3-fluoro-4-methylsulfanylphenol

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of oxone (19.6 g, 32 mmol) in water (50 mL) was added to a rapidly stirred solution of 3-fluoro-4-methylsulfanyl-phenol (2.47 g, 15.6 mmol) in tetrahydrofuran (100 mL). The mixture was stirred for 1 h at room temperature and then it was poured into aqueous sodium bicarbonate solution. The mixture was extracted three times with ethyl acetate, and the combined extracts were washed with brine, dried (magnesium sulfate), filtered, evaporated, and eluted through a short silica plug with 50% ethyl acetate/hexanes to give 3-fluoro-4-methanesulfonyl-phenol (2.31 g, 78%) as a light brown oil that solidified on standing. The mixture was extracted three times with ethyl acetate the combined extracts were washed with brine dried (magnesium sulfate) filtered evaporated eluted through a short silica plug with 50% ethyl acetate/hexanes

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Concentrated sulfuric acid (40 mL) was added to a rapidly stirred mixture of 3-fluoro-4-methylsulfanyl-phenylamine (15.5 g, 99 mmol), water (750 mL) and tetrahydrofuran (23 mL). The mixture was cooled to 0° C. and a solution of sodium nitrite (7.5 g, 163 mmol) in water (15 mL) was added. The resulting mixture was stirred for 2 h at 0° C. and it was then added dropwise over 10 min to a stirring solution of copper(II) nitrate (230 g, 1.2 mol) and copper(I) oxide (12.8 g, 89 mmol) in water (1 L). The reaction mixture was stirred for 15 min and then extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried (sodium sulfate), filtered, evaporated, and purified by column chromatography, eluting with 20% ethyl acetate/hexanes to give 3-fluoro-4-methylsulfanyl-phenol (3.73 g, 24%) as a brown oil. The reaction mixture was stirred for 15 min extracted twice with ethyl acetate The combined organic layers were washed with brine dried (sodium sulfate) filtered evaporated purified by column chromatography eluting with 20% ethyl acetate/hexanes