Formic Acid → Methyl 4-[3-carboxy-4-(4-cyanophenyl)butyl]benzoate

HRID 1913783Notes

Reaction equation

HRID 1913783 reaction equation
[C:1]([C:3]1[CH:34]=[CH:33][C:6]([CH2:7][C:8]([CH2:21][CH2:22][C:23]2[CH:28]=[CH:27][C:26]([C:29]([O:31][CH3:32])=[O:30])=[CH:25][CH:24]=2)(C(OCC=C)=O)[C:9]([O:11]CC=C)=[O:10])=[CH:5][CH:4]=1)#[N:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C.C(O)=O>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:9]([CH:8]([CH2:7][C:6]1[CH:5]=[CH:4][C:3]([C:1]#[N:2])=[CH:34][CH:33]=1)[CH2:21][CH2:22][C:23]1[CH:28]=[CH:27][C:26]([C:29]([O:31][CH3:32])=[O:30])=[CH:25][CH:24]=1)([OH:11])=[O:10]

Participants

7

Reactant 4

HCID 284Formic AcidHCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 57831378Diallyl 2-(4-cyanobenzyl)-2-[2-(4-methoxycarbonylphenyl)ethyl]malonate

Product 1

HCID 57831382Methyl 4-[3-carboxy-4-(4-cyanophenyl)butyl]benzoate

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
100 °C

Procedure

A solution of 7.5 g (16.25 mmol) of diallyl 2-(4-cyanobenzyl)-2-[2-(4-methoxycarbonylphenyl)ethyl]malonate from Example 46A, 0.3 g (1.14 mmol) of triphenylphosphine and 70 mg of palladium acetate in 170 ml of dioxane is mixed at room temperature with a solution of 7.47 ml (53.63 mmol) of triethylamine and 1.53 ml (40.63 mmol) of formic acid in 170 ml of dioxane. The reaction mixture is then stirred at 100° C. for 2 h. After conversion is complete, the reaction solution is cooled and the solvent is removed in vacuo. The residue is taken up in ethyl acetate and water and acidified with 1 N hydrochloric acid, and the organic phase is separated off. The aqueous phase is extracted three times more with ethyl acetate, and the organic phases are subsequently combined, washed with saturated brine and dried over sodium sulphate. After filtration, the solution is evaporated in vacuo. 5.48 g (89% of theory, 90% purity) of a colourless solid are obtained.

Workup

  1. temperaturethe reaction solution is cooled
  2. customthe solvent is removed in vacuo
  3. customthe organic phase is separated off
  4. extractionThe aqueous phase is extracted three times more with ethyl acetate
  5. washwashed with saturated brine
  6. dry with materialdried over sodium sulphate
  7. filtrationAfter filtration
  8. customthe solution is evaporated in vacuo
  9. custom5.48 g (89% of theory, 90% purity) of a colourless solid are obtained

Sources & evidence

ORD record
ord-96ca885e457644af93d871a16d85e098
Source dataset
uspto-grants-2013_12
Patent number
US08609727B2

Reaction notes

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