Formic Acid → Methyl 4-(2-carboxy-6-cyanohexyl)benzoate

HRID 1672699Notes

Reaction equation

HRID 1672699 reaction equation
C(N(CC)CC)C.C(O)=O.[C:11]([CH2:13][CH2:14][CH2:15][CH2:16][C:17]([CH2:30][C:31]1[CH:36]=[CH:35][C:34]([C:37]([O:39][CH3:40])=[O:38])=[CH:33][CH:32]=1)(C(OCC=C)=O)[C:18]([O:20]CC=C)=[O:19])#[N:12]>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:18]([CH:17]([CH2:16][CH2:15][CH2:14][CH2:13][C:11]#[N:12])[CH2:30][C:31]1[CH:36]=[CH:35][C:34]([C:37]([O:39][CH3:40])=[O:38])=[CH:33][CH:32]=1)([OH:20])=[O:19]

Participants

7

Reactant 3

HCID 284Formic AcidHCID 8471TriethylamineHCID 57864376Diallyl 2-(4-cyanobutyl)-2-(4-methoxycarbonylbenzyl)malonate

Product 1

HCID 57864409Methyl 4-(2-carboxy-6-cyanohexyl)benzoateYield 74.7%

Reagents, catalysts & solvents 3

HCID 11776TriphenylphosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
10 °C

Procedure

17.24 ml (123.71 mmol) of triethylamine and 4.24 ml (112.46 mmol) of formic acid in 500 ml of dioxane is added to a solution of 15.5 g (37.49 mmol) of diallyl 2-(4-cyanobutyl)-2-(4 methoxycarbonylbenzyl)malonate from Example 115A, 690 mg (2.62 mmol) of triphenylphosphine and 170 mg (0.75 mmol) of palladium acetate in 500 ml of dioxane at room temperature. The reaction mixture is then stirred at 10° C. for 12 hours. After conversion is complete, the reaction solution is cooled and the solvent is removed in vacuo. The residue is then 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 then the organic phases are combined, washed with saturated sodium chloride solution and dried over sodium sulfate. After filtration, the solution is concentrated in vacuo. 8.1 g (74% yield) of a colorless 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 sodium chloride solution
  6. dry with materialdried over sodium sulfate
  7. filtrationAfter filtration
  8. concentrationthe solution is concentrated in vacuo

Sources & evidence

ORD record
ord-209ab002386c428487b26a9f6539d930
Source dataset
uspto-grants-2011_08
Patent number
US07998988B2

Reaction notes

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