HCID 67403309, compound → Benzoic acid, 5-amino-4-cyano-2-fluoro-, methyl ester

HRID 906170Notes

Reaction equation

HRID 906170 reaction equation
[C:1]([C:3]1[C:12]([N+:13]([O-])=O)=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[C:5]([F:16])[CH:4]=1)#[N:2]>C(O)(=O)C.[Fe]>[NH2:13][C:12]1[C:3]([C:1]#[N:2])=[CH:4][C:5]([F:16])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8]

Participants

4

Reactant 1

HCID 67403309HCID 67403309, compound

Product 1

HCID 67403793Benzoic acid, 5-amino-4-cyano-2-fluoro-, methyl esterYield 68%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 176Acetic AcidSolvent

Procedure

To a solution of methyl 4-cyano-2-fluoro-5-nitrobenzoate (785 mg, 3.5 mmol) in acetic acid (15 mL) was added iron powder (1.17 g, 21.0 mmol). The mixture was stirred vigorously at room temperature for 2 h. Insoluble solids were then removed by filtration through celite. Water was added to the filtrate and the aqueous mixture was extracted with ethyl acetate. The organic extract was washed with saturated aqueous sodium bicarbonate, dried over magnesium sulfate, filtered, and concentrated. The residue was purified by column chromatography (30% ethyl acetate in hexanes) to provide methyl 5-amino-4-cyano-2-fluorobenzoate (463 mg, 2.38 mmol, 68% yield). 1H NMR (400 MHz, CDCl3): 7.30 (d, 1H), 7.19 (d, 1H), 4.41 (br s, 2H), 3.94 (s, 3H); MS (EI) for C9H7FN2O2: 193 (M−H).

Workup

  1. customInsoluble solids were then removed by filtration through celite
  2. additionWater was added to the filtrate
  3. extractionthe aqueous mixture was extracted with ethyl acetate
  4. extractionThe organic extract
  5. washwas washed with saturated aqueous sodium bicarbonate
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by column chromatography (30% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-a15f78c5d8eb4aeb911e16bcaddb7cb5
Source dataset
uspto-grants-2011_09
Patent number
US08012956B2

Reaction notes

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