Ethyl Acetoacetate → HCID 68426811, compound

HRID 642254Notes

Reaction equation

HRID 642254 reaction equation
[CH3:1][C:2]([CH3:9])([CH3:8])[CH:3]=[CH:4][N+:5]([O-])=O.[C:10]([O:16][CH2:17][CH3:18])(=[O:15])[CH2:11][C:12]([CH3:14])=O.[Na].[F:20][C:21]1[CH:27]=[CH:26][C:24](N)=[CH:23][CH:22]=1>CCOCC.C1(C)C=CC=CC=1>[CH2:17]([O:16][C:10]([C:11]1[C:3]([C:2]([CH3:9])([CH3:8])[CH3:1])=[CH:4][N:5]([C:24]2[CH:26]=[CH:27][C:21]([F:20])=[CH:22][CH:23]=2)[C:12]=1[CH3:14])=[O:15])[CH3:18]

Participants

7

Reactant 4

HCID 8868Ethyl AcetoacetateHCID 97314-FluoroanilineHCID 5360545SodiumHCID 53439675HCID 53439675, compound

Product 1

HCID 68426811HCID 68426811, compound

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
0 °C

Procedure

A mixture of 3,3-dimethyl-1-nitro-but-1-ene (6.2 g, 36 mmol) and ethyl acetoacetate, sodium salt (5.76 g, 36 mmol) in ether (50 mL) was stirred at 0° C. for 30 min; then the reaction was quenched with saturated ammonium chloride aqueous solution, the ether layer was washed with saturated NaCl aqueous solution dried over anhydrous sodium sulfate, filtered, concentrated, to give a mixture, which was used next reaction without further purification and characterization. The above mixture was refluxed with 4-fluoroaniline (4.09 mL, 43.2 mmol), and TsOH monohydrate (343 mg, 1.8 mmol) in toluene (100 mL) was refluxed overnight, the generated water was collected with a Dean-Stark distillation apparatus; then the reaction was cooled to room temperature, diluted with EtOAc, washed with diluted HCl aqueous solution, saturated sodium bicarbonate aqueous solution, and saturated NaCl aqueous solution respectively, then dried over anhydrous sodium sulfate filtered, concentrated, the residue was purified with column to give a slightly brown oil, the title product (1.904 g); The title compound, ESI MS (m/z): 304 (M+H+).

Workup

  1. customthen the reaction was quenched with saturated ammonium chloride aqueous solution
  2. washthe ether layer was washed with saturated NaCl aqueous solution
  3. dry with materialdried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto give a mixture, which
  7. customreaction
  8. customwithout further purification and characterization
  9. temperaturewas refluxed overnight
  10. distillationthe generated water was collected with a Dean-Stark distillation apparatus
  11. temperaturethen the reaction was cooled to room temperature
  12. additiondiluted with EtOAc
  13. washwashed with diluted HCl aqueous solution, saturated sodium bicarbonate aqueous solution, and saturated NaCl aqueous solution respectively
  14. dry with materialdried over anhydrous sodium sulfate
  15. filtrationfiltered
  16. concentrationconcentrated
  17. customthe residue was purified with column
  18. customto give a slightly brown oil

Sources & evidence

ORD record
ord-b91d7cb8932b4f6b83bc73a52b68d550
Source dataset
uspto-grants-2010_04
Patent number
US07696223B2

Reaction notes

Loading…