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I. Degani et al.
PAPER
(8) (a) Carvoli, G.; Degani, I.; Pallucca, E.; Fochi, R.; Serri,
Reaction of S,S-Dimethyl Carbonodithioate (13) with 30%
Aqueous Ammonia
A. M.; Cadamuro, S.; Gazzetto, S.; Migliaccio, M. (Oxon
Italia SpA) Patent IT MI2004002402, 2004. (b) Artuso, E.;
Degani, I.; Fochi, R.; Magistris, C. Synthesis 2007, 3497.
(c) Degani, I.; Fochi, R.; Magistris, C.; Migliaccio, M.
Synthesis 2009, 801.
A mixture of S,S-dimethyl carbonodithioate (13; 2.44 g, 20 mmol)
and 30% aq ammonia (8 mL) was heated to 60 °C in an oil bath with
stirring. During the reaction, the oily substance disappeared and
MeSH was formed. This was absorbed in 10–15% aq NaOH. After
2 h, a colorless soln was obtained. After elimination of H2O under
reduced pressure, pure urea was obtained as a colorless substance;
yield: 1.20 g (quant); mp 133–135 °C. This was identical to an au-
thentic, commercially available, sample (Aldrich).
(9) For syntheses and applications of S-alkyl carbamothioates,
particularly S-methyl carbamothioates, see Ref. 6 and
references cited therein.
(10) A part of this study has been patented, see:Pallucca, E.;
Degani, I.; Serri, A. M.; Fochi, R.; Gazzetto, S.; Fenoglio,
C.; Ornati, C.; Migliaccio, M.; Cadamuro, S.; Carvoli, G.;
(Oxon Italia SpA.) Patent EP 1334965, 2003; Chem. Abstr.
2003, 139, 164529.
Heating of O,S-Dimethyl Carbonodithioate (1) to 100 °C
MeSC(S)OMe (1; 1.22 g, 10 mmol) was heated to 100 °C in an oil
bath. After 1 h, GC and GC-MS analyses showed that compound 1
was practically unchanged, and after 2 h, about 2% of isomer 13 was
also present. The amount of 13 increased to 6–7% after 5 h.
(11) For some examples of isomerizations of O-alkyl
carbamothioates to the corresponding S-alkyl carbamo-
thioates, see: (a) Fujii, K.; Shuto, Y.; Kinoshita, Y. Agric.
Biol. Chem. 1990, 54, 2379. (b) Tandel, S. K.; Rajappa, S.;
Pansare, S. V. Tetrahedron 1993, 49, 7479. (c) Sakamoto,
M.; Yoshiaki, M.; Takahashi, M.; Fujita, T.; Watanabe, S.
J. Chem. Soc., Perkin Trans. 1 1995, 373. (d) Tandel, S. K.;
Naik, R. H.; Rajappa, S. (Council of Scientific and Industrial
Research, India) IN 175790, 1995; Chem. Abstr. 2003, 139,
395632. (e) Harayama, H.; Nagahama, T.; Kozera, T.;
Kimura, M.; Fugami, K.; Tanaka, S.; Tamaru, Y. Bull.
Chem. Soc. Jpn. 1997, 70, 445. (f) Böhme, A.; Gais, H.-J.
Tetrahedron: Asymmetry 1999, 10, 2511. (g) Gais, H.-J.;
Böhme, A. J. Org. Chem. 2002, 67, 1153. (h) Milosavljevi,
M. M.; Marinkovi, A. D.; Djordjevi, S. A. Hem. Ind. 2006,
60, 27; Chem. Abstr. 2006, 146, 461825. (i) Crich, D.;
Brebion, F.; Krishnamurthy, V. Org. Lett. 2006, 8, 3593.
(j) Crich, D.; Krishnamurthy, V.; Brebion, F.; Karatholuvhu,
M.; Subramanian, V.; Hutton, T. K. J. Am. Chem. Soc. 2007,
129, 10282. (k) Crich, D.; Brebion, F.; Krishnamurthy, V.
(Olson & Hierl) Patent US 2007260041, 2007; Chem. Abstr.
2007, 147, 522585.
Acknowledgment
This work was supported by the Ministero dell’Università e della
Ricerca (MIUR) and National Research Council (CNR), Italy, Na-
tional Project “New Synthetic Methodologies for Industrial Inter-
mediates and Products“, and by the University of Turin.
References
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Synthesis 2009, No. 22, 3807–3818 © Thieme Stuttgart · New York