Methyl 4-Formylbenzoate → 4-(Phenyl-1-butenyl)benzoic acid, methyl ester

HRID 845247Notes

Reaction equation

HRID 845247 reaction equation
[Br-].[C:2]1([CH2:8][CH2:9][CH2:10][P+](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH:30]([C:32]1[CH:41]=[CH:40][C:35]([C:36]([O:38][CH3:39])=[O:37])=[CH:34][CH:33]=1)=O>C1COCC1.O>[C:2]1([CH2:8][CH2:9][CH:10]=[CH:30][C:32]2[CH:41]=[CH:40][C:35]([C:36]([O:38][CH3:39])=[O:37])=[CH:34][CH:33]=2)[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 2

HCID 15294Methyl 4-FormylbenzoateHCID 109286473-Phenylpropyl triphenylphosphonium bromide

Product 1

HCID 540007444-(Phenyl-1-butenyl)benzoic acid, methyl ester

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a 0° solution of Part A (1) compound (3.55 g, 1.25 eq) in 30 ml of dry THF under Argon was added K-t-amylate (3.9 ml, 1.1 eq). After stirring for 30 minutes at 0° C. then allowing to warm to room temperature, a solution of methyl 4-formylbenzoate (1.0 g, 6.1 mmol, Fluka) in ~8 ml of dry THF was added dropwise. This solution was stirred for 3 hours at room temperature, then diluted with ~1 ml of H2O, and concentrated to remove most of the THF. EtOAc (18 200 ml) was added and the mixture was washed with H2O, 1N HCl (2X) and brine. After drying over anhydrous MgSO4 the solvent was removed in vacuo to yield a yellow oil which solidified. Column purification of this crude product on silica gel eluted with 95:5 hexane/EtOAc yielded after concentration title aldehyde 1.5 g (93%) as a clear oil.

Workup

  1. temperatureto warm to room temperature
  2. stirringThis solution was stirred for 3 hours at room temperature
  3. concentrationconcentrated
  4. customto remove most of the THF
  5. additionEtOAc (18 200 ml) was added
  6. washthe mixture was washed with H2O, 1N HCl (2X) and brine
  7. dry with materialAfter drying over anhydrous MgSO4 the solvent
  8. customwas removed in vacuo
  9. customto yield a yellow oil which
  10. customColumn purification of this crude product on silica gel
  11. washeluted with 95:5 hexane/EtOAc
  12. customyielded
  13. concentrationafter concentration title aldehyde 1.5 g (93%) as a clear oil

Sources & evidence

ORD record
ord-e1e5a0891aef48fca2731ead482ed104
Source dataset
uspto-grants-1988_07
Patent number
US04757078

Reaction notes

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