi R. Regondi V. Chem. Ind. (London)  1986,  671 
  • 17e Degani I, Fochi R, and Regondi V. inventors; IT  1173436.  , (CNR, Italy);
  • 17f Barbero M, Degani I, Fochi R, and Regondi V. inventors; Patent Application EP  234249.  , (CNR, Italy); ; Chem. Abstr. 1988, 108, 23697
  • 17g Barbero M. Cadamuro S. Degani I. Fochi R. Regondi V. Synthesis  1989,  957 
  • 18 Artuso E. Carvoli G. Degani I. Fochi R. Magistris C. Synthesis  2007,  1096 
  • 19a Carvoli G, Degani I, Pallucca E, Fochi R, Gazzetto S, Artuso E, Lazzaroni M, and Cadamuro S. inventors; Italian Patent Application MI 2005A  001284.  , (Oxon Italia S.p.A., Italy);
  • 19b Artuso E. Degani I. Fochi R. Magistris C. Synthesis  2008,  1612 
  • 19c Degani I. Fochi R. Magistris C. Synthesis  2008,  2919 
  • 20 Carvoli G, Degani I, Pallucca E, Fochi R, Serri AM, Cadamuro S, Gazzetto S, and Migliaccio M. inventors; Italian Patent Application MI 2004A  002402.  , (Oxon Italia S.p.A., Italy);
  • 21 Minato H. Takeda K. Miura T. Kobayashi M. Chem. Lett.  1977,  1095 
  • 22 Thompson RD. Baumgarten HE. Org. Synth., Coll. Vol. V   John Wiley & Sons; London: 1973.  p.709 
  • 23a Dasgupta F. Garegg PJ. Carbohydr. Res.  1988,  177:  c13 
  • 23b Silvestri MG. Wong C.-H. J. Org. Chem.  2001,  66:  910 
  • 23c Dziadek S. Brocke C. Kunz H. Chem. Eur. J.  2004,  10:  4150 
  • 23d Kurosu M. Kitagawa I. J. Carbohydr. Chem.  2006,  25:  427 
  • 24 Dictionary of Organic Compounds on CD-ROM   Version 15.2 [CD ROM]:  Chapman & Hall Electronic Publishing Division; London: 2007. 
  • 25 Mizuno T. Kino T. Ito T. Miyata T. Synth. Commun.  2000,  30:  1675 
  • 26 Ignatoski JA. inventors; DE  2248388.  , (Diamond Shamrock Corp., USA); ; Chem. Abstr. 1973, 79, 5153
  • 27 Pontes RM. Basso EA. dos Santos FP. J. Org. Chem.  2007,  72:  1901 
  • 28 Still IWJ. Kutney GW. J. Org. Chem.  1981,  46:  4911 
  • 29 Houlden CE. Bailey CD. Ford JG. Gagné MR. Lloyd-Jones GC. Booker-Milburn KI. J. Am. Chem. Soc.  2008,  130:  10066 
  • 31 Ross BD. Wong LT. True NS. J. Phys. Chem.  1985,  89:  836 
  • 32 Dupuy N. Barbry D. Bria M. Marquis S. Vrielynck L. Kister J. Spectrochim. Acta, Part A  2005,  61:  1051 
  • 33 Führer W, Kühle E, Schlee H.-G, Zumach G, Eue L, Schmidt RR, Homeyer B, Reinecke P, Hänssler G, and Santel H.-J. inventors; DE  3506236.  , (Bayer AG, Germany); ; Chem. Abstr. 1987, 106, 49798
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]