Ammonium Chloride → 5-Bromo-o-toluidine

The mixture of Fe powder (9.31 g, 167 mmol) and NH4Cl (2.48 g, 46.3 mmol) in water (50 mL) was refluxed for 30 minutes. To this hot mixture was added 4-bromo-2-nitrotoluene (10 g, 46.3 mmol) slowly and then the reaction mixture was refluxed for 48 hours. The mixture was cooled to room temperature and extracted with EtOAc (3×100 mL). The organic solution was washed with H2O (3×200 mL) and brine (200 mL), dried (Na2SO4), and concentrated. The residue was purified by flash chromatography (silica, 15% EtOAc in hexanes) to give 7.9 g (92%) of title compound as a pale yellow oil. 1H nuclear magnetic resonance (NMR) (CDCl3): 300 MHz δ 6.88 (m, 1H), 6.81 (m, 2H), 3.63 (bs, 2H), 2.09 (s, 3H).

1. temperaturewas refluxed for 30 minutes
2. temperaturethe reaction mixture was refluxed for 48 hours
3. extractionextracted with EtOAc (3×100 mL)
4. washThe organic solution was washed with H2O (3×200 mL) and brine (200 mL)
5. dry with materialdried (Na2SO4)
6. concentrationconcentrated
7. customThe residue was purified by flash chromatography (silica, 15% EtOAc in hexanes)

ORD record

ord-e18fafd17d234b82a149dc17582db7a1

Source dataset

uspto-grants-2007_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07217730B2