Ethyl Acetoacetate → HCID 69205750, compound

HRID 30620Notes

Reaction equation

HRID 30620 reaction equation
[F:1][C:2]1[CH:12]=[CH:11][C:5]([C:6]([N:8]([CH3:10])[NH2:9])=O)=[CH:4][CH:3]=1.[C:13]([O:19][CH2:20][CH3:21])(=[O:18])[CH2:14][C:15]([CH3:17])=O>C(O)C>[F:1][C:2]1[CH:12]=[CH:11][C:5]([C:6]2[N:8]([CH3:10])[N:9]=[C:15]([CH3:17])[C:14]=2[C:13]([O:19][CH2:20][CH3:21])=[O:18])=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 8868Ethyl AcetoacetateHCID 450757084-Fluorobenzoic acid N-methylhydrazide

Product 1

HCID 69205750HCID 69205750, compoundYield 44%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A mixture of 4-fluoro-N-methylbenzohydrazide (5.0 g), ethyl acetoacetate (4.84 g) and ethanol (140 ml) was stirred for 14 hrs. with heating under reflux. The reaction mixture was concentrated, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to give an oil from a fraction eluted with hexane-ethyl acetate (4:1-1:1, v/v). This oil was dissolved in ethanol (50 ml), 1,8-diazabicyclo[5.4.0]-7-undecene (0.5 ml) was added, and the mixture was stirred for 4 hrs. with heating under reflux. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate and concentrated to give ethyl 5-(4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-4-carboxylate (3.41 g, yield 44%) as colorless crystals.

Workup

  1. temperaturewith heating
  2. temperatureunder reflux
  3. concentrationThe reaction mixture was concentrated
  4. additionwater was added
  5. extractionthe mixture was extracted with ethyl acetate
  6. washThe organic layer was washed with water
  7. dry with materialdried over anhydrous magnesium sulfate
  8. concentrationconcentrated
  9. customto give an oil from a fraction
  10. washeluted with hexane-ethyl acetate (4:1-1:1
  11. dissolutionThis oil was dissolved in ethanol (50 ml)
  12. addition1,8-diazabicyclo[5.4.0]-7-undecene (0.5 ml) was added
  13. stirringthe mixture was stirred for 4 hrs
  14. temperaturewith heating
  15. temperatureunder reflux
  16. additionWater was added to the reaction mixture
  17. extractionthe mixture was extracted with ethyl acetate
  18. washThe organic layer was washed with water
  19. dry with materialdried over anhydrous magnesium sulfate
  20. concentrationconcentrated

Sources & evidence

ORD record
ord-5dd5c739e64f4e12a9259ec84e2ff7af
Source dataset
uspto-grants-2008_09
Patent number
US07423159B2

Reaction notes

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