Malonic Acid → 3-(4-Methoxy-2-nitrophenyl)prop-2-enoic acid

HRID 1914694Notes

Reaction equation

HRID 1914694 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(O)(=O)[CH2:15][C:16]([OH:18])=[O:17].N1CCCCC1>N1C=CC=CC=1>[CH3:1][O:2][C:3]1[CH:10]=[CH:9][C:6](/[CH:7]=[CH:15]/[C:16]([OH:18])=[O:17])=[C:5]([N+:11]([O-:13])=[O:12])[CH:4]=1

Participants

5

Reactant 3

HCID 867Malonic AcidHCID 8082PiperidineHCID 3576914-Methoxy-2-nitrobenzaldehyde

Product 1

HCID 241789753-(4-Methoxy-2-nitrophenyl)prop-2-enoic acidYield 65.2%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Conditions

Temperature
125 °C

Procedure

To a mixture of 4-methoxy-2-nitrobenzaldehyde (20 g, 0.11 mol) and malonic acid (28.8 g, 0.28 mol) in pyridine (200 mL) is added piperidine (1 mL, catalytic amount) and the mixture is refluxed at 125° C. under nitrogen for 12 h. After cooling to room temperature, the solvent is removed under reduced pressure and the residue is acidified with 1.5 N HCl. The product is extracted with EtOAc and the organic layer is washed with water and brine then dried over Na2SO4. The solvent is removed under reduced pressure to afford 16 g (65%) of the title compound as a pale brown solid. 1H NMR (DMSO-d6, 400 MHz) δ 12.59 (bs, 1H), 7.91-7.93 (m, 1H), 7.68-7.72 (m, 1H), 7.56 (s, 1H), 7.31-7.33 (m, 1H), 7.46-7.50 (m, 1H), 3.87 (s, 3H).

Workup

  1. temperatureAfter cooling to room temperature
  2. customthe solvent is removed under reduced pressure
  3. extractionThe product is extracted with EtOAc
  4. washthe organic layer is washed with water and brine
  5. dry with materialthen dried over Na2SO4
  6. customThe solvent is removed under reduced pressure

Sources & evidence

ORD record
ord-315012fc6e5c405ab69ae3c513dfde0a
Source dataset
uspto-grants-2013_12
Patent number
US08614215B2

Reaction notes

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