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

HRID 657147Notes

Reaction equation

HRID 657147 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 was dissolved in anhydrous THF (1 mL) and then added dropwise over 30 minutes to the dimethyl malonate solution. The reaction was stirred at ambient temperature for 16 h and then concentrated under vacuum. The residue was dissolved in EtOAc (ethyl acetate) and 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 as a colorless oil (1.68 g, 77%).

Workup

  1. stirringThe reaction was stirred at ambient temperature for 16 h
  2. concentrationconcentrated under vacuum
  3. dissolutionThe residue was dissolved in EtOAc (ethyl acetate)
  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-2432b503cfb147de8d9feaf94ac5b125
Source dataset
uspto-grants-2011_12
Patent number
US08071592B2

Reaction notes

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