Diethyl Carbonate → Diethyl 3,4-difluorophenylmalonate

HRID 71108Notes

Reaction equation

HRID 71108 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11])[CH:5]=[CH:6][C:7]=1[F:8].[H-].[Na+].[C:17](=O)([O:21]CC)[O:18][CH2:19][CH3:20].[Cl-].[NH4+]>C1COCC1>[F:1][C:2]1[CH:3]=[C:4]([CH:9]([C:17]([O:18][CH2:19][CH3:20])=[O:21])[C:10]([O:12][CH2:13][CH3:14])=[O:11])[CH:5]=[CH:6][C:7]=1[F:8]

Participants

6

Reactant 4

HCID 7766Diethyl CarbonateHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 11241070Ethyl 2-(3,4-difluorophenyl)acetate

Product 1

HCID 19767513Diethyl 3,4-difluorophenylmalonate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A mixture of ethyl (3,4-difluorophenyl)acetate (11.3 g) in THF (50 mL) was added to a mixture of sodium hydride (60%, 4.74 g), diethyl carbonate (34.2 mL) and THF (250 mL) at room temperature, and the mixture was heated under reflux for 2 hr. Saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate/hexane) to give the title compound (13.8 g).

Workup

  1. temperaturethe mixture was heated
  2. temperatureunder reflux for 2 hr
  3. extractionthe mixture was extracted with ethyl acetate
  4. washThe extract was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. customthe solvent was evaporated under reduced pressure
  7. customThe residue was purified by silica gel column chromatography (ethyl acetate/hexane)

Sources & evidence

ORD record
ord-31168b16870c43aa83c1fbe5803277a9
Source dataset
uspto-grants-2014_09
Patent number
US08822699B2

Reaction notes

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