Methoxide Ion Promoted Efficient Synthesis of 1,3-Oxathiolane-2-thiones by Reaction of Oxiranes and Carbon Disulfide

Abstract

An efficient one-pot synthesis of functionalized 1,3-­oxathiolane-2-thiones is described via reaction of carbon disulfide with oxiranes in the presence of sodium hydride (10 mol%) and methanol.

Key words

oxathiolane - oxiranes - carbon disulfide - methoxide ion

References and Notes

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21

General Procedure for the Preparation of Compounds 2 To a stirred solution of CS₂ (0.35 g, 5 mmol) in MeOH (0.064 g, 2 mmol) containing NaH (10 mol%), was added, at r.t., the oxirane derivative 1 (2 mmol). The mixture was stirred for 12 h, and filtered to remove the white precipitates (presumably, NaOMe). The residue was purified by extraction with Et₂O to afford pure 2. 5-Methyl-1,3-oxathiolane-2-thione (2a) Yellow oil; yield 0.26 g (96%). IR (KBr): ν_max = 1700, 1439, 1414, 1370, 1143, 1073 cm^-1. ¹H NMR (500.1 MHz, CDCl₃): δ 1.56 (3 H, d, ³ J = 6.7 Hz, Me), 3.62 (1 H, dd, ² J = 11.9 Hz, ³ J = 7.4 Hz, CH), 3.98 (1 H, dd, ² J = 11.9 Hz, ³ J = 6.4 Hz, CH), 4.45-4.51 (1 H, m, CH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 19.1 (Me), 50.3 (CH₂), 55.5 (CH), 228.5 (C=S). MS (EI): m/z (%) = 134 (15) [M⁺], 119 (78), 92 (100), 76 (64), 58 (48), 42 (56). Anal. Calcd (%) for C₄H₆OS₂ (134.21): C, 35.80; H, 4.51. Found: C, 35.90; H, 4.55. 5-Ethyl-1,3-oxathiolane-2-thione (2b) Yellow oil; yield 0.28 g (94%). IR (KBr): ν_max = 1711, 1627, 1507, 1431, 1327, 1273 cm^-1. ¹H NMR (500.1 MHz, CDCl₃): δ = 1.07 (3 H, t, ³ J = 7.4 Hz, Me), 1.91-1.97 (2 H, m, CH₂), 3.71 (1 H, dd, ² J = 11.9 Hz, ³ J = 7.5 Hz, CH), 3.98 (1 H, dd, ² J = 11.9 Hz, ³ J = 5.5 Hz, CH), 4.29-4.33 (1 H, m, CH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 13.1 (Me), 27.2 (CH₂), 48.3 (CH₂), 62.9 (CH), 228.5 (C=S). MS (EI): m/z (%) = 148 (10) [M⁺], 119 (68), 92 (100), 76 (84), 56 (42), 29 (24). Anal. Calcd (%) for C₅H₈OS₂ (148.24): C, 40.51; H, 5.44. Found: C, 40.41; H, 5.49. Hexahydro-1,3-benzoxathiole-2-thione (2c) Yellow crystals; yield 0.33 g (96%); mp 176-178 °C. IR (KBr): ν_max = 1628, 1431, 1326, 1272, 1094 cm^-1. ¹H NMR (500.1 MHz, CDCl₃): δ = 1.43-1.48 (2 H, m, CH₂), 1.68-1.75 (2 H, m, CH₂), 1.93-1.97 (2 H, m, CH₂), 2.17-2.22 (2 H, m, CH₂), 4.08-4.09 (1 H, m, CH), 4.09-4.11 (1 H, m, CH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 25.5 (2 CH₂), 29.5 (2 CH₂), 65.0 (2 CH), 227.6 (C=S). MS (EI): m/z (%) = 174 (5) [M⁺], 118 (78), 92 (100), 82 (64), 76 (48), 56 (45). Anal. Calcd (%) for C₇H₁₀OS₂ (174.27): C, 48.24; H, 5.78; found: C, 48.18; H, 5.79. 5-Phenyl-1,3-oxathiolane-2-thione (2d) Yellow crystals; yield 0.30 g (95%); mp 115-117 °C. IR (KBr): ν_max = 1568, 1470, 1438, 1413, 1357, 1048 cm^-1. ¹H NMR (500.1 MHz, CDCl₃): δ = 4.03 (1 H, dd, ² J = 12.0 Hz, ³ J = 5.7 Hz, CH), 4.17 (1 H, dd, ² J = 12.0 Hz, ³ J = 11.8 Hz, CH), 5.65 (1 H, dd, ² J = 10.3 Hz, ³ J = 5.7 Hz, CH), 7.37-7.44 (3 H, m, 3 CH), 7.50 (2 H, d, ³ J = 7.2 Hz, 2 CH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 49.8 (CH₂), 64.2 (CH), 127.5 (2 CH), 129.2 (2 CH), 129.3 (CH), 135.3 (C), 227.2 (C=S). MS (EI): m/z 196 (10) [M⁺], 119 (76), 104 (46), 92 (25), 77 (100). Anal. Calcd (%) for C₉H₈OS₂ (196.28): C, 55.07; H, 4.11. Found: C, 55.03; H, 4.08. 5-(Phenoxymethyl)-1,3-oxathiolane-2-thione (2e) Yellow crystals; yield 0.42 g (94%); mp 55-57 °C. IR (KBr): ν_max = 1584, 1481, 1448, 1238, 1165, 1063 cm^-1. ¹H NMR (500.1 MHz, CDCl₃): δ = 4.06 (1 H, dd, ² J = 12.3 Hz, ³ J = 4.0 Hz, CH), 4.18-4.23 (2 H, m, CH₂), 4.36 (1 H, dd, ² J = 12.2 Hz, ³ J = 4.5 Hz, CH), 4.61-4.66 (1 H, m, CH), 6.93 (2 H, d, ³ J = 7.9 Hz, 2 CH), 7.02 (1 H, t, ³ J = 7.3 Hz, CH), 7.33 (2 H, t, ³ J = 7.5 Hz, 2 CH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 45.0 (CH₂), 57.4 (CH), 66.7 (CH), 114.7 (2 CH), 121.9 (CH), 129.7 (2 CH), 157.8 (C), 227.5 (C=S). MS (EI): m/z 226 (5) [M⁺], 149 (78), 134 (64), 107 (94), 92 (46), 77 (100). Anal. Calcd (%) for C₁₀H₁₀O₂S₂ (226.31): C, 53.07; H, 4.45. Found: C, 53.05; H, 4.40. 5-(Vinyloxymethyl)-1,3-oxathiolane-2-thione (2f) Yellow oil; yield: 0.36 g (94%). IR (KBr): ν_max = 1702, 1630, 1451, 1414, 1348 cm^-1. ¹H NMR (500.1 MHz, CDCl₃): δ = 3.64 (1 H, dd, ² J = 9.8 Hz, ³ J = 5.8 Hz, CH), 3.79-3.81 (1 H, m, CH), 3.94 (1 H, dd, ² J = 12.1 Hz, ³ J = 4.7 Hz, CH), 4.04 (2 H, d, ³ J = 5.6 Hz, 2 CH), 4.07 (1 H, dd, ² J = 12.1 Hz, ³ J = 5.7 Hz, CH), 4.44-4.49 (1 H, m, CH), 5.20-5.30 (2 H, m, 2 CH), 5.83-5.91 (1 H, m, CH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 45.4 (CH₂), 58.7 (CH), 69.4 (CH₂), 72.8 (CH₂), 118.4 (CH₂), 134.3 (CH), 227.9 (C=S). MS (EI): 190 (15) [M⁺], 133 (74), 114 (58), 92 (46), 57 (100). Anal. Calcd (%) for C₇H₁₀O₂S₂ (190.27): C, 44.19; H, 5.30. Found: C, 44.15; H, 5.36. 5-(Isopropoxymethyl)-1,3-oxathiolane-2-thione (2g) Pale yellow oil; yield 0.37 g (96%). IR (KBr): ν_max = 1703, 1643, 1452, 1417, 1372, 1332 cm^-1. ¹H NMR (500.1 MHz, CDCl₃): δ = 1.12 (6 H, d, ³ J = 6.1 Hz, 2 Me), 3.53-3.62 (2 H, m, CH₂), 3.73 (1 H, m, CH), 3.89 (1 H, dd, ² J = 12.0 Hz, ³ J = 4.9 Hz, CH), 4.01 (1 H, dd, ² J = 12.0 Hz, ³ J = 5.7 Hz, CH), 4.36-44.40 (1 H, m, CH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 21.7 (Me), 21.8 (Me), 44.7 (CH₂), 58.6 (CH₂), 67.0 (CH), 72.3 (CH), 227.3 (C=S). MS (EI): m/z 192 (5) [M⁺], 149 (84), 119 (25), 116 (52), 92 (32), 43 (42), 73 (100). Anal. Calcd (%) for C₇H₁₂O₂S₂ (192.29): C, 43.72; H, 6.29. Found: C, 43.85; H, 6.26. (4 S ,5 R )-4,5-Diphenyl-1,3-oxathiolane-2-thione (2h) Yellow crystals; yield 0.48 g (88%); mp 123-125 °C. IR (KBr): ν = 1475, 1435, 1140, 1050 cm^-1. ¹H NMR (500.1 MHz, CDCl₃): δ = 4.41 (1 H, s, CH), 5.74 (1 H, s, CH), 7.13-7.17 (5 H, m, 5 CH), 7.31-7.33 (5 H, m, 5 CH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 44.5 (CH), 70.6 (CH), 127.6 (CH), 128.1 (2 CH), 128.5 (2 CH), 129.5 (2 CH), 129.6 (CH), 129.8 (2 CH), 133.6 (C), 135.5 (C), 225.3 (C=S). MS (EI): m/z (%) = 272 (15) [M⁺], 196 (78), 180 (64), 92 (58), 77 (100). Anal. Calcd (%) for C₁₅H₁₂OS₂ (272.38): C, 66.15; H, 4.44. Found: C, 66.08; H, 4.39. (4 R ,5 R )-4,5-Diphenyl-1,3-oxathiolane-2-thione (2i) Yellow crystals; yield 0.47g (86%); mp 127-129 °C. IR (KBr): ν_max = 1479, 1439, 1142, 1056 cm^-1. ¹H NMR (500.1 MHz, CDCl₃): δ = 4.08 (1 H, s, CH), 5.76 (1 H, s, CH), 7.00 (2 H, d, ³ J = 7.4 Hz, 2 CH), 7.18 (2 H, t, ³ J = 7.8 Hz, 2 CH), 7.27-7.30 (3 H, m, 3 CH), 7.38 (2 H, t, ³ J = 7.5 Hz, 2 CH), 7.54 (1 H, d, ³ J = 7.4 Hz, CH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 45.9 (CH), 68.4 (CH), 126.9 (2 CH), 128.0 (CH), 128.8 (2 CH), 129.1 (2 CH), 129.2 (2 CH), 129.3 (CH), 133.5 (C), 137.7 (C), 227.9 (C=S). MS (EI): m/z (%) = 272 (15) [M⁺], 196 (76), 180 (62), 92 (62), 77 (100). Anal. Calcd (%) for C₁₅H₁₂OS₂ (272.38): C, 66.15; H, 4.44. Found: C, 66.08; H, 4.46.