General procedure for the synthesis of 5-bromo-2-(trifluoromethyl)aniline from 4-bromo-2-nitro-trifluoromethylbenzene: to a suspension of 4-bromo-2-nitro-1-(trifluoromethyl)benzene (4.0 g, 14.9 mmol) in ethanol (230 mL), THF (85 mL), and water (40 mL), ammonium chloride (1.0 g, 18.8 mmol) and iron powder (5.06 g, 90 mmol). The reaction mixture was heated at 80 °C for 1 h and the progress of the reaction was monitored by thin layer chromatography (TLC). After complete consumption of starting materials, the reaction mixture was filtered while hot. The filtrate was concentrated under reduced pressure and the crude product was dissolved in ethyl acetate (100 mL) and washed with water (3 x 50 mL). The organic layers were combined, washed with saturated brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure to give 5-bromo-2-(trifluoromethyl)aniline as a solid (3.2 g, 90% yield).
