Sodium → Sodium

HRID 638102Notes

Reaction equation

HRID 638102 reaction equation
[Na:1].[CH2:2]([CH:6]([CH2:12][C:13]([O:15]CC)=O)[C:7]([O:9][CH2:10][CH3:11])=[O:8])[C:3]([CH3:5])=[O:4]>C(O)C>[Na:1].[O:15]=[C:13]1[CH2:5][C:3](=[O:4])[CH2:2][CH:6]([C:7]([O:9][CH2:10][CH3:11])=[O:8])[CH2:12]1

Participants

5

Reactant 2

HCID 5360545SodiumHCID 54638161,4-Diethyl 2-(2-oxopropyl)butanedioate

Product 2

HCID 5360545SodiumHCID 11252382Cyclohexanecarboxylic acid, 3,5-dioxo-, ethyl ester

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To 150 ml of ethanol containing 3.4 g of sodium was added dropwise 31 g of diethyl acetonylsuccinate (or diethyl acetmethylsuccinate) over about one hour with stirring at ambient temperature. The mixture was heated under reflux for 2 hours and then cooled to room temperature, followed by distillation off of the ethanol under reduced pressure. There was thus obtained a brown viscous liquid comprising sodium salt of ethyl 3,5-dioxocyclohexanecarboxylate as formed, to which were added 100 ml of toluene, 50 ml of ice water and 0.3 g of γ-picoline and then added dropwise 15 g of n-butyryl chloride at ambient temperature under agitation over about 2 hours. The resultant reaction mixture was agitated for further 30 minutes and then the toluene layer was separated, washed with water, dried and admixed with 0.8 g of 4-N,N-dimethylaminopyridine. The admixture was heated with agitation at a temperature of 80°-90° C. for 3 hours. The toluene was then distilled off from the reaction solution under reduced pressure and the residue was chromatographed on a column of silica gel developed with benzene to give 19.5 g (55.9%) of the object compound (Compound No. 15).

Workup

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for 2 hours
  3. temperaturecooled to room temperature
  4. distillationfollowed by distillation off of the ethanol under reduced pressure

Sources & evidence

ORD record
ord-7168874abd914816bb8a68c902890662
Source dataset
uspto-grants-1985_12
Patent number
US04560403

Reaction notes

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