A Facile, Safe and Inexpensive
Preparation of S-Methyl Arylcarbamothioates by
Methylthiocarbonylation of Primary Arylamines with O,S-Dimethyl ­Carbonodithioate

Iacopo Degani; Rita Fochi; Claudio Magistris

doi:10.1055/s-0029-1219226

PAPER

A Facile, Safe and Inexpensive Preparation of S-Methyl Arylcarbamothioates by Methylthiocarbonylation of Primary Arylamines with O,S-Dimethyl Carbonodithioate

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
e-Mail: rita.fochi@unito.it;

Abstract

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Abstract

O,S-Dimethyl carbonodithioate is proposed as a suitable and safely handled reagent that can be used in the methylthiocarbonylation of primary arylamines to give S-methyl arylcarbamothioates. Optimal conditions involved a one-step procedure that was carried out at 45 ˚C in a solvent-free system, in the presence of triethyl(methyl)ammonium S-methyl carbonodithioate as a reaction promoter. The title products were obtained pure in yields that, with one exception, varied between 72 and 91% (average yield of the 12 considered examples was 83%). The by-product S,S-dimethyl carbonodithioate is also a valuable reagent.

Key words

O,S-dimethyl carbonodithioate - arylcarbamothioates - thiocarbonylation - S,S-dimethyl carbonodithioate - toluene-2,4-dithiocarbamic acid S,S-dimethyl ester

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References

Professor Emeritus, University of Turin, Italy.

For reviews on the synthesis and applications of carbamothioates, see:

<A NAME="RZ24809SS-2A">2a</A> Rossi L. In Science of Synthesis Vol. 18: Knight JG. Thieme Verlag; Stuttgart: 2005. p.599-648 ; and references cited therein

<A NAME="RZ24809SS-2B">2b</A> Petersen U. In Houben-Weyl 4th ed., Vol. E4: Hagemann H. Georg Thieme Verlag; Stuttgart: 1983. p.293-309 ; and references cited therein

<A NAME="RZ24809SS-2C">2c</A> Melnikov NN. In Chemistry of Pesticides Gunther FA. Gunther JD. Springer Verlag; New York: 1971. p.206-222 ; and references cited therein

<A NAME="RZ24809SS-3">3</A> For recent references on the synthesis and applications of carbamothioates, see: Artuso E. Carvoli G. Degani I. Fochi R. Magistris C. Synthesis 2007, 1096 ; and references cited therein

<A NAME="RZ24809SS-4A">4a</A> Harris GH. inventors; Patent US 2863899. ; Chem. Abstr. 1959, 53, 50995

<A NAME="RZ24809SS-4B">4b</A> Freud H, and Jaeger A. inventors; Patent DE 1139694. (Schering AG) ; Chem. Abstr. 1963, 59, 1701

<A NAME="RZ24809SS-4C">4c</A> Sugiyama H, Okuda I, Kazumae N, Kimura I, and Ito H. inventors; Patent JP 48008812. (Kumiai Chemical Industry Co., Ltd., Jpn) ; Chem. Abstr. 1973, 79, 28396

<A NAME="RZ24809SS-4D">4d</A> Czajkowski AJ, and Schafer DE. inventors; Patent US 4231786. (Monsanto Co.) ; Chem. Abstr. 1980, 94, 116011

<A NAME="RZ24809SS-4E">4e</A> Cui D. Li Z. Liu R. Song G. Qian X. Org. Prep. Proced. Int. 2003, 35: 223

<A NAME="RZ24809SS-5">5</A> Lee KH. Koketsu M. Hcoi SY. Lee KJ. Lee P. Chem. Pharm. Bull. 2005, 53: 747

<A NAME="RZ24809SS-6A">6a</A> Takahashi H. Nishina A. Fukumoto R.-h. Kimura H. Koketsu M. Ishihara H. Eur. J. Pharm. Sci. 2005, 24: 291

<A NAME="RZ24809SS-6B">6b</A> Takahashi M, Sekiguchi A, Nishina A, Kimura H, and Koketsu M. inventors; Patent JP 195615. (Gunma Prefecture, Jpn) ; Chem. Abstr. 2008, 149, 299862

<A NAME="RZ24809SS-7">7</A> Koch P, and Anfossi B. inventors; Patent DE 2617918. (Anic S.p.A., Italy) ; Chem. Abstr. 1977, 86, 43427

<A NAME="RZ24809SS-8">8</A> Kim S.-m, Park S.-e, and Kim S.-j. inventors; Patent KR 9704412. (Korea Kumho Petrochemical Co., Ltd., S. Korea) ; Chem. Abstr. 2000, 133, 192768

For syntheses and applications of S-alkyl arylcarbamo-thioates, see:

<A NAME="RZ24809SS-9A">9a</A> Yoshida K. Isobe M. Yano K. Nagamatsu K. Bull. Chem. Soc. Jpn. 1985, 58: 2143

<A NAME="RZ24809SS-9B">9b</A> Sitzmann ME. Gilligan WH. J. Org. Chem. 1985, 50: 5879

<A NAME="RZ24809SS-9C">9c</A> Sonoda N. Mizuno T. Murakami S. Kondo K. Ogawa A. Ryu I. Kambe N. Angew. Chem., Int. Ed. Engl. 1989, 28: 452

<A NAME="RZ24809SS-9D">9d</A> Klimochkin YN. Moiseev IK. Abramov OV. Vladyko GV. Korobchenko LV. Boreko EI. Khimiko-Farmatsevticheskii Zhurnal 1991, 25: 49 ; Chem. Abstr. 1991, 115, 207563

<A NAME="RZ24809SS-9E">9e</A> Nagao Y. Abe Y. Misono T. Ichizen N. Shima Y. Iesaki H. Furushima M. Nippon Kagaku Kaishi 1993, 719 ; Chem. Abstr. 1994, 120, 106493

<A NAME="RZ24809SS-9F">9f</A> Harayama H. Nagahama T. Kozera T. Kimura M. Fugami K. Tanaka S. Tamaru Y. Bull. Chem. Soc. Jpn. 1997, 70: 445

<A NAME="RZ24809SS-9G">9g</A> Koketsu M. Kobayashi C. Ishihara H. Heteroat. Chem. 2003, 14: 374

<A NAME="RZ24809SS-9H">9h</A> Mizuno T. Takahashi J. Ogawa A. Tetrahedron 2003, 59: 1327

<A NAME="RZ24809SS-9I">9i</A> Zhang X. Lu S. Synlett 2005, 1535

<A NAME="RZ24809SS-9J">9j</A> Movassagh B. Zakinezhad Y. Chem. Lett. 2005, 34: 1330

<A NAME="RZ24809SS-9K">9k</A> Zhang X. Lu S. Cuihua Xuebao 2005, 26: 453 ; Chem. Abstr.; 2005, 143: 422104

<A NAME="RZ24809SS-9L">9l</A> Su W, and Zhang J. inventors; Patent CN 1785973. (Zhejiang University of Technology, CN) ; Chem. Abstr. 2006, 145, 145424

<A NAME="RZ24809SS-9M">9m</A> Zhang X, Lu S, and Wang S. inventors; Patent CN 1721402. (Dalian Institute of Chemical Physics, CN) ; Chem. Abstr. 2006, 145, 188564

<A NAME="RZ24809SS-9N">9n</A> Zhang X, and Lu S. inventors; Patent CN 1814588. (Dalian Institute of Chemical Physics, CN) ; Chem. Abstr. 2006, 145, 271467

<A NAME="RZ24809SS-9O">9o</A> Zhang X, and
Lu S. inventors; Patent CN 1824651. (Dalian Institute of Chemical Physics, CN) ; Chem. Abstr. 2006, 145, 292701

<A NAME="RZ24809SS-9P">9p</A> Zhang X, and Lu S. inventors; Patent CN 1847224. (Dalian Institute of Chemical Physics, CN) ; Chem. Abstr. 2006, 145, 471265

<A NAME="RZ24809SS-9Q">9q</A> Zhang X. Lu S. Synth. Commun. 2007, 37: 3291

<A NAME="RZ24809SS-9R">9r</A> Chaturvedi D. Mishra N. Mishra V. Synthesis 2008, 355

<A NAME="RZ24809SS-9S">9s</A> Zhang X. Lu S.-W. Gaodeng Xuexiao Huaxue Xuebao 2008, 29: 1137 ; Chem. Abstr. 2008, 150, 237190

<A NAME="RZ24809SS-10A">10a</A> Macho V, Schmidtova M, and Vojcek L. inventors; Patent SK 277855. (Chemickotechnologicka Facultà Stu.) ; Chem. Abstr. 1997, 126, 59754

<A NAME="RZ24809SS-10B">10b</A> Macho V. Petrol. Coal 1996, 38: 29; Chem Abstr. 1997, 126: 13620

<A NAME="RZ24809SS-11A">11a</A> Koch P, and Anfossi B. inventors; Patent DE 2617917. (Anic S.p.A., Italy) ; Chem. Abstr. 1977, 86, 43426

<A NAME="RZ24809SS-11B">11b</A> Giroldini V, and Neri C. inventors; Patent EP 86017. (Anic S.p.A., Italy) ; Chem. Abstr. 1982, 100, 5887

<A NAME="RZ24809SS-11C">11c</A> Mizuno T. Nishiguchi I. Sonoda N. Tetrahedron 1994, 50: 5669

<A NAME="RZ24809SS-12">12</A> Schirmer U, Becker R, and Wuerzer B. inventors; Patent DE 2926049. (BASF A.G.) ; Chem. Abstr. 1981, 95, 6871

<A NAME="RZ24809SS-13">13</A> Elderfield RC. Short FW. J. Org. Chem. 1953, 18: 1092 ; and references cited therein

For more information on the toxicity of phosgene, see for example:

<A NAME="RZ24809SS-14A">14a</A> Lewis RJ. Sax’s Dangerous Properties of Industrial Materials 11th ed., Vol. 3: Wiley; Hoboken: 2004. p.2944-2945

<A NAME="RZ24809SS-14B">14b</A> Senet J.-P. In Recent Advances in Phosgene Chemistry Vol. 1: Société Nationale des Poudres et des Explosifs; Nanterre: 1997. p.10-11

<A NAME="RZ24809SS-14C">14c</A> Cotarca L. Eckert H. Phosgenations: A Handbook Wiley-VCH; Weinheim: 2003. p.9

<A NAME="RZ24809SS-15A">15a</A> Carvoli G, Degani I, Pallucca E, Fochi R, Gazzetto S, Artuso E, Lazzaroni M, and Cadamuro S. inventors; Patent IT MI 001284. (Oxon Italia S.p.A., Italy)

<A NAME="RZ24809SS-15B">15b</A> Artuso E. Degani I. Fochi R. Magistris C. Synthesis 2008, 1612

<A NAME="RZ24809SS-15C">15c</A> Degani I. Fochi R. Magistris C. Synthesis 2008, 2919

<A NAME="RZ24809SS-16A">16a</A> Carvoli G, Degani I, Pallucca E, Fochi R, Serri AM, Cadamuro S, Gazzetto S, and Migliaccio M. inventors; Patent IT 2004MI2402. (Oxon Italia S.p.A., Italy) ; Chem. Abstr. 2009, 151, 123682

<A NAME="RZ24809SS-16B">16b</A> Artuso E. Degani I. Fochi R. Magistris C. Synthesis 2007, 3497

<A NAME="RZ24809SS-16C">16c</A> Degani I. Fochi R. Magistris C. Migliaccio M. Synthesis 2009, 801

<A NAME="RZ24809SS-17">17</A> Degani I. Fochi R. Regondi V. Synthesis 1981, 149

<A NAME="RZ24809SS-18">18</A> Degani I. Fochi R. Magistris C. Synthesis 2009, 3807

<A NAME="RZ24809SS-19">19</A> Leung M.-k. Lai J.-L. Lau K.-H. Yu H.-h. Hsiao H.-J. J. Org. Chem. 1996, 61: 4175

<A NAME="RZ24809SS-20">20</A> Delepine MM. Schving P. Bull. Soc. Chim. Fr. 1910, 7: 898

<A NAME="RZ24809SS-21A">21a</A> Degani I, Fochi R, and Regondi V. inventors; Patent EP 63327. (CNR, Italy) ; Chem. Abstr.; 1983, 98: 160238

<A NAME="RZ24809SS-21B">21b</A> Degani I. Fochi R. Regondi V. Synthesis 1983, 630

<A NAME="RZ24809SS-21C">21c</A> Degani I. Fochi R. Regondi V. Synthesis 1986, 1070

<A NAME="RZ24809SS-21D">21d</A> Cadamuro S. Degani I. Fochi R. Regondi V. Chem. Ind. (London) 1986, 671

<A NAME="RZ24809SS-21E">21e</A> Degani I, Fochi R, and Regondi V. inventors; Patent IT 1173436. (CNR, Italy)

<A NAME="RZ24809SS-22A">22a</A> Barbero M, Degani I, Fochi R, and Regondi V. inventors; Patent EP 234249. (CNR, Italy) ; Chem. Abstr. 1988, 108, 23697

<A NAME="RZ24809SS-22B">22b</A> Barbero M. Cadamuro S. Degani I. Fochi R. Regondi V. Synthesis 1989, 957

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

<A NAME="RZ24809SS-24">24</A> Bielschowsky W. Ber. Dtsch. Chem. Ges. 1882, 15: 1317

A Facile, Safe and Inexpensive Preparation of S-Methyl Arylcarbamothioates by Methylthiocarbonylation of Primary Arylamines with O,S-Dimethyl ­Carbonodithioate

A Facile, Safe and Inexpensive Preparation of S-Methyl Arylcarbamothioates by Methylthiocarbonylation of Primary Arylamines with O,S-Dimethyl Carbonodithioate