4-bromo-2-phenylmethoxyaniline

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred slurry of 2-(benzyloxy)-4-bromoaniline (12.60 g, 45.3 mmol) in concentrated HCl (150 mL) was added a solution of sodium nitrite (3.44 g, 49.9 mmol) in water (20 mL). The reaction mixture was stirred at 0° C. for 30 min before adding a slurry of tin dichloride (25.8 g, 136.0 mmol) in concentrated HCl (35 mL). The reaction mixture was stirred at 0° C. overnight, warmed to ambient temperature, made basic to pH 10 by addition of sodium hydroxide and extracted with diethyl ether. The organic layer was washed with brine, dried over sodium sulfate and treated with 1.25M HCl in methanol (10 mL). The solution was concentrated in vacuo to give (2-(benzyloxy)-4-bromophenyl)hydrazine hydrochloride (5.64 g, 38%) as a brown solid: 1H NMR (CD3OD, 300 MHz) δ 7.31-7.47 (m, 5H), 7.06 (dd, J=8.4, 2.1 Hz, 1H), 6.96 (d, J=2.1 Hz, 1H), 6.86 (d, J=8.4 Hz, 1H), 5.01 (s, 2H). The reaction mixture was stirred at 0° C. overnight warmed to ambient temperature extracted with diethyl ether The organic layer was washed with brine dried over sodium sulfate treated with 1.25M HCl in methanol (10 mL) The solution was concentrated in vacuo

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 2-(benzyloxy)-4-bromo-1-nitrobenzene (14.1 g, 45.8 mmol), iron powder (12.8 g, 229.12 mmol) and ammonium chloride (2.9 g, 55.0 mmol) was taken up in ethanol (60 mL) and water (30 mL) and heated at 90° C. for 3 h. After cooling to ambient temperature, the reaction mixture was filtered through a celite bed and the filtrate concentrated in vacuo. The aqueous residue was extracted with dichloromethane and the organic layer washed with brine, dried over sodium sulfate and concentrated in vacuo to give 2-(benzyloxy)-4-bromoaniline (12.6 g, 99%) as a purple oil: 1H NMR (CDCl3, 300 MHz) δ 7.31-7.46 (m, 5H), 6.98 (d, J=2.1 Hz, 1H), 6.92 (dd, J=8.4, 2.1 Hz, 1H), 6.60 (d, J=8.4 Hz, 1H), 5.05 (s, 2H), 3.81 (br s, 2H). the reaction mixture was filtered through a celite bed the filtrate concentrated in vacuo The aqueous residue was extracted with dichloromethane the organic layer washed with brine dried over sodium sulfate concentrated in vacuo