One-Pot Synthesis of Sulfonamides from Sodium Sulfinates and Amines via Sulfonyl Bromides

Abstract

a new and convenient procedure has been developed for the preparation of sulfonamides from sodium sulfinates and amines with (n-C₄H₉)₄NBr as bromine source and m-chloroperbenzoic acid as oxidant. This S–N bond formation reaction proceeds efficiently via sulfonyl bromides under neutral conditions to afford the corresponding sulfonamides in good yields at room temperature.

Key words

sulfonamides - sodium sulfinates - amines - (n-C₄H₉)₄NBr - sulfonyl bromides

• References and Notes

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• 10 A Typical Procedure for the Preparation of Sulfonamides In mixed solvent THF–MeOH (30:1, 2.0 mL), sodium sulfinates 1 (0.45 mmol), amines 2 (0.30 mmol), (n-Bu)₄NBr (0.36 mmol), and m-CPBA (0.3 mmol) were added successively. The suspension mixture was vigorously stirred at r.t. for 12 h. Upon completion, the reaction was quenched by addition of sat. aq Na₂S₂O₃ (2 mL), sat. aq Na₂CO₃ (8 mL), and H₂O (5 mL), respectively. The mixture was extracted with CH₂Cl₂ (3 × 5 mL) and the combined organic phase was dried over anhydrous Na₂SO₄, filtered, and concentrated under reduced pressure. The residue was then purified on a silica gel plate (PE–EtOAc = 3:1) to furnish products 3. N-Benzylbenzenesulfonamide (3a) White solid; mp 82–83 °C (lit.¹² 85–87 °C). IR (KBr): 3329, 1326, 1162, 1093, 1061, 750, 687 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 7.86 (d, J = 7.2 Hz, 2 H), 7.59–7.54 (m, 1 H), 7.50–7.45 (m, J = 7.7 Hz, 2 H), 7.27–7.21 (m, 3 H), 7.20–7.16 (m, 2 H), 5.43 (t, J = 6.1 Hz, 1 H), 4.12 (d, J = 6.3 Hz, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 139.8, 136.2, 132.5, 129.0, 128.5, 127.7, 127.6, 126.9, 47.0. ESI-MS: m/z (%) = 265 (100) [M + NH₄]⁺. N-(4-Methoxybenzyl)benzenesulfonamide (3b) White solid; mp 71–72 °C (lit.¹³ 72–75°C). IR (KBr): 3281, 1513, 1321, 1254, 1158, 1091, 1031, 858, 730, 685, 590 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 7.85–7.81 (m, 2 H), 7.57–7.52 (m, 1 H), 7.47 (t, J = 7.7 Hz, 2 H), 7.08 (d, J = 8.6 Hz, 2 H), 6.75 (d, J = 8.7 Hz, 2 H), 5.38 (t, J = 6.1 Hz, 1 H), 4.04 (d, J = 6.1 Hz, 2 H), 3.73 (s, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 159.0, 139.8, 132.4, 129.1, 128.9, 128.2, 126.9, 113.8, 55.1, 46.5. ESI-MS: m/z (%) = 295 (100) [M + NH₄]⁺. 4-(Phenylsulfonyl)morpholine (3f) White solid; mp 107–108 °C (lit.¹⁴ 117–119 °C). IR (KBr): 2979, 2862, 1450, 1347, 1261, 1168, 1109, 943, 746, 693, 579, 532 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 7.78–7.73 (m, 2 H), 7.66–7.60 (m, 1 H), 7.58–7.53 (m, 2 H), 3.73 (t, J = 4.8 Hz, 4 H), 3.00 (t, J = 4.7 Hz, 4 H). ¹³C NMR (125 MHz, CDCl₃): δ = 135.1, 133.0, 129.1, 127.8, 66.0, 45.9. ESI-MS: m/z (%) = 228 (100) [M + H]⁺. N-(4-Chlorobenzyl)-4-methylbenzenesulfonamide (3k) White solid; mp 92–93 °C (lit.¹⁵ 88 °C). IR (KBr): 3234, 1641, 1492, 1319, 1157, 1091, 816, 549 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 7.71 (d, J = 8.3 Hz, 2 H), 7.28 (d, J = 8.0 Hz, 3 H), 7.21 (d, J = 8.5 Hz, 2 H), 7.12 (d, J = 8.5 Hz, 2 H), 5.27 (t, J = 6.3 Hz, 1 H), 4.07 (d, J = 6.4 Hz, 2 H), 2.44 (s, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 143.6, 136.8, 135.0, 133.6, 129.8, 129.2, 128.7, 127.1, 46.5, 21.5. ESI-MS: m/z (%) = 313 (73) [M + NH₄]⁺.
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