Hydrochloric Acid → Methyl 3-amino-4-chloro-5-methoxybenzoate

Temperature

70 °C

A suspension of methyl 4-chloro-3-methoxy-5-nitrobenzoate (3) (900 mg, 3.66 mmol) and iron powder (614 mg, 11.0 mmol) in a mixture of EtOH (15 mL) and water (15 mL) was heated to 70° C. and degassed with nitrogen for 20 min. Conc. HCl (44.5 μL, 1.47 mmol) was added and the reaction mixture was stirred at 70° C. for 3 h. Celite (1 g) was added and the suspension stirred for 10 min then filtered through a celite pad. The solvent was removed in vacuo and the residue was partitioned between EtOAc (15 mL) and water (15 mL). The phases were separated and the organic solution was washed with brine (2×15 mL). The solvent was removed in vacuo to afford methyl 3-amino-4-chloro-5-methoxybenzoate (0.82 g, 100% yield) as a yellow solid: 1H NMR (400 MHz, DMSO-d6) δ: 7.10 (1H, d), 6.78 (1H, d), 5.68 (2H, s), 3.81 (6H, m).

1. customdegassed with nitrogen for 20 min
2. additionCelite (1 g) was added
3. stirringthe suspension stirred for 10 min
4. filtrationthen filtered through a celite pad
5. customThe solvent was removed in vacuo
6. customthe residue was partitioned between EtOAc (15 mL) and water (15 mL)
7. customThe phases were separated
8. washthe organic solution was washed with brine (2×15 mL)
9. customThe solvent was removed in vacuo

ORD record

ord-38d487cc6a3448259e1d0f0584f4dc03

Source dataset

uspto-grants-2016_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09447028B2