Ammonium Chloride → 5-Bromo-4-fluoro-2-methylaniline

The mixture of iron powder (17.8 g, 318 mmol) and NH4Cl (5.10 g, 95.4 mmol) in water (100 mL) was refluxed for 30 minutes. To this hot mixture was added 4-bromo-3-fluoro-6-nitrotoluene (18.6 g, 79.5 mmol) slowly and then the reaction mixture was refluxed for 48 hours. The mixture was cooled to room temperature and extracted with EtOAc (3×200 mL). The organic solution was washed with H2O (3×300 mL) and brine (300 mL), dried (Na2SO4), and concentrated. The residue was purified by flash chromatography (silica, 20% EtOAc in hexanes) to give 11.7 g (72%) of title compound as a pale yellow solid. 1H NMR (CDCl3): 300 MHz δ 6.82 (m, 2H), 3.49 (bs, 2H), 2.11 (s, 3H).

1. temperaturewas refluxed for 30 minutes
2. temperaturethe reaction mixture was refluxed for 48 hours
3. extractionextracted with EtOAc (3×200 mL)
4. washThe organic solution was washed with H2O (3×300 mL) and brine (300 mL)
5. dry with materialdried (Na2SO4)
6. concentrationconcentrated
7. customThe residue was purified by flash chromatography (silica, 20% EtOAc in hexanes)

ORD record

ord-b60b9c4855e04d9ebc30b11ba110602b

Source dataset

uspto-grants-2007_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07217730B2