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

Publication History

Received: 22 May 2020

Accepted after revision: 10 July 2020

Article published online:
28 August 2020

• References and Notes

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• 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.
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