4-Nitrobenzyl chloride → Diethyl benzyl-4-nitrobenzylmalonate

HRID 1683944Notes

Reaction equation

HRID 1683944 reaction equation
[N+:1]([C:4]1[CH:11]=[CH:10][C:7]([CH2:8]Cl)=[CH:6][CH:5]=1)([O-:3])=[O:2].[CH2:12]([CH:19]([C:25]([O:27][CH2:28][CH3:29])=[O:26])[C:20]([O:22][CH2:23][CH3:24])=[O:21])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.[H-].[Na+]>CN(C)C=O>[CH2:12]([C:19]([CH2:8][C:7]1[CH:10]=[CH:11][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=1)([C:20]([O:22][CH2:23][CH3:24])=[O:21])[C:25]([O:27][CH2:28][CH3:29])=[O:26])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

5

Reactant 3

HCID 74824-Nitrobenzyl chlorideHCID 24758Sodium hydrideHCID 69090Diethyl 2-benzylpropanedioate

Product 1

HCID 53932722Diethyl benzyl-4-nitrobenzylmalonateYield 71.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a stirred solution of p-nitrobenzyl chloride (15 g) and diethyl benzylmalonate (22 g) in N,N-dimethylformamide (150 ml) was added NaH (60% in oil, 3.8 g). After stirring at room temperature for 2 days, the reaction mixture was concentrated under reduced pressure and the residue was suspended in ethyl acetate. The ethyl acetate layer was washed with aqueous citric acid solution, water, saturated aqueous sodium hydrogen carbonate solution and brine, and dried (MgSO4). The organic solvent was evaporated off and the residual oil was purified by column chromatography on silica gel. Elution with ethyl acetate-hexane (1:6, v/v) gave diethyl benzyl-4-nitrobenzylmalonate (24 g, 71%) as crystals. Melting point: 70°-71° C.

Workup

  1. concentrationthe reaction mixture was concentrated under reduced pressure
  2. washThe ethyl acetate layer was washed with aqueous citric acid solution, water, saturated aqueous sodium hydrogen carbonate solution and brine
  3. dry with materialdried (MgSO4)
  4. customThe organic solvent was evaporated off
  5. customthe residual oil was purified by column chromatography on silica gel
  6. washElution with ethyl acetate-hexane (1:6, v/v)

Sources & evidence

ORD record
ord-e7f4e3027832487ba445de718ebfc921
Source dataset
uspto-grants-1997_06
Patent number
US05639781

Reaction notes

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