Methanol → Dimethyl (4-methoxy-2-nitrophenyl)methylidenemalonate

HRID 2269723Notes

Reaction equation

HRID 2269723 reaction equation
CO.[CH3:3][O:4][C:5]1[CH:12]=[CH:11][C:8]([CH:9]=O)=[C:7]([N+:13]([O-:15])=[O:14])[CH:6]=1.[C:16]([O:23][CH3:24])(=[O:22])[CH2:17][C:18]([O:20][CH3:21])=[O:19].N1CCCCC1>C(O)(=O)C>[CH3:3][O:4][C:5]1[CH:12]=[CH:11][C:8]([CH:9]=[C:17]([C:16]([O:23][CH3:24])=[O:22])[C:18]([O:20][CH3:21])=[O:19])=[C:7]([N+:13]([O-:15])=[O:14])[CH:6]=1

Participants

6

Reactant 4

HCID 887MethanolHCID 7943Dimethyl malonateHCID 8082PiperidineHCID 3576914-Methoxy-2-nitrobenzaldehyde

Product 1

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

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

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

Workup

  1. temperatureunder reflux for 24 hours
  2. concentrationThe reaction mixture was concentrated, to which
  3. additionwas added 1N hydrochloride
  4. extractionthe mixture was extracted with ethyl acetate
  5. washThe organic layer was washed with 10% aqueous potassium carbonate solution
  6. dry with materiala saturated aqueous sodium chloride solution, then dried
  7. concentrationconcentrated
  8. customThe residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/2)

Sources & evidence

ORD record
ord-b3404023938c4442b38cfb9226c75108
Source dataset
uspto-grants-2001_12
Patent number
US06329389B1

Reaction notes

Loading…