Sulfuric Acid → 3-Fluoro-4-(methylthio)phenol

Participants

Reaction Conditions

Reaction Steps

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.

Provenance & Evidence