Oxygen → Ethyl 2-methylacetoacetate

HRID 898500Notes

Reaction equation

HRID 898500 reaction equation
O=O.[CH3:3]C(C)([O-])C.[K+].[C:9]([O:15][CH2:16][CH3:17])(=[O:14])[CH2:10][C:11]([CH3:13])=[O:12].CI>C1COCC1.O>[CH3:3][CH:10]([C:11](=[O:12])[CH3:13])[C:9]([O:15][CH2:16][CH3:17])=[O:14]

Participants

7

Reactant 4

HCID 977OxygenHCID 6328Methyl iodideHCID 8868Ethyl AcetoacetateHCID 23665647Potassium tert-butoxide

Product 1

HCID 701Ethyl 2-methylacetoacetateYield 70%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

Under nitrogen atmosphere free of water and oxygen, to a three-necked flask equipped with a dropping funnel were successively added 0.15 mol of potassium tert-butoxide and 150 ml of THF, then stirrer was started. 0.12 Mol of ethyl acetoacetate was slowly dropped to the reactor cooled in an ice-water bath. Upon completion of the dropping, the reaction was continued at room temperature for further 1 hr. Then 0.18 mol of methyl iodide was slowly dropped at room temperature, and then the reaction was continued at room temperature for further 24 hrs. At the end of the reaction, solvent was evaporated by using a rotatory evaporator, and saturated saline was added to just dissolve the solid. Organic phase was separated, and aqueous phase was extracted with a suitable amount of diethyl ether for three times. The combined organic phase was washed well with saturated saline, then dried over anhydrous sodium sulfate. Solvent was removed by using a rotatory evaporator, and the residue was distilled under reduced pressure to give 0.084 mol of product. Yield 70%.

Workup

  1. customstirrer was started
  2. temperaturecooled in an ice-water bath
  3. waitthe reaction was continued at room temperature for further 24 hrs
  4. customAt the end of the reaction, solvent
  5. customwas evaporated
  6. customa rotatory evaporator, and saturated saline
  7. additionwas added
  8. dissolutionto just dissolve the solid
  9. customOrganic phase was separated
  10. extractionaqueous phase was extracted with a suitable amount of diethyl ether for three times
  11. washThe combined organic phase was washed well with saturated saline
  12. dry with materialdried over anhydrous sodium sulfate
  13. customSolvent was removed
  14. customa rotatory evaporator
  15. distillationthe residue was distilled under reduced pressure

Sources & evidence

ORD record
ord-084ff40fe8ad4e03b31a17c32d9012c7
Source dataset
uspto-grants-2008_04
Patent number
US07351778B2

Reaction notes

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