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

Temperature

80 °C

To a stirred solution of methyl 5-bromo-2-methyl-3-nitrobenzoate (290 g, 1058.39 mmol) in ethanol (1.5 L) was added aqueous ammonium chloride (283 g, 5290 mmol dissolved in 1.5 L water). The resulting mixture was stirred and heated at 80° C. followed by addition of iron powder (472 g, 8451 mmol) in portions at 80° C. The resulting reaction mixture was heated at 80° C. for 12 h. The reaction mixture was then hot filtered through Celite® and the Celite® bed washed well methanol (5 L) and then with 30% MeOH in DCM (5 L). The combined filtrates were concentrated in vacuo and the residue obtained was diluted with aqueous bicarbonate (2 L) and extracted with ethyl acetate (3×5 L). The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to afford methyl 3-amino-5-bromo-2-methylbenzoate as a brown solid (220 g, 89.41% yield).

1. customThe resulting reaction mixture
2. temperaturewas heated at 80° C. for 12 h
3. filtrationThe reaction mixture was then hot filtered through Celite®
4. washthe Celite® bed washed well methanol (5 L)
5. concentrationThe combined filtrates were concentrated in vacuo
6. customthe residue obtained
7. extractionextracted with ethyl acetate (3×5 L)
8. dry with materialThe combined organic layers were dried over anhydrous sodium sulfate
9. filtrationfiltered
10. concentrationconcentrated under reduced pressure

ORD record

ord-37a54c40f9884dba90c4a4b3b61be0b3

Source dataset

uspto-grants-2014_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08765732B2