Ethyl Acetoacetate → HCID 59128637, compound

HRID 1991002Notes

Reaction equation

HRID 1991002 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([CH3:10])=[C:6](Br)[CH:5]=1.[CH2:13]([O:15][C:16](=[O:21])[CH2:17]C(=O)C)[CH3:14].[O-]P([O-])([O-])=O.[K+].[K+].[K+]>C1(C)C=CC=CC=1.C([O-])(=O)C.C([O-])(=O)C.[Pd+2]>[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([CH3:10])=[C:6]([CH2:17][C:16]([O:15][CH2:13][CH3:14])=[O:21])[CH:5]=1

Participants

6

Reactant 3

HCID 8868Ethyl AcetoacetateHCID 62657Potassium Phosphate, TribasicHCID 7015747Methyl 3-bromo-4-methylbenzoate

Product 1

HCID 59128637HCID 59128637, compoundYield 10.7%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

3-Bromo-4-methyl-benzoic acid methyl ester (20.0 g, 87.31 mmol) was dissolved in 220 mL toluene, and 3-oxo-butyric acid ethyl ester (25.0 g, 192.08 mmol), K3PO4 (102 g, 480 mmol), biphen-2-yl-P(t-Bu)2 (2.60 g, 8.73 mmol), and palladium diacetate (980 mg, 4.36 mmol) were added. The reaction mixture was evacuated and purged with argon, and then heated to 90° C. for 15 hours. The reaction mixture was cooled and partitioned between water and ethyl acetate. The organic layer was washed with water, brine, dried (MgSO4), filtered, and concentrated under reduced pressure. The residue was purified by flash chromatography (10%-15% EtOAc/hexanes) to provide 2.20 g of 3-ethoxycarbonylmethyl-4-methyl-benzoic acid methyl ester, MS (M+H)=237.

Workup

  1. customThe reaction mixture was evacuated
  2. custompurged with argon
  3. temperatureThe reaction mixture was cooled
  4. custompartitioned between water and ethyl acetate
  5. washThe organic layer was washed with water, brine
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by flash chromatography (10%-15% EtOAc/hexanes)

Sources & evidence

ORD record
ord-8729f38732b14bc1ae134d3b44c74149
Source dataset
uspto-grants-2010_01
Patent number
US07645764B2

Reaction notes

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