Utility of N-Bromosuccinimide–Water Combination as a Green Reagent for Synthesis of N,S-Heterocycles and Dithiocarbamates from Styrenes

Abstract

An efficient and unprecedented green protocol has been developed for the synthesis of N,S-heterocycles from styrenes and alkyl dithiocarbamates with high to excellent yields. The reaction of primary or secondary amines, CS₂, and styrenes was carried out in water in the presence of a catalytic amount of an inorganic base. All products were made by using an N-bromosuccinimide–H₂O combination as a green and inexpensive reagent.

Key words

dithiocarbamates - styrenes - green chemistry - thiazoles - bromosuccinimide

• References and Notes

• 1a Tomotsu N, Ishihara N, Newman TH, Malanga MT. J. Mol. Catal. A: Chem 1998; 128: 167
• 1b Chien JC. W, Salajka Z, Dong S. Macromolecules 1992; 25: 3199
• 2 Cheng K, Huang L, Zhang Y. Org. Lett. 2009; 11: 2908
• 3 Reddi RN, Prasad PK, Sudalai A. Org. Lett. 2014; 16: 5674
• 4 Prasad PK, Reddi RN, Sudalai A. Org. Lett. 2016; 18: 500
• 5 Wu C.-S, Liu R.-X, Ma D.-Y, Luo C.-P, Yang L. Org. Lett. 2019; 21: 6117
• 6a Li G, Yan Q, Gan Z, Li Q, Dou X, Yang D. Org. Lett. 2019; 21: 7938
• 6b Halimehjani AZ, Hasani L, Alaei MA, Saidi MR. Tetrahedron Lett. 2016; 57: 883
• 6c Azizi N, Aryanasab F, Torkiyan L, Ziyaei A, Saidi MR. J. Org. Chem. 2006; 71: 3634
• 6d Azizi N, Aryanasab F, Saidi MR. Org. Lett. 2006; 8: 5275
• 6e Khoudary K, Mona S, Matar M, Haffar S. Asian J. Chem. 2013; 25: 962
• 6f Gan S.-F, Wan J.-P, Pan Y.-J, Sun C.-R. Synlett 2010; 973
• 7a Marinovich M, Viviani B, Capra V, Corsini E, Anselmi L, D’Agostino G, Di Nucci A, Binaglia M, Tonini M, Galli CL. Chem. Res. Toxicol. 2002; 15: 26
• 7b Nieuwenhuizen PJ, Ehlers AW, Haasnoot JG, Janse SR, Reedijk J, Baerends EJ. J. Am. Chem. Soc. 1999; 121: 163
• 7c Lai JT, Shea R. J. Polym. Sci., Part A: Polym. Chem. 2006; 44: 4298
• 7d Bala V, Jangir S, Mandalapu D, Gupta S, Chhonker YS, Lal N, Kushwaha B, Chandasana H, Krishna S, Rawat K. Bioorg. Med. Chem. Lett. 2015; 25: 881
• 8a Shaabani A, Hooshmand SE. Ultrason. Sonochem. 2018; 40: 84
• 8b Gabillet S, Lecerclé D, Loreau O, Carboni M, Dézard S, Gomis J.-M, Taran F. Org. Lett. 2007; 9: 3925
• 8c Hajibabaei K, Zali-Boeini H. Synlett 2015; 26: 108
• 9 Zou L.-H, Li Y.-C, Li P.-G, Zhou J, Wu Z. Eur. J. Org. Chem. 2018; 2018: 5639
• 10a Wang Z, Lin L, Zhou P, Liu X, Feng X. Chem. Commun. 2017; 53: 3462
• 10b Li W, Zhou P, Li G, Lin L, Feng X. Adv. Synth. Catal. 2020; 362: 1982
• 10c Cai Y, Liu X, Hui Y, Jiang J, Wang W, Chen W, Lin L, Feng X. Angew. Chem. Int. Ed. 2010; 49: 6160
• 11 Miltsov S, Goikhman M, Yakimansky A, Misharev A, Puyol M, Alonso J. Tetrahedron Lett. 2019; 60: 151005
• 12 Gao Y, Wu W, Huang Y, Huang K, Jiang H. Org. Chem. Front. 2014; 1: 361
• 13 2-(Alkylsulfanyl)-4-aryl-1,3-thiazoles 3a–l; General Procedure NBS (2.0 mmol) was added to a solution of the appropriate styrene 1 (1.0 mmol) in H₂O (2 mL), and the mixture was stirred for 12 h. The appropriate alkyl dithiocarbamate 2 (1.0 mmol) was added, and the mixture was stirred at 80 °C for 3 h. The resulting mixture was cooled to rt and extracted with EtOAc (3 × 5 mL). The combined organic phase was dried (Na₂SO₄), filtered, and concentrated in vacuo. The residue was purified by chromatography [silica gel, hexane–EtOAc (9:1)]. 2-(Benzylsulfanyl)-4-phenyl-1,3-thiazole (3a) White crystalline solid; yield: 243 mg (86%); mp 58–60 °C. IR (KBr): 3102, 3065, 2918, 1953, 1888, 1590, 1443, 1039 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 4.56 (s, 2 H), 7.30–7.41 (m, 5 H), 7.46–7.50 (m, 4 H), 7.97 (d, J = 8.0, Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 38.8, 112.8, 126.3, 127.7, 128.2, 128.6, 129.1, 134.5, 136.7, 138.1, 155.4, 163.9. Anal. Calcd for C₁₆H₁₃NS₂: C, 67.81; H, 4.62; N, 4.94. Found: C, 67.91; H, 4.72; N, 4.62.
• 14 3-Alkyl-4-aryl-4-hydroxy-1,3-thiazolidine-2-thiones 6a–i; General Procedure NBS (2.0 mmol) was added to a solution of the appropriate styrene 1 (1.0 mmol) in H₂O (2 mL), and the mixture was stirred for 12 h at rt, then cooled to 0 °C. A mixture of the appropriate primary amine (1.5 mmol) and CS₂ (3 mmol) in H₂O (1 mL) was added, followed by K₂CO₃ (0.25 mmol), and the resulting mixture was stirred for 5 h. The mixture was then extracted with EtOAc (3 × 5 mL) and the organic layers were combined, washed with brine, dried (Na₂SO₄), filtered, and concentrated in vacuo. Finally, the residue was purified by chromatography [silica gel, hexane–EtOAc (1:2)]. 3-Benzyl-4-hydroxy-4-phenyl-1,3-thiazolidine-2-thione (6a) White solid; yield: 229 mg (76%); mp 138–140 °C. IR (KBr): 3745, 3230, 3050, 2923, 2743, 1964, 1490, 1442, 1143, 699 cm^–1. ¹H NMR (500 MHz, DMSO-d ₆): δ = 3.63 (d, J = 12.5 Hz, 1 H), 3.75 (d, J = 12.5 Hz, 1 H), 4.50 (d, J = 15.5 Hz, 1 H), 4.83 (d, J = 15.5 Hz, 1 H), 7.14–7.21 (m, 5 H), 7.31–7.42 (m, 5 H), 7.79 (s, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 42.9, 49.2, 100.9, 126.1, 127.1, 128.1, 128.2, 128.9, 129.2, 137.1, 141.2, 196.0. Anal. Calcd for C₁₆H₁₅NOS₂: C, 63.75; H, 5.02; N, 4.65. Found: C, 63.72; H, 5.11; N, 4.01.
• 15 2-Aryl-2-Oxoethyl Dithiocarbamates 7a–i; General Procedure NBS (2.0 mmol) was added to a solution of the appropriate styrene 1 (1.0 mmol) in H₂O (2 mL), and the mixture was stirred for 12 h at rt, then cooled to 0 °C. A mixture of the appropriate secondary amine (1.5 mmol) and CS₂ (3 mmol) in H₂O (1 mL) was added, followed by K₂CO₃ (0.25 mmol), and the resulting mixture was stirred for 5 h. The mixture was extracted with EtOAc (3 × 5 mL), and the organic layers were combined, washed with brine, dried (Na₂SO₄), filtered, and concentrated in vacuo. Finally, the residue was purified by chromatography [silica gel, hexane–EtOAc (1:2)]. 2-Oxo-2-phenylethyl Diethyldithiocarbamate (7a) White solid; yield: 222 mg (83%); mp 108–110 °C. IR (KBr): 3736, 3354, 3058, 2978, 2930, 2874, 1683, 1586, 1492, 1205, 991, 687 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 1.29 (t, J = 7.0 Hz, 3 H), 1.37 (t, J = 7.0 Hz, 3 H), 3.82–3.87 (m, 2 H), 4.02–4.06 (m, 2 H), 4.92 (s, 2 H), 7.51 (t, J = 7.5 Hz, 2 H), 7.61 (t, J = 7.0 Hz, 1 H), 8.09 (dd, J = 9.5 and 1.5 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 11.5, 12.6, 45.1, 47.1, 50.1, 128.6, 128.7, 133.5, 136.2, 193.5, 194.0. Anal. Calcd for C₁₃H₁₇NOS₂: C, 58.39; H, 6.41; N, 5.24. Found: C, 58.44; H, 6.47; N, 4.96.
• 16 Shinde MH, Kshirsagar UA. Org. Biomol. Chem. 2016; 14: 858