1227210-36-7

1227210-35-6

1227210-36-7

General procedure for the synthesis of 3-bromo-6-fluoro-2-methylaniline from 1-bromo-4-fluoro-2-methyl-3-nitrobenzene: In a 100 mL single-necked round-bottomed flask equipped with a magnetic stirrer, a reflux condenser tube, and a nitrogen introduction tube, 1-bromo-4-fluoro-2-methyl-3-nitrobenzene (700 mg, 2.58 mmol), stannous chloride dihydrate (2.62 g, 11.6 mmol), hydrochloric acid (6.5 mL), and methanol (6.mL) were added. 11.6 mmol), hydrochloric acid (6.5 mL) and methanol (6.5 mL). The reaction mixture was heated and stirred at 40°C for 2 hours. Upon completion of the reaction, potassium carbonate was added to adjust the pH of the reaction solution to 12, and the resulting suspension was extracted with dichloromethane (2 x 50 mL). The organic phases were combined, dried with anhydrous sodium sulfate, filtered and concentrated under reduced pressure. Purification of the residue by fast column chromatography afforded 3-bromo-6-fluoro-2-methylaniline as a yellow solid in 98% yield (598 mg) with a melting point of 49-50 °C.1H NMR (500 MHz, CDCl3) δ 6.91 (dd, 1H, J = 9.0, 5.0 Hz), 6.76 (dd, 1H, J = 10.0, 9.0 Hz), 6.76 (dd, 1H, J = 10.0, 9.0 Hz), and 3.77 (br s, 2H), 2.28 (s, 3H); MS (ESI+) m/z 203.9 ([M+H]+).