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Synlett 2023; 34(11): 1247-1252
DOI: 10.1055/a-2015-7526
letter

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

Stanislav A. Grabovskii  ∗
,
Nadezhda M. Andrijashina
,
Alexandr N. Lobov 
,
Arkadiy V. Antipin
,
Rustam L. Safiullin
This research was carried out on state assignment theme No. 122031400201-0. MESRF (Ministry of Education and Science of Russia).
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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

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2015-7526.
  • Supporting Information


Publication History

Received: 17 November 2022

Accepted after revision: 18 January 2023

Accepted Manuscript online:
18 January 2023

Article published online:
15 February 2023

© 2023. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 

  • References and Notes

  • 4 Selvam JJ. P, Suresh V, Rajesh K, Babu C, Suryakiran N, Venkateswarlu Y. Tetrahedron Lett. 2008; 49: 3463
    CrossrefSearch in Google Scholar
  • 8 Kluge R, Schulz M, Liebsch S. Tetrahedron 1996; 52: 5773
    CrossrefSearch in Google Scholar
  • 9 Sylvian S, Wanger A, Mioskowosky C. Tetrahedron Lett. 1997; 38: 1043
    CrossrefSearch in Google Scholar
  • 10 Kowalski P, Mitka K, Ossowska K, Kolarska Z. Tetrahedron 2005; 61: 1933
    CrossrefSearch in Google Scholar
  • 13 Andriyashina NM, Grabovskii SA, Safiullin RL. Lett. Org. Chem. 2023; in press
    Crossref
  • 16 Jiang X, Yao C, Tong C, Bai R, Zhou T, Xie Y. Chin. J. Org. Chem. 2020; 40: 1752
    CrossrefSearch in Google Scholar
  • 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.
    • 18a Ulendeeva AD, Nikitina TS, Baeva LA, Spitikhin LV, Karachurina LT, Khisamutdinova RYu, Makara NS, Zarudii FS, Lyapina NK. Pharm. Chem. J. 2004; 38: 659
      CrossrefSearch in Google Scholar
    • 18b Ulendeeva AD, Baeva LA, Nikitina TS, Spitikhin LV, Vasil’eva EV, Lyapina NK. Pet. Chem. 2004; 44: 388
      Search in Google Scholar