Allyl Alcohol → Ethyl 4-(3-oxopropyl)benzoate

HRID 1108439Notes

Reaction equation

HRID 1108439 reaction equation
I[C:2]1[CH:12]=[CH:11][C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][CH:3]=1.C(=O)(O)[O-].[Na+].[CH2:18]([OH:21])[CH:19]=[CH2:20]>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.CN(C)C=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH2:9]([O:8][C:6]([C:5]1[CH:11]=[CH:12][C:2]([CH2:20][CH2:19][CH:18]=[O:21])=[CH:3][CH:4]=1)=[O:7])[CH3:10]

Participants

7

Reactant 3

HCID 7858Allyl AlcoholHCID 142891Ethyl 4-iodobenzoateHCID 516892Sodium Bicarbonate

Product 1

HCID 2757377Ethyl 4-(3-oxopropyl)benzoateYield 98%

Reagents, catalysts & solvents 3

HCID 74236Tetrabutylammonium BromideCatalystHCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Procedure

To a solution of 20 g (69.9 mmol) of ethyl 4-iodobenzoate, 0.47 g (2.1 mmol) of palladium acetate, 14.7 g (175 mmol) of sodium bicarbonate, and 22.5 g (70 mmol) of tetrabutylammonium bromide in 200 mL of dimethyl formamide were added, under nitrogen, 6.89 g (118.8 mmol) of allyl alcohol. The reaction mixture was stirred at room temperature for 42 hours. The dimethyl formamide was then removed by evaporation under reduced pressure and the residue was dissolved in 300 mL of ethyl acetate. This was washed with water (3×50 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residual solid was purified by column chromatography on silica gel, eluting with 7:3 hexane:ethyl acetate to give 13.3 g (98%) of 3-(4-ethoxycarbonylphenyl)-1-propanal as a light yellow oil. 1H NMR (CDCl3) δ 10.02 (1H, s), 8.18 (2H, d, J=7.3 Hz), 7 47 (2H, d, J=7.3 Hz), 4.56 (2H, q, J=6.5 Hz), 3,21 (2H, t, J=6.5 Hz), 3.02 (2H, t, J=6.5 Hz), 1,59 (3H, t, J=6.5 Hz), Taylor, E. C. et al., J. Org. Chem., 57, 3218 (1992); J. Org. Chem., 60, 6684 (1995).

Workup

  1. customThe dimethyl formamide was then removed by evaporation under reduced pressure
  2. dissolutionthe residue was dissolved in 300 mL of ethyl acetate
  3. washThis was washed with water (3×50 mL)
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe residual solid was purified by column chromatography on silica gel
  7. washeluting with 7:3 hexane

Sources & evidence

ORD record
ord-b306a315b8fa4dd1beb39accb8822bc8
Source dataset
uspto-grants-2000_05
Patent number
US06066732

Reaction notes

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