Aniline → 2-(Anilinomethyl)-4-bromophenol

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 (1 H, br. s.), 7.18-7.46 (4 H, m), 6.95 (1 H, t, J=7.48 Hz), 6.80-6.90 (2 H, m), 6.77 (1 H, d, J=8.58 Hz), 4.39 (2 H, s), 3.98 (1 H, br. s.). Mass spectrum m/z 278, 280 (M+H)+.

1. waitAfter four days
2. stirringThe mixture was stirred at rt for 3 h
3. customThe phases were separated
4. extractionthe aqueous phase was extracted with DCM (2×50 mL)
5. customThe combined organic phases were dried
6. concentrationconcentrated
7. additionThe residue was treated with toluene (25 mL) and hexanes (25 mL)
8. stirringthe mixture was stirred for 30 min
9. washThe precipitate was washed with 1:1 mixture of toluene-hexanes (3 mL)
10. customdried under vacuum

ORD record

ord-17cbc2e65f1443408dfbd264094f64a1

Source dataset

uspto-grants-2013_01

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08362065B2