Dimethyl malonate → 3-Ethyl 1,1-dimethyl 1,1,3-propanetricarboxylate

HRID 657105Notes

Reaction equation

HRID 657105 reaction equation
[C:1]([O:8][CH3:9])(=[O:7])[CH2:2][C:3]([O:5][CH3:6])=[O:4].[H-].[Na+].[C:12]([O:16][CH2:17][CH3:18])(=[O:15])[CH:13]=[CH2:14]>C1COCC1>[CH:2]([C:1]([O:8][CH3:9])=[O:7])([C:3]([O:5][CH3:6])=[O:4])[CH2:14][CH2:13][C:12]([O:16][CH2:17][CH3:18])=[O:15]

Participants

5

Reactant 3

HCID 7943Dimethyl malonate2×HCID 8821Ethyl AcrylateHCID 24758Sodium hydride

Product 1

HCID 130424803-Ethyl 1,1-dimethyl 1,1,3-propanetricarboxylateYield 77%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of dimethyl malonate (2.5 g, 18.9 mmol) in anhydrous THF (20 mL) was added NaH (0.038 g, 0.95 mmol, 60% in mineral oil). The reaction was stirred at ambient temperature for 15 minutes. In a separate flask, ethyl acrylate (1.02 mL, 9.45 mmol) was dissolved in anhydro is THF (1 mL) and then added dropwise over 30 minutes to the dimethyl malonate solution. The reaction was stirred at ambient temperature overnight and then concentrated under vacuum. The residue was dissolved in EtOAc, washed with saturated NH4Cl solution and brine. The organic phase was dried over Na2SO4, filtered, and concentrated under vacuum. The crude residue was purified by column chromatography (silica gel) using an EtOAc/hexanes gradient to yield the desired compound (1.68 g, 77%).

Workup

  1. stirringThe reaction was stirred at ambient temperature overnight
  2. concentrationconcentrated under vacuum
  3. dissolutionThe residue was dissolved in EtOAc
  4. washwashed with saturated NH4Cl solution and brine
  5. dry with materialThe organic phase was dried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated under vacuum
  8. customThe crude residue was purified by column chromatography (silica gel)

Sources & evidence

ORD record
ord-70be9b4623ea41b8b4daec88fc2aee1d
Source dataset
uspto-grants-2011_12
Patent number
US08071592B2

Reaction notes

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