Diethyl Malonate → Diethyl 2-(2-nitrobenzylidene)malonate

HRID 2194502Notes

Reaction equation

HRID 2194502 reaction equation
[N+:1]([C:4]1[CH:11]=[CH:10][CH:9]=[CH:8][C:5]=1[CH:6]=O)([O-:3])=[O:2].[C:12]([O:20][CH2:21][CH3:22])(=[O:19])[CH2:13][C:14]([O:16][CH2:17][CH3:18])=[O:15].C(=O)([O-])O.[Na+]>C(OC(=O)C)(=O)C>[N+:1]([C:4]1[CH:11]=[CH:10][CH:9]=[CH:8][C:5]=1[CH:6]=[C:13]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[C:12]([O:20][CH2:21][CH3:22])=[O:19])([O-:3])=[O:2]

Participants

5

Reactant 3

HCID 7761Diethyl MalonateHCID 111012-NitrobenzaldehydeHCID 516892Sodium Bicarbonate

Product 1

HCID 231460Diethyl 2-(2-nitrobenzylidene)malonateYield 60.1%

Reagents, catalysts & solvents 1

HCID 7918Acetic AnhydrideSolvent

Procedure

32.3 g (0.21 mol) of 2-nitrobenzaldehyde and 35.0 g (0.21 mol) of diethyl malonate were added to 100 mL of acetic anhydride at room temperature. 27.0 g (0.32 mol) of sodium hydrogen carbonate was added to this mixture, and the resulting mixture was allowed to react overnight at 100° C. The reaction mixture was concentrated under reduced pressure to approximately a half of the original volume, and ice water was added to this reaction mixture. The reaction mixture was extracted with ethyl acetate. The organic phase was washed with an aqueous solution of sodium hydrogen carbonate and water in this order, and was dried and concentrated under reduced pressure. The residue was purified by column chromatography (ethyl acetate:n-hexane=1:9 to 1:4), and thus 37.0 g (yield: 59%) of the title compound was obtained as light yellow crystals.

Workup

  1. customto react overnight at 100° C
  2. concentrationThe reaction mixture was concentrated under reduced pressure to approximately a half of the original volume, and ice water
  3. additionwas added to this reaction mixture
  4. extractionThe reaction mixture was extracted with ethyl acetate
  5. washThe organic phase was washed with an aqueous solution of sodium hydrogen carbonate and water in this order
  6. customwas dried
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by column chromatography (ethyl acetate:n-hexane=1:9 to 1:4)

Sources & evidence

ORD record
ord-f9027566b52444b29a7ce744c83be2e9
Source dataset
uspto-grants-2012_12
Patent number
US08334236B2

Reaction notes

Loading…