Cyclopropyl methyl ketone → 1-Cyclopropyl-butane-1,3-dione

HRID 892425Notes

Reaction equation

HRID 892425 reaction equation
[CH3:1][C:2]([CH:4]1[CH2:6][CH2:5]1)=[O:3].[O-:7][CH2:8][CH3:9].[Na+]>C(OCC)(=O)C.C(O)C>[CH:4]1([C:2](=[O:3])[CH2:1][C:8](=[O:7])[CH3:9])[CH2:6][CH2:5]1

Participants

5

Reactant 2

HCID 13004Cyclopropyl methyl ketoneHCID 2723922Sodium ethoxide

Product 1

HCID 110188691-Cyclopropyl-butane-1,3-dione

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a stirred solution of 8.4 g (0.1 mol) of cyclopropyl methyl ketone in 100 mL of ethyl acetate under nitrogen was added dropwise 39 mL (0.1 mol) of a 21 wt % solution of sodium ethoxide in absolute ethanol. The flask was fitted with a condenser and Dean-Stark trap and was heated. The ethanol was removed by azeotropic distillation. Additional ethyl acetate was added to the flask as needed. After three hours the temperature of the distillate had reached 75° C. and the reaction was allowed to cool and stand overnight. The white solid which precipitated out was collected by filtration and the filtrate was set aside. The solid was dissolved in water and this solution was acidified at 0° C. with 10% aqueous hydrochloric acid. This solution was extracted three times with ethyl ether. The ethyl acetate filtrate was washed with water three times, acidified with 10% aqueous hydrochloric acid, and extracted with ethyl ether. The ether extracts from both extractions were combined, dried over magnesium sulfate, and filtered. Removal of solvents gave 3.5 g of 1-cyclopropyl-1,3-butanedione as an oil. Analysis by GC showed 75% purity. This intermediate was used without further purification.

Workup

  1. customThe flask was fitted with a condenser
  2. temperatureDean-Stark trap and was heated
  3. customThe ethanol was removed by azeotropic distillation
  4. additionAdditional ethyl acetate was added to the flask
  5. temperatureto cool
  6. waitstand overnight
  7. customThe white solid which precipitated out
  8. filtrationwas collected by filtration
  9. dissolutionThe solid was dissolved in water
  10. customwas acidified at 0° C. with 10% aqueous hydrochloric acid
  11. extractionThis solution was extracted three times with ethyl ether
  12. washThe ethyl acetate filtrate was washed with water three times
  13. extractionextracted with ethyl ether
  14. extractionThe ether extracts from both extractions
  15. dry with materialdried over magnesium sulfate
  16. filtrationfiltered
  17. customRemoval of solvents

Sources & evidence

ORD record
ord-266efad57da44f0ab2717d529f04e223
Source dataset
uspto-grants-1992_06
Patent number
US05118681

Reaction notes

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