Dimethyl malonate → Dimethyl bis-(3,4-methylenedioxyphenylmethyl)-malonate

HRID 976040Notes

Reaction equation

HRID 976040 reaction equation
[H-].[Na+].[C:3]([O:10][CH3:11])(=[O:9])[CH2:4][C:5]([O:7][CH3:8])=[O:6].[CH2:12]1[O:22][C:21]2[CH:20]=[CH:19][C:16]([CH2:17]Cl)=[CH:15][C:14]=2[O:13]1>C1COCC1>[CH2:12]1[O:22][C:21]2[CH:20]=[CH:19][C:16]([CH2:17][C:4]([CH2:17][C:16]3[CH:19]=[CH:20][C:21]4[O:22][CH2:12][O:13][C:14]=4[CH:15]=3)([C:3]([O:10][CH3:11])=[O:9])[C:5]([O:7][CH3:8])=[O:6])=[CH:15][C:14]=2[O:13]1

Participants

5

Reactant 3

HCID 7943Dimethyl malonateHCID 24758Sodium hydrideHCID 887131,3-Benzodioxole, 5-(chloromethyl)-

Product 1

HCID 19968591Dimethyl bis-(3,4-methylenedioxyphenylmethyl)-malonateYield 68.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A suspension of 6.6 g (0.165 mol) of NaH.oil (60%) in 200 mL THF was cooled in ice and treated dropwise with 10 g (0.075 mol) of dimethyl malonate. After stirring for 0.5 hour, the solution was treated with a solution of 27.3 g (0.16 mol) of 3,4-methylenedioxybenzyl chloride (50% in CH2Cl2). After stirring at room temperature overnight, the solution was heated at reflux overnight. The mixture was filtered and the solvent removed under reduced pressure. The residue was taken up in EtOAc and washed with 1N HCl, then saturated NaCl. Drying over MgSO4 and removal of the solvent under reduced pressure gave the crude product. Recrystallization from EtOAc/hexane gave 20.58 g (68.6% yield) of the product as a solid. The structure was confirmed by NMR spectroscopy.

Workup

  1. stirringAfter stirring at room temperature overnight
  2. temperaturethe solution was heated
  3. temperatureat reflux overnight
  4. filtrationThe mixture was filtered
  5. customthe solvent removed under reduced pressure
  6. washwashed with 1N HCl
  7. dry with materialDrying over MgSO4 and removal of the solvent under reduced pressure
  8. customgave the crude product
  9. customRecrystallization from EtOAc/hexane

Sources & evidence

ORD record
ord-5187dca1ff464b14b59773ad9c23aa7e
Source dataset
uspto-grants-1997_03
Patent number
US05610177

Reaction notes

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