Diethyl Oxalate → ethyl acetoacetate, sodium salt

HRID 1948337Notes

Reaction equation

HRID 1948337 reaction equation
[C:1]([O:8][CH2:9][CH3:10])(=[O:7])[C:2]([O:4]CC)=O.[CH2:11]([Mg]Br)[CH3:12].C(=O)=O.CC(C)=O>CCOCC>[O:4]=[C:2]([CH2:11][CH3:12])[C:1]([O:8][CH2:9][CH3:10])=[O:7]

Participants

5

Reactant 3

HCID 7268Diethyl OxalateHCID 18522661Acetone cardiceHCID 178418443HCID 178418443, compound

Product 1

HCID 85195ethyl acetoacetate, sodium saltYield 86%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

Diethyl oxalate (10 g; 68 mmol) was dissolved in Et2O (100 ml) and cooled to −78 C. Ethyl magnesium bromide (1.0 M in THF; 72 ml; 71.8 mmol; 1.05 equiv.) was added slowly via syringe. The dry ice/acetone bath was allowed to melt and warm to 10 C. Monitored the reaction by 1H NMR. The reaction was cooled to 0 C and quenched with saturated NH4Cl. Dilute with H2O and separate phases. The organic layer was dried over Na2SO4, filtered and concentrated. Isolation gave 7.6 g of a crude yellow oil in 86% yield. No further purification.

Workup

  1. temperaturecooled to −78 C
  2. temperaturewarm to 10 C
  3. customMonitored the reaction by 1H NMR
  4. temperatureThe reaction was cooled to 0 C
  5. customquenched with saturated NH4Cl
  6. additionDilute with H2O
  7. customseparate phases
  8. dry with materialThe organic layer was dried over Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated

Sources & evidence

ORD record
ord-22cf3ba8356c45edb857eab1138ed47f
Source dataset
uspto-grants-2013_03
Patent number
US08399489B2

Reaction notes

Loading…