Ammonium Iodide-Mediated Sulfenylation of 4-Hydroxycoumarins or 4-Hydroxyquinolinones with a Sulfonyl Chloride as a Sulfur Source

Abstract

A novel ammonium iodide-induced sulfenylation of 4-hydroxycoumarins or 4-hydroxyquinolinones by using an aryl- or alkylsulfonyl chloride as the sulfur source gave a wide range of 3-sulfanyl-4-hydroxycoumarins or 3-sulfanyl-4-hydroxyquinolinones, respectively, in moderate to good yields. This method provides as a simple approach to the direct formation of C–S bonds, which is of high value and utility in the pharmaceutical industry.

Key words

sulfanylhydroxycoumarins - sulfanylhydroxyquinolinones - C–S bond formation - sulfenylation - sulfonyl chlorides - ammonium ­iodide

• References and Notes

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• 14 4-Hydroxy-3-sulfanylquinolin-2(1H)-ones 3a–o and 4-Hydroxy-3-sulfanyl-2H-chromen-2-ones 5a–q; General Procedure 1,4-Dioxane (0.5 mL) was added to flask charged with the appropriate 4-hydroxyquinolinone or 4-hydroxycoumarin (0.25 mmol), sulfonyl chloride (0.25 mmol), and NH₄I (1 mmol), and the mixture was stirred at 110 °C under air for 6–12 hours until the reaction was complete (TLC). The mixture was then cooled to r.t., diluted with EtOAc (20 mL), and washed with H₂O (10 mL). The aqueous layer was extracted with EtOAc (2 × 5 mL), and the organic phases were combined and dried (Na₂SO₄). After evaporation of the solvents, the residue was purified by flash column chromatography [silica gel, PE–EtOAc (4:1 to 1:1)] to afford the desired product 3 or 5. 4-Hydroxy-1-methyl-3-(4-tolylsulfanyl)quinolin-2(1H)-one (3a)[11]
  Yellow solid; yield: 58 mg (78%); mp 234–236 °C. IR (KBr): 2922, 2362, 1614, 1583, 1500, 1159, 1074, 802, 756 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 2.26 (s, 3 H), 3.71 (s, 3 H), 7.03 (d, J = 8.0 Hz, 2 H), 7.22–7.30 (m, 3 H), 7.36 (d, J = 8.8 Hz, 1 H), 7.65 (td, J = 1.6, 8.8 Hz, 1 H), 7.90 (s, 1 H), 8.06 (dd, J = 1.2, 8.0 Hz, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 21.1, 30.3, 103.2, 114.3, 114.4, 122.1, 125.1, 128.7, 130.1, 130.7, 132.8, 137.0, 140.4, 161.8, 163.2. HRMS: m/z [M + H]⁺ calcd for C₁₇H₁₆NO₂S: 298.0896; found: 298.0909. 4-Hydroxy-3-(phenylsulfanyl)-2H-chromen-2-one (5a)[11] Yellow solid; yield: 54 mg (80 %); mp 198–200 °C. ¹H NMR (400 MHz, DMSO-d ₆): δ = 7.15–7.21 (m, 3 H), 7.29 (d, J = 8.0 Hz, 2 H), 7.40–7.45 (m, 2 H), 7.70–7.75 (m, 1 H), 7.97 (dd, J = 1.2, 8.0 Hz, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 94.3, 115.7, 116.5, 124.2, 124.4, 125.5, 126.2, 129.1, 133.7, 135.9, 153.0, 160.9, 168.5. HRMS: m/z [M + H]⁺ calcd for C₁₅H₁₁O₃S: 271.04234; found: 271.04205.