Iodoethane → HCID 66796962, compound

Participants

Reaction Conditions

Reaction Steps

To thick-walled, reaction pressure tube was added 2,4-difluorobenzenethiol (1500 mg, 10.26 mmol), iodoethane (1.095 mL, 13.34 mmol), acetonitrile (20 mL), and triethylamine (1.860 mL, 13.34 mmol). The vessel was capped and heated at 80° C. for 2 hours. After cooling to room temperature, the reaction mixture was concentrated in vacuo. Methylene chloride was added and the mixture was washed with water three times. The organic layer was concentrated to provide crude 4-(ethylthio)-1,3-difluorobenzene which was used without further purification. To this material (1700 mg, 9.76 mmol) in acetic acid (10 mL) was added hydrogen peroxide (30% in H2O, 4.7 mL, 48.8 mmol). The mixture was refluxed for 2 hours. After cooling to room temperature, the reaction mixture was added to methylene chloride and washed with water three times. The organic layer was dried with sodium sulfate, filtered, and concentrated. The resulting residue was purified by flash chromatography (silica gel, 0-100% ethyl acetate/hexane) to give 1-(ethylsulfinyl)-2,4-difluorobenzene (1.2 g, 6.31 mmol) as white oil. 1H NMR (CDCl3, 500 MHz) δ 7.69-7.86 (m, 1H), 7.03-7.17 (m, 1H), 6.80-6.94 (m, 1H), 3.05 (dd, J=13.75, 7.15 Hz, 1H), 2.83 (dd, J=13.75, 7.15 Hz, 1H), 1.22 (t, J=7.42 Hz, 3H); MS (ESI) 191.1 (M+H). To a solution of 1-(ethylsulfinyl)-2,4-difluorobenzene (1100 mg, 5.78 mmol) in 2-propanol (10 mL) was added water (10 mL) and OXONE® (4622 mg, 7.52 mmol). The mixture was stirred at room temperature for 16 hours. The reaction mixture was then filtered and the filtrate was concentrated. The resulting crude material was dissolved in ethyl acetate and was washed with saturated aqueous sodium chloride twice. The organic layer was dried with sodium sulfate, filtered, and concentrated. The residue obtained was then purified by flash chromatography (silica gel, 0-100% ethyl acetate/hexane) to give Intermediate 9 (600 mg, 50% yield) as a white oil. 1H NMR (CDCl3, 500 MHz) δ 7.90-8.02 (1H, m), 6.90-7.12 (2H, m), 3.30 (2H, q, J=7.3 Hz), 1.30 (3H, t, J=7.4 Hz); MS (ESI) 207.1 (M+H).

Provenance & Evidence