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

HRID 1162525Notes

Reaction equation

HRID 1162525 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]>[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 935NickelCatalyst

Conditions

Temperature
110 °C

Procedure

A solution of (3-cyanophenyl)acetic acid methyl ester 47 (0.86 g, 4.9 mmol) in 88% formic acid (6 mL) is combined with Raney nickel alloy (0.48 g) and heated to reflux for 24 hours at 110° C. After cooling to room temperature, the alloy is removed by filtration over Celite. The filtrate is concentrated to ˜10% of the original volume and diluted with EtOAc (50 mL) and washed three times with water (20 mL). The organic layer is dried (MgSO4), filtered and concentrated to afford crude product, which is purified by silica gel chromatography using an EtOAc/hexane gradient to give (3-formylphenyl)-acetic acid methyl ester 48 as an oil: 1H-NMR (400 MHz, CDCl3) δ=9.97 (s, 1H), 7.40-7.52 (m, 4H), 3.68 (s, 3H), 3.67 (s, 2H). MS calculated for C10H11O3 (M+H+) 179.1, found 179.1.

Workup

  1. temperatureheated
  2. temperatureAfter cooling to room temperature
  3. customthe alloy is removed by filtration over Celite
  4. concentrationThe filtrate is concentrated to ˜10% of the original volume
  5. additiondiluted with EtOAc (50 mL)
  6. washwashed three times with water (20 mL)
  7. dry with materialThe organic layer is dried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customto afford crude product, which
  11. customis purified by silica gel chromatography

Sources & evidence

ORD record
ord-7508677c4abc447c9a8e8a7a9d1ee34d
Source dataset
uspto-grants-2010_10
Patent number
US07820705B2

Reaction notes

Loading…