Methanol → 6-bromo-N1-methylbenzene-1,2-diamine

Temperature

90 °C

A mixture of (2-bromo-6-nitrophenyl)methylamine (4.16 g, 18 mmol), ammonium chloride (5.6 g, 108 mmol) and iron powder (4.09 g, 72 mmol) in H2O (32 mL) and MeOH (80 mL) was stirred vigorously for 5 h at 90° C. After cooling to RT, the reaction mixture was filtered through Celite®, washed with MeOH/DCM and the filtrate concentrated in vacuo. The resulting residue was taken up in EtOAc (75 mL) and washed with H2O (75 mL). The aqueous was further extracted with EtOAc (2×75 mL). The combined organic fractions were washed with brine (50 mL), dried (Na2SO4) and concentrated in vacuo. The resulting residue was purified by column chromatography (Si—PPC, gradient 10-75% EtOAc/cyclohexane) to afford the title compound as a red oil (1.46 g, 40%). LCMS (Method C): RT 1.79 min [M+H]+ 211 (for 79Br). 1H NMR (CDCl3, 400 MHz): δ 6.92 (1H, dd, J=8.0, 1.5 Hz), 6.75 (1H, dd, 8.0, 8.0 Hz), 6.64 (1H, dd, J=8.0, 1.5 Hz), 4.02 (2H, bs), 3.25 (1H, bs), 2.68 (3H, s).

1. temperatureAfter cooling to RT
2. filtrationthe reaction mixture was filtered through Celite®
3. washwashed with MeOH/DCM
4. concentrationthe filtrate concentrated in vacuo
5. washwashed with H2O (75 mL)
6. extractionThe aqueous was further extracted with EtOAc (2×75 mL)
7. washThe combined organic fractions were washed with brine (50 mL)
8. dry with materialdried (Na2SO4)
9. concentrationconcentrated in vacuo
10. customThe resulting residue was purified by column chromatography (Si—PPC, gradient 10-75% EtOAc/cyclohexane)

ORD record

ord-e0c55eda4d9241e696e6f087da1f461b

Source dataset

uspto-grants-2014_02

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08653089B2