Acetic Acid → Dimethyl (4-methoxy-2-nitrophenyl)methylidenemalonate

HRID 854032

Reaction equation

HRID 854032 reaction equation
[CH3:1][O:2][C:3]1[CH:10]=[CH:9][C:6]([CH:7]=O)=[C:5]([N+:11]([O-:13])=[O:12])[CH:4]=1.[C:14]([O:21][CH3:22])(=[O:20])[CH2:15][C:16]([O:18][CH3:19])=[O:17].N1CCCCC1.C(O)(=O)C>CO>[CH3:1][O:2][C:3]1[CH:10]=[CH:9][C:6]([CH:7]=[C:15]([C:14]([O:21][CH3:22])=[O:20])[C:16]([O:18][CH3:19])=[O:17])=[C:5]([N+:11]([O-:13])=[O:12])[CH:4]=1

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 7943Dimethyl malonateHCID 8082PiperidineHCID 3576914-Methoxy-2-nitrobenzaldehyde

Product 1

HCID 54325413Dimethyl (4-methoxy-2-nitrophenyl)methylidenemalonateYield 72%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A mixture of 4-methoxy-2-nitrobenzaldehyde (21.3 g, Org. Synth., Vol. V, p-139, 1973), dimethyl malonate (16.5 g), piperidine (2.5 ml), and acetic acid (0.25 ml) in methanol (125 ml) was heated under reflux for 24 hr. The reaction mixture was concentrated, diluted with 1 N aqueous hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with 10% aqueous potassium carbonate and saturated aqueous sodium chloride, dried, and concentrated. The residue was purified by silica gel column chromatography (eluent:ethyl acetate:hexane=1:2) to obtain the titled compound (25 g).

Workup

  1. temperaturewas heated
  2. temperatureunder reflux for 24 hr
  3. concentrationThe reaction mixture was concentrated
  4. additiondiluted with 1 N aqueous hydrochloric acid
  5. extractionextracted with ethyl acetate
  6. washThe organic layer was washed with 10% aqueous potassium carbonate and saturated aqueous sodium chloride
  7. customdried
  8. concentrationconcentrated
  9. customThe residue was purified by silica gel column chromatography (eluent:ethyl acetate:hexane=1:2)

Sources & evidence

ORD record
ord-7d47fd831cff477c9378c9ecd6969386
Source dataset
uspto-grants-2007_08
Patent number
US07256204B2

Linked notes

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