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Synlett 2023; 34(11): 1247-1252
DOI: 10.1055/a-2015-7526
DOI: 10.1055/a-2015-7526
letter
Catalyst-Free Oxidation of Sulfides to Sulfoxides by gem-Dihydroperoxide under Mild Conditions
Autoren
This research was carried out on state assignment theme No. 122031400201-0. MESRF (Ministry of Education and Science of Russia).
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.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2015-7526.
- Supporting Information (PDF) (opens in new window)
Publikationsverlauf
Eingereicht: 17. November 2022
Angenommen nach Revision: 18. Januar 2023
Accepted Manuscript online:
18. Januar 2023
Artikel online veröffentlicht:
15. Februar 2023
© 2023. Thieme. All rights reserved
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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: νmax = 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: νmax = 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, C3–5H2), 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: νmax = 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, C4–6H2), 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: νmax = 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: νmax = 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: νmax = 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, CH3(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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