The general procedure for the synthesis of 3-bromo-4-(tert-butyl)aniline from 2-bromo-1-(tert-butyl)-4-nitrobenzene is as follows: to a solution of ethanol (50 mL) containing 2-bromo-1-(tert-butyl)-4-nitrobenzene (5.00 g, 19.37 mmol) and stannous dichloride dihydrate (21.86 g, 96.86 mmol) was heated to 70°C and reacted for 3 hours. After completion of the reaction, the reaction mixture was cooled and poured into 1N sodium hydroxide solution (50 mL) and the pH was adjusted to 5 with 5N sodium hydroxide. the resulting solid was removed by filtration and washed with ethyl acetate (50 mL). The aqueous layer was extracted with ethyl acetate (100 mL), the organic phases were combined and washed with brine (100 mL), dried over anhydrous magnesium sulfate and concentrated. Purification by silica gel column chromatography, eluting first with hexane/ethyl acetate (10:1) and subsequently with hexane/ethyl acetate (3:1), afforded the target product 3-bromo-4-(tert-butyl)aniline as a brown oil (3.53 g, 80% yield). The product was confirmed by 1H NMR (400 MHz, CDCl3): δ 7.16 (d, J = 8.6 Hz, 1H), 6.97 (d, J = 3.0 Hz, 1H), 6.59 (dd, J = 8.4,2.8 Hz, 1H), 1.43 (s, 9H).
