Aniline → 2-(Anilinomethyl)-4-bromophenol

Participants

Reaction Steps

Step 1 Aniline (1.50 mL, 16.42 mmol) was added to a solution of 5-bromo-2-hydroxybenzaldehyde (3.00 g, 14.92 mmol) in 1,2-dichloroethane (100 mL). After 10 min at rt, sodium triacetoxyborohydride (4.74 g, 22.39 mmol) was added. The mixture was stirred at rt. After four days, additional aniline (1.50 mL, 16.42 mmol) and sodium triacetoxyborohydride (4.74 g, 22.39 mmol) were added. After two more days, saturated aqueous ammonium chloride (200 mL) was added. The mixture was stirred at rt for 3 h. The phases were separated and the aqueous phase was extracted with DCM (2×50 mL). The combined organic phases were dried and concentrated. The residue was treated with toluene (25 mL) and hexanes (25 mL) and the mixture was stirred for 30 min. The precipitate was washed with 1:1 mixture of toluene-hexanes (3 mL) and dried under vacuum to give 4-bromo-2-((phenylamino)methyl)phenol as a white solid (2.64 g, 64%). 1H NMR (400 MHz, DMSO-d6) δ 8.70 (1H, br. s.), 7.18-7.46 (4H, m), 6.95 (1H, t, J=7.48 Hz), 6.80-6.90 (2H, m), 6.77 (1H, d, J=8.58 Hz), 4.39 (2H, s), 3.98 (1H, br. s.). Mass spectrum m/z 278, 280 (M+H)+.

Provenance & Evidence