Acetic Acid → Methyl 2-(4-amino-3-bromophenyl)acetate

HRID 350446Notes

Reaction equation

[Br:1][C:2]1[CH:3]=[C:4]([CH2:11][C:12]([O:14][CH3:15])=[O:13])[CH:5]=[CH:6][C:7]=1[N+:8]([O-])=O.C(O[Na])(C)=O.O.O.O.CC(O)=O>CO.O>[NH2:8][C:7]1[CH:6]=[CH:5][C:4]([CH2:11][C:12]([O:14][CH3:15])=[O:13])=[CH:3][C:2]=1[Br:1]

Participants

Conditions

Temperature: 90 °C

Procedure

A mixture of methyl 3-bromo-4-nitrophenylacetate (14.8 g, 53.8 mmol), reduced iron powder (9.62 g, 172 mmol), AcONa.3H2O (7.32 g, 53.8 mmol) and AcOH (20.0 ml) in MeOH/H2O (150/600 ml) was heated at 90° C. for 1 h. After cooled to room temperature, the reaction mixture was filtered through Celite and the filtered cake was washed with MeOH. The combined filtrate were evaporated and extracted with EtOAc. The extracts were washed with brine, dried over Na2SO4 and concentrated in vacuo. The residue was chromatographed on silica gel [400 g, CHCl3/EtOAc (20/1)] to give methyl 4-amino-3-bromophenylacetate (9.01 g, 69%) as a brown oil. 1H-NMR (CDCl3) δ 3.48 (s, 2H), 3.68 (s, 3H), 4.05 (br, 2H), 6.69 (d, J=8.3 Hz, 1H), 7.00 (dd, J=8.1, 2.0 Hz, 1H), 7.32 (d, J=2.0 Hz, 1H).

Workup

temperatureAfter cooled to room temperature
filtrationthe reaction mixture was filtered through Celite
washthe filtered cake was washed with MeOH
customThe combined filtrate were evaporated
extractionextracted with EtOAc
washThe extracts were washed with brine
dry with materialdried over Na2SO4
concentrationconcentrated in vacuo
customThe residue was chromatographed on silica gel [400 g, CHCl3/EtOAc (20/1)]

Sources & evidence

ORD record: ord-34b91b524ede4458baa24574c7e61c92
Source dataset: uspto-grants-2007_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07179819B2

Reaction notes

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