p-Anisoyl chloride → Benzenepropanoic acid, 4-methoxy-beta-oxo-, ethyl ester

HRID 1195799Notes

Reaction equation

HRID 1195799 reaction equation
[C:1]([O:7][CH2:8][CH3:9])(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4].[OH-].[Na+].[CH3:12][O:13][C:14]1[CH:22]=[CH:21]C(C(Cl)=O)=[CH:16][CH:15]=1.[NH4+].[Cl-]>O>[CH3:12][O:13][C:14]1[CH:22]=[CH:21][C:5]([C:3]([CH2:2][C:1]([O:7][CH2:8][CH3:9])=[O:6])=[O:4])=[CH:16][CH:15]=1

Participants

6

Reactant 4

HCID 7477p-Anisoyl chlorideHCID 8868Ethyl AcetoacetateHCID 14798Sodium Hydroxide2×HCID 25517Ammonium Chloride

Product 1

HCID 76150Benzenepropanoic acid, 4-methoxy-beta-oxo-, ethyl ester

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
5 °C

Procedure

To a liquid mixture consisting of 25 ml of solvent naphtha and 50 ml of water, 19.5 g (0.15 mol) of ethyl acetoacetate were added, followed by cooling to 5° C. A 33% aqueous sodium hydroxide solution (6.5 ml) was added to the resultant liquid mixture, followed by vigorous agitation. A 33% aqueous sodium hydroxide solution (27 ml) and 27.6 g (0.16 mol) of 4-methoxybenzoyl chloride were simultaneously added in small portions over 30 minutes, whereby they were reacted while the internal temperature and pH were maintained below about 10° C. and at about 11, respectively. After completion of the dropwise addition, the reaction mixture was stirred at room temperature for 2.5 hours to allow the reaction to proceed further. After completion of the reaction, 8 g (0.15 mol) of NH4Cl were added further and the resulting mixture was allowed to stand overnight. An oil thus formed was extracted with ethyl acetate. The organic layer was washed with water and then dried. The solvent was distilled off and the residue was purified by silica gel column chromatography (solvent: hexane/ethyl acetate=5/1), whereby the title compound was obtained as a colorless oil. Yield: 16.1 g (48%)

Workup

  1. additionwere added
  2. customwhereby they were reacted while the internal temperature
  3. temperaturepH were maintained below about 10° C. and at about 11
  4. additionAfter completion of the dropwise addition
  5. customthe reaction
  6. additionwere added further
  7. waitto stand overnight
  8. customAn oil thus formed
  9. extractionwas extracted with ethyl acetate
  10. washThe organic layer was washed with water
  11. customdried
  12. distillationThe solvent was distilled off
  13. customthe residue was purified by silica gel column chromatography (solvent: hexane/ethyl acetate=5/1), whereby the title compound
  14. customwas obtained as a colorless oil

Sources & evidence

ORD record
ord-0adbf21947474ce89e9ee0c32ff04ecd
Source dataset
uspto-grants-1992_05
Patent number
US05112841

Reaction notes

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