Acetic Acid → 4-(Acetyloxy)-2-[(3-nitrophenyl)methylene]-3-oxobutanoic acid, ethyl ester

HRID 1029806Notes

Reaction equation

HRID 1029806 reaction equation
[C:1]([O:4][CH2:5][C:6](=[O:13])[CH2:7][C:8]([O:10][CH2:11][CH3:12])=[O:9])(=[O:3])[CH3:2].[N+:14]([C:17]1[CH:18]=[C:19]([CH:22]=[CH:23][CH:24]=1)[CH:20]=O)([O-:16])=[O:15].CC(O)=O.N1CCCCC1>C1C=CC=CC=1.CCOCC.CCCCCC>[C:1]([O:4][CH2:5][C:6](=[O:13])[C:7](=[CH:20][C:19]1[CH:22]=[CH:23][CH:24]=[C:17]([N+:14]([O-:16])=[O:15])[CH:18]=1)[C:8]([O:10][CH2:11][CH3:12])=[O:9])(=[O:3])[CH3:2]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 74493-NitrobenzaldehydeHCID 8082PiperidineHCID 11480907Ethyl 4-acetoxyacetoacetate

Product 1

HCID 539714314-(Acetyloxy)-2-[(3-nitrophenyl)methylene]-3-oxobutanoic acid, ethyl ester

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 21584099Diethylether hexaneSolvent

Procedure

A solution of ethyl 4-acetoxyacetoacetate (23.0 g, 0.122 mole, Tet., 28, 967 (1972)) and 3-nitrobenzaldehyde (18.47 g, 0.122 mole) in 125 ml of benzene was treated with HOAc (0.6 ml) and piperidine (0.6 ml) and heated at reflux temperature. Collection of water ceased after 0.5 hour; therefore, additional HOAc (1 ml) and piperidine (1 ml) were added and refluxing continued. A total of 2.0 ml water was collected. The cooled mixture was washed with water (2x) and saturated brine, dried over anhydrous magnesium sulfate, treated with Darco to remove color and concentrated in vacuo to give an oil that solidified on standing. Trituration with IPE/Et2O/Hexane and stirring overnight to pulverize the solids afforded 24.2 g of the title

Workup

  1. temperatureheated
  2. temperatureat reflux temperature
  3. customCollection of water
  4. additiontherefore, additional HOAc (1 ml) and piperidine (1 ml) were added
  5. temperaturerefluxing
  6. customA total of 2.0 ml water was collected
  7. washThe cooled mixture was washed with water (2x) and saturated brine
  8. dry with materialdried over anhydrous magnesium sulfate
  9. additiontreated with Darco
  10. customto remove color
  11. concentrationconcentrated in vacuo
  12. customto give an oil that
  13. customafforded 24.2 g of the title

Sources & evidence

ORD record
ord-15737b46f45049a7b1529d268356b374
Source dataset
uspto-grants-1992_04
Patent number
US05103006

Reaction notes

Loading…