Citation: Jin-Wu Zhao, Jing-Xiu Xu, Xiu-Zhen Guo. Green synthesis of 1,2,4-thiadizoles from thioamides in water using molecular oxygen as an oxidant[J]. Chinese Chemical Letters, ;2014, 25(11): 1499-1502. doi: 10.1016/j.cclet.2014.05.019 shu

Green synthesis of 1,2,4-thiadizoles from thioamides in water using molecular oxygen as an oxidant

1.
School of Pharmacy, Guangdong Medical College, Dongguan 523808, China

Corresponding author: Jin-Wu Zhao,
Received Date: 13 March 2014
Available Online: 5 May 2014
Fund Project: We thank Guangdong Medical College (No. XK1110) for financial support. (No. XK1110)

We present here an efficient green process for the synthesis of 1,2,4-thiadiazoles via iodine-catalyzed, oxidative dimerization of thioamides in water using molecular oxygen as a terminal oxidant. Under the optimized reaction conditions, aryl thioamides produced 3,5-diaryl-1,2,4-thiadiazoles in good to excellent yields. Alkyl thioamides and substituted thioureas could also provide corresponding 1,2,4- thiadiazole products.
- 1,2,4-Thiadizole,
- Thioamide,
- Water,
- Oxygen
1. [1]
  [1] (a) W.J.W. Watson, How do the fine chemical, pharmaceutical, and related industries approach green chemistry and sustainability? Green Chem. 14 (2012) 251-259; (b) P.J. Dunn, The importance of green chemistry in process research and development, Chem. Soc. Rev. 41 (2012) 1452-1461; (c) P.J. Dunn, Pharmaceutical green chemistry process changes - how long does it take to obtain regulatory approval? Green Chem. 15 (2013) 3099-3104.
2. [2]
  [2] (a) M.O. Simona, C.J. Li, Green chemistry oriented organic synthesis in water, Chem. Soc. Rev. 41 (2012) 1415-1427; (b) R.N. Butler, A.G. Coyne, Water: nature's reaction enforcer-comparative effects for organic synthesis "in-water" and "on-water", Chem. Rev. 110 (2010) 6302- 6337; (c) T. Chang, L.Q. He, L. Bian, et al., Brønsted acid-surfactant-combined catalyst for the Mannich reaction in water, RSC Adv. 4 (2014) 727-731.
3. [3]
  [3] (a) W.Q. Wu, H.F. Jiang, Palladium-catalyzed oxidation of unsaturated hydrocarbons using molecular oxygen, Acc. Chem. Res. 45 (2012) 1736-1748; (b) Z.Z. Shi, C. Zhang, C.H. Tang, N. Jiao, Recent advances in transition-metal catalyzed reactions using molecular oxygen as the oxidant, Chem. Soc. Rev. 41 (2012) 3381-3430; (c) G.Y. Liu, R.R. Tang, Z.Wang, Metal-free allylic oxidation with molecular oxygen catalyzed by g-C3N4 and N-hydroxyphthalimide, Catal. Lett. 144 (2014) 717-722.
4. [4]
  [4] A. Castro, T. Castañ o, A. Encinas, W. Porcal, C. Gil, Advances in the synthesis and recent therapeutic applications of 1,2,4-thiadiazole heterocycles, Bioorg. Med. Chem. 14 (2006) 1644-1652.
5. [5]
  [5] A.S. Mayhoub, L. Marler, T.P. Kondratyuk, R. Gupta, K. Shah, Optimizing thiadiazole analogues of resveratrol versus three chemopreventive targets, Bioorg. Med. Chem. 20 (2012) 510-520.
6. [6]
  [6] D. Kumar, N.M. Kumar, K.H. Chang, et al., Synthesis and in-vitro anticancer activity of 3,5-bis(indolyl)-1,2,4-thiadiazoles, Bioorg. Med. Chem. Lett. 21 (2011) 5897-5900.
7. [7]
  [7] F. Ren, G.H. Deng, H.L. Wang, et al., Discovery of novel 1,2,4-thiadiazole derivatives as potent, orally active agonists of sphingosine 1-phosphate receptor subtype 1 (S1P1), J. Med. Chem. 55 (2012) 4286-4296.
8. [8]
  [8] (a) E.A.F. Fordyce, A.J. Morrison, R.D. Sharp, et al., Microwave-induced generation and reactions of nitrile sulfides: an improved method for the synthesis of isothiazoles and 1,2,4-thiadiazoles, Tetrahedron 66 (2010) 7192-7200; (b) H.A. Beeley, S. Degorce, C.S. Harris, et al., One-pot synthesis of bis(amino)- 1,2,4-thiadiazoles via direct SNAr, Tetrahedron Lett. 54 (2013) 788-791; (c) J. Noei, A.R. Khosropour, A novel process for the synthesis of 3,5-diaryl-1,2,4- thiadiazoles from aryl nitriles, Tetrahedron Lett. 54 (2013) 9-11; (d) Y.L. Xu, J.X. Chen, W.X. Gao, et al., Solvent-free synthesis of 3,5-di(hetero)aryl- 1,2,4-thiadiazoles by grinding of thioamides under oxidative conditions, J. Chem. Res. 34 (2010) 151-153.
9. [9]
  [9] (a) A.A. Shah, Z.A. Khan, N. Choudhary, et al., Iodoxolone-based hypervalent iodine reagents, Org. Lett. 11 (2009) 3578-3581; (b) P.C. Patil, D.S. Bhalerao, P.S. Dangate, et al., IBX/TEAB-mediated oxidative dimerization of thioamides: synthesis of 3,5-disubstituted 1,2,4-thiadiazoles, Tetrahedron Lett. 50 (2009) 5820-5822.
10. [10]
  [10] (a) A.S. Mayhoub, E. Kiselev, M. Cushman, An unexpected synthesis of 3,5-diaryl- 1,2,4-thiadiazoles from thiobenzamides and methyl bromocyanoacetate, Tetrahedron Lett. 52 (2011) 4941-4943; (b) H.Z. Boeini, M. Mobin, An unexpected result of the reaction of benzothioamide derivatives with 2-aryl-2-bromoacetonitriles, Helv. Chim. Acta 94 (2011) 2039-2044.
11. [11]
  [11] (a) A.R. Khosropour, J. Noei, TCT-DMSO/[bmim]BF4: a novel promoter system for the synthesis of 3,5-diaryl-1,2,4-thiadiazoles at ambient temperature, J. Heterocycl. Chem. 48 (2010) 226-229; (b) Y. Takikawa, K. Shimada, K. Sato, et al., Convenient preparations of 3,5- disubstituted 1,2,4-thiadiazoles by oxidative dimerization of thioamides, Bull. Chem. Soc. Jpn. 58 (1985) 995-999.
12. [12]
  [12] (a) T. Fukumoto, T. Matsuki, N.X. Hu, Benzenetellurinic mixed anhydrides as mild oxidizing agents, Chem. Lett. 19 (1990) 2269-2272; (b) M.T.M. El-Wassimy, K.A. Jorgensen, S.O. Lawesson, The reaction of t-butyl hypochlorite with thiocarbonyl compound - a convenient method for the transformation, Tetrahedron 39 (1983) 1729-1734.
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沈阳化工大学材料科学与工程学院沈阳 110142