Download PDF
Synlett 2015; 26(18): 2547-2552
DOI: 10.1055/s-0035-1560482
letter
© Georg Thieme Verlag Stuttgart · New York

Selective Synthesis of Sulfoxides through Oxidation of Sulfides with Sodium Hypochlorite Pentahydrate Crystals

Tomohide Okada
a   R&D Department of Chemicals, Nippon Light Metal Company, Ltd., 480 Kambara, Shimizu-ku, Shizuoka 421-3203, Japan
,
Hiroaki Matsumuro
b   Department of Materials and Life Science, Shizuoka Institute of Science and Technology, 2200-2 Toyosawa, Fukuroi, Shizuoka 437-8555, Japan   Email: kirihara@ms.sist.ac.jp
,
Saori Kitagawa
b   Department of Materials and Life Science, Shizuoka Institute of Science and Technology, 2200-2 Toyosawa, Fukuroi, Shizuoka 437-8555, Japan   Email: kirihara@ms.sist.ac.jp
,
Toshiaki Iwai
b   Department of Materials and Life Science, Shizuoka Institute of Science and Technology, 2200-2 Toyosawa, Fukuroi, Shizuoka 437-8555, Japan   Email: kirihara@ms.sist.ac.jp
,
Kento Yamazaki
b   Department of Materials and Life Science, Shizuoka Institute of Science and Technology, 2200-2 Toyosawa, Fukuroi, Shizuoka 437-8555, Japan   Email: kirihara@ms.sist.ac.jp
,
Yukari Kinoshita
b   Department of Materials and Life Science, Shizuoka Institute of Science and Technology, 2200-2 Toyosawa, Fukuroi, Shizuoka 437-8555, Japan   Email: kirihara@ms.sist.ac.jp
,
Yoshikazu Kimura
c   Research and Development Department, Iharanikkei Chemical Industry Co. Ltd., 5700-1 Kambara, Shimizu-ku, Shizuoka 421-3203, Japan
,
Masayuki Kirihara*
b   Department of Materials and Life Science, Shizuoka Institute of Science and Technology, 2200-2 Toyosawa, Fukuroi, Shizuoka 437-8555, Japan   Email: kirihara@ms.sist.ac.jp
› Author Affiliations
Further Information

Publication History

Received: 08 July 2015

Accepted after revision: 21 August 2015

Publication Date:
29 September 2015 (online)

    Permissions and Reprints All articles of this category


Abstract

Oxidation of sulfides with sodium hypochlorite pentahydrate crystals (1.1 equiv) in an aqueous acetonitrile solution selectively produces the corresponding sulfoxides in high yields. This procedure is catalyst-free and environmentally benign.

Key words

sodium hypochlorite - sulfoxide - oxidation - catalyst-free
 

  • References and Notes

  • 4 For a review, see: Kaczorowska K, Kolarska Z, Mitka K, Kowalski P. Tetrahedron 2005; 61: 8315
    CrossrefSearch in Google Scholar
  • 7 Varma RS, Naicker KP. Org. Lett. 1999; 189
  • 8 Gómez MV, Caballero R, Vázquez E, Moreno A, de la Hoz A, Díaz-Ortiz Á. Green Chem. 2007; 9: 331
    CrossrefSearch in Google Scholar
  • 9 Siedlecka R, Skarżewski J. Synthesis 1994; 401
    Thieme Connect
  • 10 Asawa T, Tsuneizumi T, Iwasaki Y. Japanese Patent 4211130, 2008
  • 11 NaOCl·5H2O is commercially available from Wako Pure Chemical Industries, Tokyo Chemical Industry Co., and Junsei Chemical Co. in Japan. It is also available from TCI Europe N. V and TCI America. Large quantities of NaOCl·5H2O can be obtained directly from the Nippon Light Metal Company.
  • 12 Okada T, Asawa T, Sugiyama Y, Kirihara M, Iwai T, Kimura Y. Synlett 2014; 25: 596
    Thieme ConnectSearch in Google Scholar
  • 13 Okada T, Matsumuro H, Iwai T, Kitagawa S, Yamazaki K, Akiyama T, Asawa T, Sugiyama Y, Kimura Y, Kirihara M. Chem. Lett. 2015; 44: 185
    CrossrefSearch in Google Scholar
  • 14 Representative Procedure for the Synthesis of Sulfoxides through the Reaction of Sulfides with NaOCl·5H2O: To a solution of thioanisole (1a; 248 mg, 2.0 mmol) in MeCN (10 mL) and H2O (2 mL), NaOCl·5H2O (362 mg, 2.2 mmol) was added and the mixture was stirred at r.t. for 18 min. H2O (20 mL) and CHCl3 (15 mL) were added, the organic layer was separated, and the aqueous phase was extracted with CHCl3 (3 × 15 mL). The extracts were dried over anhydrous magnesium sulfate, and evaporated. The residue was purified by silica gel column chromatography (n-hexane–EtOAc, 1:2 v/v) to provide methyl phenyl sulfoxide (2a; 275 mg, 98%) as colorless crystals. Methyl phenyl sulfone (3a; 6 mg, 2%) was also obtained as colorless crystals. Methyl Phenyl Sulfoxide (2a) 16 Mp 28–29 °C (Lit.17 26–29 °C). 1H NMR (CDCl3): δ = 7.67–7.65 (m, 2 H), 7.56–7.50 (m, 3 H), 2.73 (s, 3 H); 13C NMR (CDCl3): δ = 145.34, 130.87, 129.18, 123.28, 43.71. MS: m/z = 140 [M]+ Methyl Phenyl Sulfone (3a) 16 Mp 85–87 °C (Lit.17 85–87 °C). 1H NMR (CDCl3): δ = 7.95–7.93 (m, 2 H), 7.59–7.55 (m, 3 H), 3.06 (s, 3 H). 13C NMR (CDCl3): δ = 140.37, 133.48, 129.15, 127.03, 44.20. MS: m/z = 156 [M]+. p-Methoxyphenyl Methyl Sulfoxide (2b) 18 Yield: 339 mg (99%); colorless crystals; mp 32–33 °C (Lit.19 32–33 °C). 1H NMR (CDCl3): δ = 7.60 (d, J = 8.6 Hz, 2 H), 7.04 (d, J = 8.6 Hz, 2 H), 3.86 (s, 3 H), 2.70 (s, 3 H). 13C NMR (CDCl3): δ = 161.93, 136.58, 125.41, 114.81, 55.49, 43.97. MS: m/z = 170 [M]+. p-Methoxyphenyl Methyl Sulfone (3b) 20 Yield: 2 mg (1%); colorless crystals; mp 102–110 °C (Lit.21 110–113 °C). 1H NMR (CDCl3): δ = 7.88 (d, J = 9.0 Hz, 2 H), 7.03 (d, J = 9.0 Hz, 2 H), 3.89 (s, 3 H), 3.03 (s, 3 H). 13C NMR (CDCl3): δ = 163.68, 132.29, 129.54, 114.49, 55.70, 44.84. MS: m/z = 186 [M]+. p-Chlorophenyl Methyl Sulfoxide (2c) 18 Yield: 325 mg (93%); colorless crystals; mp: 45–46 °C (Lit.19 45–46 °C). 1H NMR (CDCl3): δ = 7.60 (d, J = 8.7 Hz, 2 H), 7.52 (d, J = 8.7 Hz, 2 H), 2.72 (s, 3 H). 13C NMR (CDCl3): δ = 144.22, 137.21, 129.62, 124.94, 44.02. MS: m/z = 176 [M+ for 37Cl], 174 [M+ for 35Cl] p-Chlorophenyl Methyl Sulfone (3c) 20 Yield: 19 mg (5%); colorless crystals; mp 87–92 °C (Lit.22 92–95 °C). 1H NMR (CDCl3): δ = 7.89 (d, J = 8.5 Hz, 2 H), 7.56 (d, J = 8.5 Hz, 2 H), 3.06 (s, 3 H). 13C NMR (CDCl3): δ = 140.49, 139.03, 129.72, 128.92, 44.56. MS: m/z = 192 [M+ for 37Cl], 190 [M+ for 35Cl]. p-Nitrophenyl Methyl Sulfoxide (2d) 18 Yield: 308 mg (83%); colorless crystals; mp 150–152 °C (Lit.23 152–153 °C). 1H NMR (CDCl3): δ = 8.40 (d, J = 9.0 Hz, 2 H), 7.84 (d, J = 9.0 Hz, 2 H), 2.80 (s, 3 H). 13C NMR (CDCl3): δ = 153.26, 149.52, 124.67, 124.51, 43.90. p-Nitrophenyl Methyl Sulfone (3d) 20 Yield: 30 mg (7%); colorless crystals; mp 123–130 °C (Lit.24 127–129.5 °C). 1H NMR (CDCl3): δ = 8.44 (d, J = 9.0 Hz, 2 H), 8.17 (d, J = 9.0 Hz, 2 H), 3.12 (s, 3 H). 13C NMR (CDCl3): δ = 150.87, 145.95, 128.98, 124.64, 44.28. Allyl Phenyl Sulfoxide (2e) 25 Yield: 286 mg (86%); colorless oil. 1H NMR (CDCl3): δ = 7.64–7.48 (m, 5 H), 5.71–5.60 (m, 1 H), 5.34 (d, J = 13.6 Hz, 1 H), 5.20 (d, J = 13.6 Hz, 1 H), 3.61–3.49 (m, 2 H). 13C NMR (CDCl3): δ = 142.62, 131.08, 129.03, 125.25, 124.34, 123.82, 60.87. MS: m/z = 166 [M]+. Allylphenyl Sulfone (3e) 26 Yield: 6 mg (2%); colorless oil. 1H NMR (CDCl3): δ = 7.89–7.86 (m, 2 H), 7.57–7.53 (m, 3 H), 5.83–5.74 (m, 1 H), 5.33 (d, J = 17.2 Hz, 1 H), 5.15 (d, J = 17.2 Hz, 1 H), 3.81 (d, J = 7.6 Hz, 2 H). 13C NMR (CDCl3): δ = 138.34, 133.71, 129.02, 128.47, 124.65, 124.63, 60.85. MS: m/z = 182 [M]+. Benzyl Phenyl Sulfoxide (2f) 27 Yield: 372 mg (86%); colorless crystals; mp 124 °C (Lit.27 123–124 °C). 1H NMR (CDCl3): δ = 7.46–7.36 (m, 5 H), 7.29–7.23 (m, 3 H), 6.99–6.97 (m, 2 H), 4.10 (d, J = 12.4 Hz, 1 H), 4.00 (d, J = 12.4 Hz, 1 H). 13C NMR (CDCl3): δ = 142.77, 131.13, 130.33, 129.12, 128.81, 128.42, 128.21, 124.41, 63.58. MS: m/z = 216 [M]+. Dibenzyl Sulfoxide (2g) 28 Yield: 412 mg (89%); colorless crystals; mp 136 °C (Lit.28 135–136 °C). 1H NMR (CDCl3): δ = 7.40–7.26 (m, 10 H), 3.91 (q, 4 H). 13C NMR (CDCl3): δ = 130.13, 130.11, 128.94, 128.35, 57.30. MS: m/z = 230 [M]+. Benzyl Methyl Sulfoxide (2h) 29 Yield: 234 mg (76%); colorless oil. 1H NMR (CDCl3): δ = 7.41–7.28 (m, 5 H), 4.07 (d, J = 13.0 Hz, 1 H), 3.93 (d, J = 13.0 Hz, 1 H), 2.46 (s, 3 H). 13C NMR (CDCl3): δ = 129.98, 129.66, 128.94, 128.40, 60.33, 37.27. MS: m/z = 154 [M]+. Decyl Methyl Sulfoxide (2i) 30 Yield: 410 mg (quant); colorless crystals; mp 48–50 °C (Lit.30 48–51 °C). 1H NMR (CDCl3): δ = 2.63–2.80 (m, 2 H), 2.58 (s, 3 H), 1.72–1.79 (m, 2 H), 1.40–1.50 (m, 2 H), 1.27–1.35 (m, 12 H), 0.87 (t, J = 6.8 Hz, 3 H). 13C NMR (CDCl3): δ = 55.03, 38.77, 32.15, 29.77, 29.64, 29.55, 29.49, 29.10, 23.96, 22.86, 14.40. MS: m/z = 188 [M+ – O]. Diphenyl Sulfoxide (2j) 16 Yield: 386 mg (95%); colorless crystals; mp 72 °C (Lit.17 69–71 °C). 1H NMR (CDCl3): δ = 7.67–7.61 (m, 4 H), 7.46–7.39 (m, 6 H). 13C NMR (CDCl3): δ = 145.49, 131.00, 129.26, 124.68. MS: m/z = 202 [M]+. Diphenyl Sulfone (3j) 16 Yield: 21 mg (5%); colorless crystals; mp 125 °C (Lit.26 123–124 °C). 1H NMR (CDCl3): δ = 7.94–7.90 (m, 4 H), 7.58–7.48 (m, 6 H). 13C NMR (CDCl3): δ = 141.57, 133.15, 129.24, 127.63. MS: m/z = 218 [M]+. 2-(Methylsulfinyl)pyridine (2k) 31Yield: 237 mg (84%); colorless oil. 1H NMR (CDCl3): δ = 8.64–8.61 (m, 1 H), 8.05–7.96 (m, 2 H), 7.41–7.39 (m, 1 H), 2.87 (s, 3 H). 13C NMR (CDCl3): δ = 165.75, 149.43, 138.05, 125.52, 119.14, 41.18. MS: m/z = 141 [M]+. 2-(Methylsulfonyl)pyridine (3k) 20 Yield: 21 mg (7%); colorless oil. 1H NMR (CDCl3): δ = 8.76–8.74 (m, 1 H), 8.12–7.93 (m, 2 H), 7.59–7.56 (m, 1 H), 3.25 (s, 3 H). 13C NMR (CDCl3): δ = 158.04, 150.08, 138.28, 127.45, 121.09, 40.01. MS: m/z = 157 [M]+. Dibenzothiophene Sulfoxide (2l) 32 Yield: 344 mg (86%); pale-yellow crystals; mp 207 °C (Lit.32 204–205 °C). 1H NMR (CDCl3): δ = 8.00 (d, J = 7.6 Hz, 2 H), 7.82 (d, J = 7.6 Hz, 2 H), 7.58–7.62 (m, 2 H). 13C NMR (CDCl3): δ = 145.08, 137.06, 132.53, 129.52, 127.50, 121.89. MS: m/z = 200 [M]+. Dibenzothiophene Sulfone 33 Yield: 28 mg (6%); pale-yellow crystals; mp 262 °C (Lit.33 246–250 °C). 1H NMR (CDCl3): δ = 7.83–7.81 (m, 2 H), 7.80–7.78 (m, 2 H), 7.65–7.61 (m, 2 H), 7.54–7.50 (m, 2 H). 13C NMR (CDCl3): δ = 137.68, 133.86, 131.58, 130.35, 122.14, 121.56. MS: m/z = 216 [M]+.
  • 15 Gram-Scale Synthesis of 2a through Reaction of 1a with NaOCl·5H2O Caution: Oxidation using NaOCl·5H2O is exothermic, therefore a water bath (ca. 20 °C) must be used to control the reaction temperature for a gram-scale synthesis. Thioanisole (1a; 2.48 g, 20 mmol) was dissolved in MeCN (100 mL), and the reaction flask was submerged in a water bath. Aqueous 20.6% NaOCl (7.59 g, 21 mmol, prepared from NaOCl·5H2O and H2O)34 was added slowly over 5 min to the mixture, which was then stirred for 15 min. Sat. aq sodium sulfite (30 mL) and EtOAc (40 mL) were added to the reaction mixture, the organic layer was separated, and the aqueous phase was extracted with EtOAc (3 × 30 mL). The extracts were dried over anhydrous magnesium sulfate, and evaporated. The residue was purified by silica-gel column chromatography (n-hexane–EtOAc, 1:2 v:v) to provide methyl phenyl sulfoxide (2a; 2.68 g, 96%) as colorless crystals. Methyl phenyl sulfone (3a; 84 mg, 3%) was also obtained as colorless crystals.
  • 16 Sato K, Hyodo M, Aoki M, Zheng X, Noyori R. Tetrahedron 2001; 57: 2469
    CrossrefSearch in Google Scholar
  • 17 ALDRICH Chemistry: Handbook of Fine Chemistry. Sigma–Aldrich; St. Louis: 2012
    Search in Google Scholar
  • 18 Kamata K, Hirano T, Mizuno N. Chem. Commun. 2009; 3958
  • 19 Hanson P, Hendrickx RA A. J, Smith JR. L. Org. Biomol. Chem. 2008; 745
  • 20 Fukuda N, Ikemoto T. J. Org. Chem. 2010; 75: 4629
    CrossrefPubMedSearch in Google Scholar
  • 21 Yang H, Li Y, Jiang M, Wang J, Fu H. Chem. Eur. J. 2011; 17: 5652
    CrossrefSearch in Google Scholar
  • 22 Kice JL, Kupczyk-Subotkowska L. J. Org. Chem. 1991; 56: 1424
    CrossrefSearch in Google Scholar
  • 23 Bordwell FG, Boutan PJ. J. Am. Chem. Soc. 1957; 79: 717
    CrossrefSearch in Google Scholar
  • 24 Caccia-Bava AM, Vitali T. Ann. Chim. 1950; 40: 21
    Search in Google Scholar
  • 25 Lindén AA, Krüger L, Bäckvall JE. J. Org. Chem. 2003; 68: 5890
    CrossrefSearch in Google Scholar
  • 26 Clifford G, Squies TG, Chen YY, Gregory PH, Juliana CS, Smith BF. J. Org. Chem. 1982; 47: 3773
    CrossrefSearch in Google Scholar
  • 27 Kageyama T, Okamura M. Synthesis 1983; 815
    Thieme Connect
  • 28 Caupene C, Boudou C, Perrio S, Metzner P. J. Org. Chem. 2005; 70: 2812
    CrossrefSearch in Google Scholar
  • 29 Rabai J, Kapovits I, Tanacs B, Tamas J. Synthesis 1990; 847
    Thieme Connect
  • 30 Capozzi MA. M, Cardellicchio C, Naso F, Tortorella P. J. Org. Chem. 2000; 65: 2843
    CrossrefPubMedSearch in Google Scholar
  • 31 Furukawa N, Takahashi F, Kawai T, Kishimoto K, Ogawa S, Oae S. Phosphorus Sulfur Relat. Elem. 1983; 16: 167
    CrossrefSearch in Google Scholar
  • 32 Nelsen FS, Luo Y, Weaver MN, Lockand JV. J. Org. Chem. 2006; 71: 1493
    CrossrefSearch in Google Scholar
  • 33 Klemm LH, Pou S, Detlefsen WD, Higgins C, Lawrence RF. J. Heterocycl. Chem. 1984; 21: 1293
    CrossrefSearch in Google Scholar
  • 34 Aqueous 20.6% NaOCl was prepared from NaOCl·5H2O (56.24 g) and H2O (61.89 g).