Solvent-Selective Synthesis of Diaryl Disulfides and Arylthio Acetic Acids Using Thioglycolic Acid and Copper Catalysts

Abstract

An efficient Cu-catalytic protocol for the synthesis of diaryl disulfides from aryl iodides using thioglycolic acid as the sulfur source has been developed. This transformation was successful only in aqueous DMSO, and when the solvent system was switched to aqueous DMF, arylthio acetic acids, the immediate C–S coupling products, were obtained. Each synthetic protocol was optimized and applied to various aryl iodides to afford the corresponding products in good to excellent yields.

Key words

diaryl disulfide - thioglycolic acid - arylthio acetic acid - copper catalyst - C–S coupling

Publication History

Received: 22 August 2023

Accepted after revision: 19 September 2023

Accepted Manuscript online:
19 September 2023

Article published online:
24 October 2023

• References and Notes

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• 35 General Procedure for the Synthesis of Diaryl Disulfides Cu(OAc)₂·H₂O (0.1 mmol) and K₂CO₃ (2.0 mmol) were charged in a test tube, which was degassed and filled with argon. Aryl iodide (1.0 mmol), DMSO (2.0 mL), and H₂O (1.0 mL) were added in the test tube, followed by thioglycolic acid (3.0 mmol). The reaction mixture was stirred at 120 °C for 16 h. After cooled to room temperature, the reaction mixture was neutralized with 1 N HCl solution. Then, the aqueous phase was extracted with ethyl acetate (2 × 30 mL). The combined organic layers were washed with H₂O and brine, dried over Na₂SO₄, and concentrated in vacuo. Purification of the crude product by column chromatography on silica gel afforded the desired product (eluent: n-hexane to n-hexane–ethyl acetate (20:1)). 1,2-Di-p-tolyldisulfane (2b) ¹H NMR (500 MHz, chloroform-d): δ = 7.38 (d, J = 8.2 Hz, 4 H), 7.10 (d, J = 7.9 Hz, 4 H), 2.32 (s, 6 H).¹³C{1H} NMR (125 MHz, chloroform-d): δ = 137.4, 133.9, 129.8, 128.5, 21.1. MS (EI): m/z = 246.05.
• 36 General Procedure for the Synthesis of Arylthio Acetic Acid CuI (0.05 mmol) and K₂CO₃ (4.0 mmol) were charged in a test tube, which was degassed and filled with argon. Aryl iodide (1.0 mmol), DMF (2.0 mL), and H₂O (1.0 mL) were added followed by thioglycolic acid (3.0 mmol). The reaction mixture was stirred at 120 °C for 20 h. After cooled to room temperature, the reaction mixture was acidified with 1 N HCl solution. The aqueous phase was extracted with ethyl acetate twice, and the combined organic layers were washed with H₂O and brine, dried over Na₂SO₄, and concentrated in vacuo. Purification of the crude product by column chromatography on silica gel afforded the desired product [eluent: n-hexane: ethyl acetate (1:2) to ethanol–dichloromethane (1:9)]. 4-Methyl Phenyl Thioacetic Acid (3b) FT-IR: 2917, 2688, 1696, 1200, 798 cm^–1. ¹H NMR (500 MHz, chloroform-d): δ = 7.38–7.29 (m, 2 H), 7.13 (d, J = 8.4 Hz, 2 H), 3.62 (s, 2 H), 2.33 (s, 3 H). ¹³C{1H} NMR (125 MHz, chloroform-d): δ = 175.3, 137.7, 131.0, 130.6, 129.9, 37.3, 21.1. HR-MS (EI): m/z calcd for C₉H₁₀O₂S: 182.0404; found: 182.0402.