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

HRID 365047Notes

Reaction equation

HRID 365047 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.[CH3:30][O:31][C:32](=[O:41])[C:33]1[CH:38]=[CH:37][C:36]([CH:39]=O)=[CH:35][CH:34]=1>C1COCC1.O>[C:2]1([CH2:8][CH2:9][CH:10]=[CH:39][C:36]2[CH:37]=[CH:38][C:33]([C:32]([O:31][CH3:30])=[O:41])=[CH:34][CH:35]=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 phenylpropyl triphenylphosphonium bromide (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 4-formylbenzoic acid methyl ester (1.0 g, 6.1 mmol) 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 (~200 ml) was added and the mixture was washed with H2O, 1N HCl (2×) and brine. After drying over anhydrous MgSO4, the solvent was removed in vacuo to yield a yellow oil which solidified soon after. Column purification of this crude product was done on a 50 mm column on silica gel eluted with 95:5 hexane/EtOAc. Product containing fractions were combined to yield after concentration title compound, 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 (~200 ml) was added
  6. washthe mixture was washed with H2O, 1N HCl (2×) and brine
  7. dry with materialAfter drying over anhydrous MgSO4
  8. customthe solvent was removed in vacuo
  9. customto yield a yellow oil which
  10. customColumn purification of this crude product
  11. washeluted with 95:5 hexane/EtOAc
  12. additionProduct containing fractions
  13. customto yield
  14. concentrationafter concentration title compound, 1.5 g (93%) as a clear oil

Sources & evidence

ORD record
ord-e7eb046364194948818c9999a268ad93
Source dataset
uspto-grants-1986_08
Patent number
US04607053

Reaction notes

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