Catalyst-Free Oxidation of Sulfides to Sulfoxides by gem-Dihydroperoxide under Mild Conditions

Abstract

A facile and efficient method for the oxidation of sulfides (dialkyl, phenylalkyl, benzylalkyl) to sulfoxides under mild conditions without using any catalysts is reported. This method afforded a series of sulfoxides with good yields (>95%). The ready accessibility and low cost of the gem-dihydroperoxides will endow it with attractive applications in chemical synthesis as oxidants.

Key words

sulfides - sulfoxides - gem-dihydroperoxides - oxidation - catalyst-free

Publication History

Received: 17 November 2022

Accepted after revision: 18 January 2023

Accepted Manuscript online:
18 January 2023

Article published online:
15 February 2023

• References and Notes

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• 17 General Method for the Preparation of Sulfoxides Sulfide 2–12 (1 mmol) was dissolved in an appropriate solvent, and a gem-dihydroperoxide 1a ^1d (0.6 mmol) solution in the same solvent was added. The reaction mass was left protected from light. The reaction progress was monitored by TLС or HPLC. At the end of the reaction, the solvent was evaporated and purification by flash chromatography on silica gel was performed. Methyl Pentyl Sulfoxide (2a) Colorless oil. IR: ν_max = 2957, 2930, 2860, 1466, 1423, 1379, 1303, 1022, 962, 941, 729, 694 cm^–1. ¹H NMR (500 MHz, СD₃OD): δ = 2.87–2.72 (m, 2 H, SCH₂), 2.621 (s, 3 H, SCH₃), 1.82–1.68 (m, 2 H, C²H₂), 1.54–1.34 (m, 4 H, C³,⁴H₂), 0.944 (t, J  = 7.15  Hz, 3 H, CH₂CH ₃). ¹³C NMR (125 MHz, СD₃OD): δ = 54.86 (SCH₂), 38.10 (SCH₃), 31.90 (C³H₂), 23.34 (C²,⁴H₂), 14.17 (CH₂ CH₃). HRMS: m/z calcd for C₆H₁₅OS [M + H]: 135.0844; found: 135.0841. Anal. Calcd (%): C, 53.68; H, 10.51, S, 23.89%. Found: C, 53.73; H, 10.32; S, 24.0. Methyl Heptyl Sulfoxide (3a) Colorless oil. IR: ν_max = 2954, 2927, 2856, 1466, 1417, 1379, 1304, 1034, 943, 723, 692 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 2.76–2.68 (m, 1 H, SCH₂), 2.67–2.58 (m, 1 H, SCH₂), 2.538 (s, 3 H, SCH₃), 1.73–1.65 (m, 2 H, C²H₂), 1.48–1.34 (m, 2 H, C⁶H₂), 1.34–1.19 (m, 6 H, C^3–5H₂), 0.838 (t, J  = 6.75  Hz, 3 H, CH₂CH ₃). ¹³C NMR (125 MHz, CDCl₃): δ = 54.56 (SCH₂), 38.33 (SCH₃), 31.45 (CH₂), 28.77 (CH₂), 28.66 (CH₂), 22.50 (C²H₂), 22.45 (C⁶H₂), 13.94 (CH₂ CH₃). HRMS: m/z calcd for C₈H₁₉OS [M + H]: 163.1157; found: 163.1166. Anal. Calcd (%): C, 59.21; H, 11.18; S, 19.76. Found: C, 59.09; H, 11.13; S, 19.79. Diheptyl Sulfoxide (4a) White crystals, mp 66 °C. IR: ν_max = 2953, 2912, 2852, 1463, 1377, 1010, 989 cm^–1. ¹H NMR (500 MHz, СD₃OD): δ = 2.84–2.70, (m, 4 H, C¹H₂), 1.81–1.69 (m, 4 H, C²H₂), 1.54–1.41 (m, 4 H, C³H₂), 1.41–1.27 (m, 12 H, C^4–6H₂), 0.910 (t, J  = 6.8 Hz, 6 H, CH₃). ¹³C NMR (125 MHz, СD₃OD): δ = 52.82 (C¹H₂), 32.76 (C⁴H₂), 30.00 (C⁵H₂), 29.75 (C³H₂), 23.79 (C²H₂), 23.62 (C⁶H₂), 14.38 (CH₃). HRMS: m/z calcd for C₁₄H₃₁OS [M + H]: 247.2096; found: 247.2100. Anal. Calcd (%): C, 68.23; H, 12.27; S, 13.01. Found: C, 68.07; H, 12.30; S, 13.15. tert-Amyl Ethyl Sulfoxide (5a) Colorless oil. IR: ν_max = 2969, 2936, 2880, 1462, 1382, 1365, 1044, 1010, 972 cm^–1. ¹H NMR (500 MHz, СD₃OD): δ = 2.75–2.65, 2.61–2.51 (2 m, total 2 H, SCH ₂Me), 1.77–1.66 (m, 1 H, MeCH ₂CMe₂), 1.63–1.52 (m, 1 H, MeCH ₂CMe₂), 1.368 (t, J  = 7.5  Hz, 3 H, SCH₂CH ₃), 1.227 (s, 3 H, SC(CH₃)₂), 1.182 (s, 3 H, SC(CH₃)₂), 1.008 (t, J =7.6  Hz, 3 H, CH ₃CH₂CMe₂). ¹³C NMR (125 MHz, СD₃OD): δ = 57.64 (SCMe₂), 39.17 (SCH₂Me), 30.01 (MeCH₂CMe₂), 19.71 and 19.41 (SC(CH₃)₂), 8.73 (SCH₂ CH₃), 8.15 (CH₃CH₂CMe₂). HRMS: m/z calcd for C₇H₁₇OS [M + H]: 149.1000; found: 149.1000. Anal. Calcd (%): C, 56.71; H, 10.88; S, 21.63. Found: C, 56.94; H, 10.79; S, 21.45. Diisobutyl Sulfoxide (6a) IR: ν_max = 2922, 2854, 1456, 1379, 1016 cm^–1. ¹H NMR (500 MHz, СD₃OD): δ = 2.74–2.69, 2.61–2.55 (2 m, 4 H, CH₂), 2.21–2.11 (m, 2 H, CH), 1.12–1.08 (m, 12 H, CH₃). ¹³C NMR (125 MHz, СD₃OD): δ = 62.41 (CH₂), 25.15 (CH), 23.06 (CH₃), 21.74 (CH₃). HRMS: m/z calcd for C₈H₁₉OS [M + H]: 163.1157; found: 163.1151. Anal. Calcd (%): C, 59.21; H, 11.18; S, 19.76. Found: C, 59.29; H, 11.32; S, 20.12. 3,5-Dimethyl-4-[(pentylsulfinyl)methyl]-1H-pyrazole (12a) White crystals, mp 87 °C. IR: ν_max = 2949, 2923, 2853, 1590, 1461, 1415, 1377, 1308, 1207, 1139, 1109, 1072, 1034, 1017, 1003, 949, 875, 835, 758, 729 cm^–1. ¹H NMR (500 MHz, DMSO-d ₆): δ = 12.206 (s, wide, 1 H, NH), 3.861 (d, J = 7.0  Hz, 1 H, SCH ₂-pyrazole), 3.719 (d, J = 7.0  Hz, 1 H, SCH ₂-pyrazole), 2.71–2.62 (m, 1 H, SCH ₂CH₂), 2.60–2.53 (m, 1 H, SCH ₂CH₂), 2.129 (s, 6 H, CH_3(pyrazole)), 1.72–1.55 (m, 2 H, SCH₂CH ₂), 1.43–1.25 (m, 4 H, CH₂), 0.872 (t, 3 H, CH₂CH ₃). ¹³C NMR (125 MHz, DMSO-d ₆): δ = 128.23, 104.90 (SCH₂-pyrazole), 50.08, 46.52, 30.35, 26.73, 21.76, 21.70, 13.66, 10.66 (br, 2 Me). HRMS: m/z calcd for C₁₁H₂₁OS [M + H]: 229.1375; found: 229.1379. Anal. Calcd (%): C, 57.86; H, 8.83; N, 12.27; S, 14.04. Found: C, 57.91; H, 8.95; N, 12.28; S, 14.19.
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