Formic Acid → 4-[4-(Methoxycarbonyl)phenyl]-2-{2-[4-(methoxycarbonyl)phenyl]ethyl}butanoic acid

HRID 1015929Notes

Reaction equation

HRID 1015929 reaction equation
C(N(CC)CC)C.C(O)=O.[CH3:11][O:12][C:13]([C:15]1[CH:20]=[CH:19][C:18]([CH2:21][CH2:22][C:23]([CH2:36][CH2:37][C:38]2[CH:43]=[CH:42][C:41]([C:44]([O:46][CH3:47])=[O:45])=[CH:40][CH:39]=2)(C(OCC=C)=O)[C:24]([O:26]CC=C)=[O:25])=[CH:17][CH:16]=1)=[O:14].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCOCC1.O.C(OCC)(=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:47][O:46][C:44]([C:41]1[CH:40]=[CH:39][C:38]([CH2:37][CH2:36][CH:23]([CH2:22][CH2:21][C:18]2[CH:17]=[CH:16][C:15]([C:13]([O:12][CH3:11])=[O:14])=[CH:20][CH:19]=2)[C:24]([OH:26])=[O:25])=[CH:43][CH:42]=1)=[O:45]

Participants

9

Reactant 4

HCID 284Formic AcidHCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 59397503Diallyl bis{2-[4-(methoxycarbonyl)phenyl]ethyl}malonate

Product 1

HCID 593974954-[4-(Methoxycarbonyl)phenyl]-2-{2-[4-(methoxycarbonyl)phenyl]ethyl}butanoic acid

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
100 °C

Procedure

At room temperature, a solution of 20.48 ml (146.9 mmol) of triethylamine and 4.2 ml (111.29 mmol) of formic acid in 50 ml of dioxane is added to a solution of 22.64 g (44.52 mmol) of diallyl bis{2-[4-(methoxycarbonyl)phenyl]ethyl}malonate, 0.82 g (3.12 mmol) of triphenylphosphine and 200 mg of palladium acetate in 250 ml of dioxane. The reaction mixture is then stirred at 100° C. overnight. After the reaction has gone to completion, the reaction solution is cooled and the solvent is removed under reduced pressure. The residue obtained is taken up in water and ethyl acetate. The aqueous phase is extracted three times with ethyl acetate, and the combined organic phases are washed with saturated sodium chloride solution and dried over magnesium sulfate. After filtration, the solvent is removed under reduced pressure and the residue is purified by flash chromatography on silica gel (mobile phase: cyclohexane/ethyl acetate 4:1). This gives 10.4 g (27.1 mmol, 61% of theory) of a colorless solid.

Workup

  1. temperaturethe reaction solution is cooled
  2. customthe solvent is removed under reduced pressure
  3. customThe residue obtained
  4. extractionThe aqueous phase is extracted three times with ethyl acetate
  5. washthe combined organic phases are washed with saturated sodium chloride solution
  6. dry with materialdried over magnesium sulfate
  7. filtrationAfter filtration
  8. customthe solvent is removed under reduced pressure
  9. customthe residue is purified by flash chromatography on silica gel (mobile phase: cyclohexane/ethyl acetate 4:1)

Sources & evidence

ORD record
ord-aefdf7acbfdc4f13bcb4fd9d170d2d4e
Source dataset
uspto-grants-2011_07
Patent number
US07985876B2

Reaction notes

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