HCID 131719407, compound → HCID 131719406, compound

HRID 440574Notes

Reaction equation

HRID 440574 reaction equation
[CH3:1][C:2]1([CH3:9])[O:6][CH:5]([CH2:7][OH:8])[CH2:4][O:3]1.[C:10]([O-:16])(=[O:15])[CH2:11][C:12]([CH3:14])=[O:13].[H][H]>[Ni].C(OC(=O)C)C>[CH3:1][C:2]1([CH3:9])[O:6][CH:5]([CH2:7][OH:8])[CH2:4][O:3]1.[OH:13][CH:12]([CH3:14])[CH2:11][C:10]([O-:16])=[O:15]

Participants

5

Reactant 2

HCID 131719407HCID 131719407, compoundHCID 178418361HCID 178418361, compound3×

Product 1

HCID 131719406HCID 131719406, compoundYield 92%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
60 °C

Procedure

A Zipperclave Autoclave (Autoclave Engineers) was charged with ethylacetate (2.4 L), solketal acetoacetate from Example 1 (609.5 g, 2.82 mole) and Raney Nickel (25 g, W-2 grade, PM-77, water wet) under an inert atmosphere of nitrogen. The nitrogen was displaced with hydrogen to a pressure of approximately 1100 psi. The reaction mixture was then heated with vigorous stirring (1500 rpm) at 60° C. for approximately seven hours. A small (ca. 5 ml) sample of the reaction mixture was removed from the reactor, filtered through celite and concentrated in vacuo. Proton NMR analysis revealed that roughly 2 mole % of unreduced acetoacetate remained. The crude reaction mixture was then heated at 60° C. and 1000 psi hydrogen with vigorous stirring for an additional 5 hours. The autoclave was cooled to room temperature and the hydrogen atmosphere was displaced with nitrogen. The crude reaction mixture was filtered through celite. The resulting solution was extracted in a separatory funnel with saturated aqueous sodium chloride. The organic phase was isolated, filtered through magnesium sulfate and sodium sulfate. The resulting filtrate was concentrated in vacuo to provide an oil (565.11 g, 2.59 mole, approximately 92%). This oil was not purified further but was shown by NMR to be of high purity. Small amounts, <15 total mole %, of ethyl acetate and acetone were also detected.

Workup

  1. temperatureThe reaction mixture was then heated
  2. customA small (ca. 5 ml) sample of the reaction mixture was removed from the reactor
  3. filtrationfiltered through celite and
  4. concentrationconcentrated in vacuo
  5. customThe crude reaction mixture
  6. temperaturewas then heated at 60° C.
  7. temperatureThe autoclave was cooled to room temperature
  8. customThe crude reaction mixture
  9. filtrationwas filtered through celite
  10. extractionThe resulting solution was extracted in a separatory funnel with saturated aqueous sodium chloride
  11. customThe organic phase was isolated
  12. filtrationfiltered through magnesium sulfate and sodium sulfate
  13. concentrationThe resulting filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-604caa4ab9c94ce9af6e1980576003b6
Source dataset
uspto-grants-1996_05
Patent number
US05519161

Reaction notes

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