Formic Acid → Methyl 2-(3-formylphenyl)acetate

HRID 890797Notes

Reaction equation

HRID 890797 reaction equation
[CH3:1][O:2][C:3](=[O:13])[CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([C:11]#N)[CH:6]=1.C(O)=[O:15]>[Al].[Ni]>[CH3:1][O:2][C:3](=[O:13])[CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([CH:11]=[O:15])[CH:6]=1

Participants

4

Reactant 2

HCID 284Formic AcidHCID 1514291Methyl (3-cyanophenyl)acetate

Product 1

HCID 11819590Methyl 2-(3-formylphenyl)acetate

Reagents, catalysts & solvents 1

HCID 6336846Nickel aluminideCatalyst

Procedure

A mixture of (3-cyano-phenyl)-acetic acid methyl ester (1.56 g, 8.91 mmol), aluminum-nickel alloy (1.63 g) and 75% formic acid (25 mL) was heated at reflux for 1.75 h. The mixture was cooled to room temperature and the solids were removed by filtration through Celite with the aid of boiling EtOH. Water was added and the aqueous solution was washed with CH2Cl2 (3×). Aqueous saturated NaHCO3 was carefully added to the organic solution until the pH was about 8–9. The organic solution was washed with brine, dried over MgSO4, and concentrated. Purification by flash chromatography (5:1 hexanes:EtOAc) provided the title compound as a clear and colorless oil (870 mg). 1H NMR (400 MHz, CDCl3) δ 9.98 (s, 1H), 7.77 (m, 2H), 7.55–7.46 (m, 2H), 3.68 (s, 5H).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 1.75 h
  3. customthe solids were removed by filtration through Celite with the aid of boiling EtOH
  4. additionWater was added
  5. washthe aqueous solution was washed with CH2Cl2 (3×)
  6. additionAqueous saturated NaHCO3 was carefully added to the organic solution until the pH was about 8–9
  7. washThe organic solution was washed with brine
  8. dry with materialdried over MgSO4
  9. concentrationconcentrated
  10. customPurification by flash chromatography (5:1 hexanes:EtOAc)

Sources & evidence

ORD record
ord-858b198abc244663a56831dde370cbf8
Source dataset
uspto-grants-2006_02
Patent number
US06998423B2

Reaction notes

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