Ammonium Chloride → Methyl 3-Amino-5-bromo-2-methylbenzoate

To a stirred solution of methyl 5-bromo-2-methyl-3-nitrobenzoate (7.60 g, 27.7 mmol) in aq. EtOH (100 mL of EtOH and 20 mL of H2O) was added ammonium chloride (4.45 g, 83.1 mmol) and iron (4.64 g, 83.1 mmol). The reaction mixture was stirred at 80° C. for 5 hours. Then the mixture was filtered through Celite and the Celite bed was washed with ethyl acetate. The combined filtrate was concentrated in vacuo. The resultant residue was dissolved in ethyl acetate and water. The aqueous layer was extracted with ethyl acetate (twice). The combined organic layer dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to afford the titled compound as a brown oil (6.67 g, 99%). 1H-NMR (400 MHz, CDCl3) δ ppm; 7.37 (s, 1H), 6.92 (s, 1H), 3.94 (s, 3H), 3.80 (brs, 2H), 2.31 (s, 3H).

1. filtrationThen the mixture was filtered through Celite
2. washthe Celite bed was washed with ethyl acetate
3. concentrationThe combined filtrate was concentrated in vacuo
4. dissolutionThe resultant residue was dissolved in ethyl acetate
5. extractionThe aqueous layer was extracted with ethyl acetate (twice)
6. dry with materialThe combined organic layer dried over anhydrous sodium sulfate
7. filtrationfiltered
8. concentrationconcentrated under reduced pressure

ORD record

ord-49df4f83a0944e34abfd478f8722e593

Source dataset

uspto-grants-2015_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09006242B2