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PRACTICAL SYNTHETIC PROCEDURES
3-Methyl-1,3-benzothiazole-2(3H)-thione (1l)
White solid; yield: 0.63 g (70%); mp 95–97 °C.
1H NMR (CDCl3, 300 MHz): d = 3.84 (s, 3 H), 7.20 (d, J = 8.3 Hz,
1 H), 7.27–7.32 (m, 1 H), 7.39–7.48 (m, 2 H).
13C NMR (CDCl3, 75 MHz): d = 33.2, 112.4, 121.3, 124.9, 127.0,
127.5, 142.0, 189.4.
(2) (a) Zhang, L.; Fan, J.; Vu, K.; Hong, K.; Le Brazidec, J.-Y.;
Shi, J.; Biamonte, M.; Busch, D. J.; Lough, R. E.; Grecko,
R.; Ran, Y.; Sensintaffar, J. L.; Kamal, A.; Lundgren, K.;
Burrows, F. J.; Mansfield, R.; Timony, G. A.; Ulm, E. H.;
Kasibhatla, S. R.; Boehm, M. F. J. Med. Chem. 2006, 40,
5352. (b) Dumas, J.; Brittelli, D.; Chen, J.; Dixon, B.;
Hatoum-Mokdad, H.; König, G.; Sibley, R.; Witowsky, J.;
Wong, S. Bioorg. Med. Chem. Lett. 1999, 9, 2531.
(c) Franchini, C.; Muraglia, M.; Corbo, F.; Florio, M. A.;
Di Mola, A.; Rosato, A.; Matucci, R.; Nesi, M.; Bambeke,
F.; Vitali, C. Arch. Pharm. (Weinheim, Ger.) 2009, 342,
605. (d) Cressier, D.; Prouillac, C.; Hernandez, P.;
Amourette, C.; Diserbo, M.; Lion, C.; Rima, G. Bioorg.
Med. Chem. 2009, 17, 5275. (e) Jiang, L.-L.; Tan, Y.; Zhu,
X.-L.; Wang, Z.-F.; Zuo, Y.; Chen, Q.; Xi, Z.; Yang, G.-F.
J. Agric. Food Chem. 2010, 58, 2643.
(3) (a) Demartin, F.; Deplano, P.; Devillanova, F. A.; Isaia, F.;
Lippolis, V.; Verani, G. Inorg. Chem. 1993, 32, 3694.
(b) Katkova, M. A.; Borisov, A. V.; Fukin, G. K.; Baranov,
E. V.; Averyushkin, A. S.; Vitukhnovsky, A. G.; Bochkarev,
M. N. Inorg. Chim. Acta 2006, 359, 4289. (c) Mishra, L.;
Vilaplana, R.; Singh, V. K.; Yadaw, A. K.; González-
Vilchez, F. J. Inorg. Biochem. 2001, 86, 581.
ESI-MS: m/z = 182.2 [M + H].
HRMS: m/z [M + H]+ calcd for C8H7NS2: 182.0093; found:
182.0091.
3-Ethyl-1,3-benzothiazole-2(3H)-thione (1m)
White solid; yield: 0.63 g (65%); mp 82–84 °C.
1H NMR (CDCl3, 300 MHz): d = 1.40 (t, J = 7.2 Hz, 3 H), 4.50 (q,
J = 7.2 Hz, 2 H), 7.23 (d, J = 8.3 Hz, 1 H), 7.28–7.33 (m, 1 H),
7.40–7.45 (m, 1 H), 7.50 (d, J = 7.9 Hz, 1 H).
13C NMR (CDCl3, 75 MHz,): d = 12.0, 41.5 112.4, 121.6 124.8,
127.1, 128.1, 141.2, 188.7.
ESI-MS: m/z = 196.4 [M + H].
HRMS: m/z [M + H]+ calcd for C9H9NS2: 196.0249; found:
196.0251.
(4) (a) Teppema, J.; Sebrell, L. B. J. Am. Chem. Soc. 1927, 49,
1779. (b) Teppema, J.; Sebrell, L. B. J. Am. Chem. Soc.
1927, 49, 1748. (c) Sebrell, L. B.; Boord, C. E. J. Am. Chem.
Soc. 1923, 45, 2390. (d) Ballabeni, M.; Ballini, R.; Bigi, F.;
Maggi, R.; Parrini, M.; Predieri, G.; Sartori, G. J. Org.
Chem. 1999, 64, 1029. (e) Zhu, N.; Zhang, F.; Liu, G.
J. Comb. Chem. 2010, 12, 531.
(5) (a) Huang, W.; Tan, Y.; Ding, M.-W.; Yang, G.-F. Synth.
Commun. 2007, 37, 369. (b) Zhu, L.; Zhang, M.; Dai, M.
J. Heterocycl. Chem. 2005, 42, 727. (c) Harizi, A.;
Romdhane, A.; Mighri, Z. Tetrahedron Lett. 2000, 41,
5833. (d) Karlsson, H. J.; Lincoln, P.; Westman, G. Bioorg.
Med. Chem. 2003, 11, 1035. (e) Zhu, L.; Zhang, M. J. Org.
Chem. 2004, 69, 7371. (f) Chaudhuri, N. C. Synth. Commun.
1996, 26, 3783. (g) Singh, B.; Pennock, P. O.; Lesher, G. Y.;
Bacon, E. R.; Page, D. F. Heterocycles 1993, 36, 133.
(h) Ma, D.; Lu, X.; Shi, L.; Zhang, H.; Jiang, Y.; Liu, X.
Angew. Chem. Int. Ed. 2011, 50, 1118.
3,6-Dimethyl-1,3-benzothiazole-2(3H)-thione (1n)
White solid; yield: 0.72 g (74%); mp 126–128 °C.
1H NMR (CDCl3, 300 MHz,): d = 2.41 (s, 3 H), 3.82 (s, 3 H), 7.08
(d, J = 8.3 Hz, 1 H), 7.22 (d, J = 8.3 Hz, 1 H), 7.27 (s, 1 H).
13C NMR (CDCl3, 75 MHz): d = 21.2, 33.2, 112.1, 121.4, 127.6,
128.1, 135.1, 140.1, 188.8.
ESI-MS: m/z = 196.4 [M + H].
HRMS: m/z [M + H]+ calcd for C9H9NS2: 196.0249; found:
196.0247.
Acknowledgment
This work was supported by the National Natural Science Founda-
tion of China (20972085 and 21032004) and the National Basic Re-
search Program of China (2012CB933402).
(6) (a) Wang, F.; Cai, S.; Wang, Z.; Xi, C. Org. Lett. 2011, 13,
3202. (b) Wang, F.; Zhao, P.; Xi, C. Heterocycles 2012, 84,
209.
References
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(b) Espinoza-Fonseca, L. M.; Trujillo-Ferrara, J. G.
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(8) Časar, Z.; Lorcy, D.; Leban, I.; Maréchal, A. M.-L. Acta
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(1) These compounds can exist in two tautomeric forms: the
1,3-benzothiazole-2(3H)-thione or the 1,3-benzothiazole-2-
thiol. X-ray determination and calculation suggest that the
1,3-benzothiazole-2(3H)-thione tautomer is generally
favored; see: (a) Curtiss, L. A.; Redfern, P. C.;
Raghavachari, K.; Pople, J. A. J. Chem. Phys. 2001, 114,
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Synthesis 2012, 44, 1477–1480
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