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

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


Reviews:
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• 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.
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• 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]⁺.
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