Potassium Acetate → 2-Benzyloxy-4-formylbenzoic acid

HRID 1583038Notes

Reaction equation

HRID 1583038 reaction equation
[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([CH:14]=[CH:15][C:16]=1S(C(F)(F)F)(=O)=O)[CH:12]=[O:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:24]([O-:27])(=[O:26])C.[K+]>CS(C)=O.C([O-])(=O)C.C([O-])(=O)C.[Pd+2].C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([CH:12]=[O:13])[CH:14]=[CH:15][C:16]=1[C:24]([OH:27])=[O:26])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 2

HCID 517044Potassium AcetateHCID 227168263-Benzyloxy-4-trifluoromethanesulfonylbenzaldehyde

Product 1

HCID 227168252-Benzyloxy-4-formylbenzoic acid

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 679Dimethyl SulfoxideSolvent

Procedure

A mixture of 3-benzyloxy-4-trifluoromethanesulfonylbenzaldehyde (350 mg, 0.97 mmol, 1 eq), potassium acetate (380 mg, 3.89 mmol, 4 eq), palladium (II) diacetate (32 mg, 0.05 mmol, 0.05 eq) and 1,1′-bis-(diphenylphosphino)ferrocene (dppf) (108 mg, 0.19 mmol, 0.2 eq) in anhydrous dimethylsulfoxide (6 mL) was purged with carbon monoxide and stirred for 5 min. The reaction mixture was then heated to 60□C. and stirred under a carbon monoxide balloon for 3 h. The solution was allowed to cool to room temperature, and acidified to pH 1 with 10% HCl and then extracted with ethyl acetate (2×20 mL). The organic extracts were combined and washed with brine, then extracted with saturated aqueous sodium bicarbonate (3×20 mL). The aqueous extracts were combined, washed with ethyl acetate (2×20 mL), acidified to pH 1 with 10% HCl and back extracted with ethyl acetate (2×20 mL). The organic solution was dried over sodium sulfate and evaporated in vacuo to give a cream coloured powder (146 mg, 59%). 1H NMR (CDCl3) δ10.08 (s, 1H, O═C—H), 5.39 (s, 2H, OCH2Ph).

Workup

  1. customwas purged with carbon monoxide
  2. temperatureThe reaction mixture was then heated to 60□C
  3. stirringand stirred under a carbon monoxide balloon for 3 h
  4. extractionextracted with ethyl acetate (2×20 mL)
  5. washwashed with brine
  6. extractionextracted with saturated aqueous sodium bicarbonate (3×20 mL)
  7. washwashed with ethyl acetate (2×20 mL)
  8. extractionback extracted with ethyl acetate (2×20 mL)
  9. dry with materialThe organic solution was dried over sodium sulfate
  10. customevaporated in vacuo
  11. customto give a cream

Sources & evidence

ORD record
ord-599fd53d25074add8d9dd4f5311f4801
Source dataset
uspto-grants-2004_05
Patent number
US06740670B2

Reaction notes

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