Copper-Catalyzed Synthesis of S-Aryl Dithiocarbamates from Tetraalkylthiuram Disulfides and Aryl Iodides in Water

Abstract

An efficient approach for the copper-catalyzed synthesis of aryl dithiocarbamates from aryl iodides and tetraalkylthiuram disulfides in water is described. Without additional ligand and organic solvent, the coupling reaction could provide a series of S-aryl dithiocarbamates in moderate to good yields.

Key words

copper - aryl dithiocarbamate - aryl iodide - tetraalkylthiuram disulfide - water

• References

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• 18 General Procedure Aryl iodides (1.0 mmol), tetraalkylthiuram disulfides (1.0 mmol), Cu(acac)₂ (0.1 mmol), Na₂CO₃ (1.0 mmol), n-Bu₄NBr (0.1 mmol), and H₂O (2.0 mL) were taken in a 25 mL sealed tube. The reaction mixture was stirred at 100 °C for 12 h. After cooling to room temperature, the product was diluted with H₂O (5 mL) and extracted with EtOAc (3 × 10 mL). The extracts were combined and washed by brine (3 × 10 mL), dried over MgSO₄, filtered, evaporated, and purified by chromatography on silica gel to obtain the desired products with ethyl acetate/hexane (v/v = 1:3 to ca. 1:10). The products were characterized by their spectral and analytical data and compared with those of the known compounds (see Supporting Information). Typical Data for Representative Compound Dimethyl-dithiocarbamic Acid 3-Methylthio-phenyl Ester (Table2, Entry 17) ¹H NMR (CDCl₃, 300 MHz): δ = 7.34–7.33 (m, 3 H), 7.25–7.24 (m, 1 H), 3.54 (s, 3 H), 3.47 (s, 3 H), 2.48 (s, 3 H). ¹³C NMR (CDCl₃, 75 MHz): δ = 197.0, 139.6, 134.3, 133.3, 132.4, 129.3, 128.0, 45.7, 42.1, 15.8. GC–MS (EI): m/z = 243 [M⁺].
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