Copper-Catalyzed Methylthiolation of Aryl Iodides and Bromides with Dimethyl Disulfide in Water

Abstract

An efficient route to aryl methyl sulfides through the copper-catalyzed coupling reaction of aryl iodides or bromides with dimethyl disulfide in water is described. Electron-donating and electron-withdrawing functional groups in the substrates were tolerated, and the corresponding products were obtained in moderate to good yields.

Key words

methylthiolation - aryl halides - dimethyl disulfide - aryl methyl sulfides - copper catalysis

• References and Notes

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• 32 (Het)aryl Methyl Sulfides; General Procedure A 25-mL sealable tube was charged with the appropriate aryl iodide or bromide (1.0 mmol), dimethyl disulfide (1.2 mmol), Cu(OAc)₂·H₂O (0.1 mmol), KOH (2.0 mmol), TBAB (0.05 mmol), and H₂O (2.0 mL). The mixture was stirred at 100 °C (130 °C for bromides) for 12 h under air then cooled to r.t. The mixture was diluted with H₂O (5 mL) and extracted with EtOAc (4 × 10 mL). The extracts were combined, washed with brine (3 × 10 mL), dried (MgSO₄), filtered, and concentrated. The residue was purified by chromatography [silica gel, EtOAc–hexane (1:30 to 1:100)]. 4-(Methylsulfanyl)aniline (Table [2], entry 9) Yellow oil; yield: 107 mg (77%). ¹H NMR (300 MHz, CDCl₃): δ = 7.16 (d, J = 8.7 Hz, 2 H), 6.60 (d, J = 8.4 Hz, 2 H), 3.62 (s, 2 H), 2.39 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 145.2, 131.1, 125.7, 115.9, 18.8. GC/MS (EI): m/z = 139 [M+]. 1-Methoxy-4-(methylsulfanyl)benzene; Gram-Scale Synthesis A 50 mL sealable tube was charged with p-iodoanisole (5 mmol, 1.17 g), dimethyl disulfide (6 mmol, 0.56 g), Cu(OAc)₂·H₂O (0.5 mmol, 100 mg), KOH (10 mmol, 5.6 g), TBAB (0.25 mmol, 81 mg), and H₂O (10 mL). The mixture was stirred at 100 °C for 12 h under air, then cooled to r.t., diluted with H₂O (5 mL), and extracted with EtOAc (4 × 15 mL). The extracts were combined and washed with brine (3 × 15 mL), dried (MgSO₄), filtered, and concentrated. The residue was purified by chromatography [silica gel, EtOAc–hexane (1:30)] to give a pale-yellow oil; yield: 0.56 g (73%).
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