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

HRID 2117603Notes

Reaction equation

HRID 2117603 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 prepared of Preparation 13, Step A (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-ab7b5f2c26f24a29ac809bb81f6e18b8
Source dataset
uspto-grants-2008_10
Patent number
US07442702B2

Reaction notes

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