Methyl 5-bromo-4-fluoro-2-methoxy-3-nitrobenzoate → Methyl 3-amino-5-bromo-4-fluoro-2-methoxybenzoate

HRID 17521Notes

Reaction equation

[Br:1][C:2]1[C:3]([F:17])=[C:4]([N+:14]([O-])=O)[C:5]([O:12][CH3:13])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8]>C(O)(=O)C.[Fe]>[NH2:14][C:4]1[C:5]([O:12][CH3:13])=[C:6]([CH:11]=[C:2]([Br:1])[C:3]=1[F:17])[C:7]([O:9][CH3:10])=[O:8]

Participants

Conditions

Temperature: 130 °C

Procedure

Methyl 5-bromo-4-fluoro-2-methoxy-3-nitrobenzoate (I-229) (1.0 g, 3.25 mmol) was dissolved in acetic acid (10 ml), and at room temperature, iron powder (544 mg, 9.74 mmol) was added, followed by stirring at 130° C. for 4 hours. After cooling to room temperature, the insoluble matter was separated by filtration with washing with ethyl acetate. The organic layer of the filtrate was evaporated under reduced pressure, and the resulting residue was fractionated with ethyl acetate and aqueous 1 M sodium hydroxide solution. The organic layer was washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was evaporated away, and the resulting residue was purified by middle-pressure liquid chromatography (eluent, hexane:ethyl acetate=4:1) to obtain the entitled compound (798 mg, 88%) as a colorless gel substance.

Workup

temperatureAfter cooling to room temperature
customthe insoluble matter was separated by filtration
washwith washing with ethyl acetate
customThe organic layer of the filtrate was evaporated under reduced pressure
washThe organic layer was washed with saturated brine
dry with materialdried over anhydrous sodium sulfate
customThe solvent was evaporated away
customthe resulting residue was purified by middle-pressure liquid chromatography (eluent, hexane:ethyl acetate=4:1)

Sources & evidence

ORD record: ord-f740c8c8ae614833aaad2673564ab398
Source dataset: uspto-grants-2010_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07737166B2

Reaction notes

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