Methyl 4-amino-2-fluoro-5-nitrobenzoate → Methyl 4,5-diamino-2-fluorobenzoate

HRID 470361Notes

Reaction equation

HRID 470361 reaction equation
[NH2:1][C:2]1[C:11]([N+:12]([O-])=O)=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([F:15])[CH:3]=1>CO.[Pd]>[NH2:1][C:2]1[C:11]([NH2:12])=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([F:15])[CH:3]=1

Participants

4

Reactant 1

HCID 53419670Methyl 4-amino-2-fluoro-5-nitrobenzoate

Product 1

HCID 53419644Methyl 4,5-diamino-2-fluorobenzoateYield 40.2%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

A suspension of methyl 4-amino-2-fluoro-5-nitrobenzoate (6.84 g, 31.9 mmol) and 10% Pd/C (1.2 g) in methanol (200 mL) was hydrogenated under an atmosphere of hydrogen (balloon) for 20 h, filtered through Celite and the filtrate concentrated in vacuo to a residue. The residue was purified by flash chromatography (20% EtOAc/DCM) to afford the desired methyl 4,5-diamino-2-fluorobenzoate as a pink solid (2.36 g, 40%). 1H NMR (CDCl3) δ 7.90 (s, 1H), 7.93 (s, 1H), 7.13 (d, J=8.7 Hz, 1H), 6.88 (s, 1H), 6.37 (d, J=13.5 Hz, 1H), 3.60 (t, J=6.9 Hz, 2H), 2.86 (t, J=6.9 Hz, 12H).

Workup

  1. filtrationfiltered through Celite
  2. concentrationthe filtrate concentrated in vacuo to a residue
  3. customThe residue was purified by flash chromatography (20% EtOAc/DCM)

Sources & evidence

ORD record
ord-40b134644311482d8890b040abbc059e
Source dataset
uspto-grants-2014_01
Patent number
US08629147B2

Reaction notes

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