Pivalic anhydride → 3-(3-Hydroxy-4-methoxyphenyl)prop-2-enal

HRID 1007621

Reaction equation

HRID 1007621 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([CH:10]=[CH:11][C:12]=1[O:13][CH3:14])[CH:5]=[CH:6][C:7](O)=[O:8].C(OC(=O)C(C)(C)C)(=O)C(C)(C)C.[H][H]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(C)C=CC(P(C2C=CC(C)=CC=2)C2C=CC(C)=CC=2)=CC=1>[OH:1][C:2]1[CH:3]=[C:4]([CH:10]=[CH:11][C:12]=1[O:13][CH3:14])[CH:5]=[CH:6][CH:7]=[O:8]

Participants

6

Reactant 3

HCID 15234Pivalic anhydrideHCID 921263-(3-Hydroxy-4-methoxyphenyl)prop-2-enoic acidHCID 178418361HCID 178418361, compound2×

Product 1

HCID 540251573-(3-Hydroxy-4-methoxyphenyl)prop-2-enalYield 49.4%

Reagents, catalysts & solvents 2

HCID 13956Phosphine, tris(4-methylphenyl)-CatalystHCID 167845palladium(II) acetateCatalyst

Conditions

Temperature
80 °C

Procedure

Palladium acetate (58 mg, 0.257 mmol), tri(p-tolyl) phosphine (157 mg, 0.515 mmol), 3-hydroxy-4-methoxycinnamic acid (5.00 g, 25.7 mmol) and pivalic acid anhydride (14.4 g, 77.2 mmol) were added thereto, and thereafter the mixture was bubbled with nitrogen gas for 30 minutes to substitute nitrogen gas completely for the gas in the system of reaction, whereby the system was filled with nitrogen gas. Next, hydrogen gas was added thereinto to substitute hydrogen gas for the gas in the system, and then the mixture was stirred under hydrogen pressure of 3.4 MPa at 80° C. for 24 hours for reaction. Thus obtained reaction solution was concentrated under reduced pressure to remove tetrahydrofuran by vaporization. The remaining residue was subjected to a purification process with a silica gel column chromatography (eluting solvent: toluene/ethyl acetate=4/1) to obtain 3-hydroxy-4-methoxycinnamaldehyde (2.26 g, 12.7 mmol, yield: 49%).

Workup

  1. customthe mixture was bubbled with nitrogen gas for 30 minutes
  2. customin the system of reaction, whereby the system
  3. additionwas filled with nitrogen gas
  4. customfor reaction
  5. customThus obtained reaction solution
  6. concentrationwas concentrated under reduced pressure
  7. customto remove tetrahydrofuran by vaporization
  8. washThe remaining residue was subjected to a purification process with a silica gel column chromatography (eluting solvent: toluene/ethyl acetate=4/1)

Sources & evidence

ORD record
ord-5fbb8291ec95476a9ec895955de679cc
Source dataset
uspto-grants-2004_09
Patent number
US06794531B2

Linked notes

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