Triethyl phosphonoacetate → ethyl N-ethoxycarbonyl-4-piperidylideneacetate

HRID 982336Notes

Reaction equation

HRID 982336 reaction equation
[H-].[Na+].C(OP([CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])(OCC)=O)C.[CH2:17]([O:19][C:20]([N:22]1[CH2:27][CH2:26][C:25](=O)[CH2:24][CH2:23]1)=[O:21])[CH3:18]>COCCOC>[CH2:17]([O:19][C:20]([N:22]1[CH2:27][CH2:26][C:25](=[CH:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH2:24][CH2:23]1)=[O:21])[CH3:18]

Participants

5

Reactant 3

HCID 13345Triethyl phosphonoacetateHCID 24758Sodium hydrideHCID 34767Ethyl 4-oxo-1-piperidinecarboxylate

Product 1

HCID 14801831ethyl N-ethoxycarbonyl-4-piperidylideneacetateYield 106.6%

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent

Procedure

To a suspension of 4 g oily sodium hydride (60%) in 200 ml of anhydrous 1,2-dimethoxyethane, was added dropwise 23.6 g ethyl diethylphosphonoacetate at about 20° C., and the mixture was stirred at that temperature for about one hour. To the solution thus obtained, was added dropwise 17.1 g N-ethoxycarbonyl-4-piperidone at temperatures below 30° C., the mixture was stirred for an additional two hours, and the solvent was distilled off under reduced pressure. Ice water (100 ml) and ethyl acetate (100 ml) were added to the residue, the mixture was shaken, and the layers were separated. The aqueous layer was extracted twice with 100 ml ethyl acetate, and all the organic solutions were combined, washed with water and dried over anhydrous magnesium sulfate. Distilling off the solvent from the dried solution gave 25.7 g of ethyl N-ethoxycarbonyl-4-piperidylideneacetate as colorless solid.

Workup

  1. customTo the solution thus obtained
  2. stirringthe mixture was stirred for an additional two hours
  3. distillationthe solvent was distilled off under reduced pressure
  4. additionIce water (100 ml) and ethyl acetate (100 ml) were added to the residue
  5. stirringthe mixture was shaken
  6. customthe layers were separated
  7. extractionThe aqueous layer was extracted twice with 100 ml ethyl acetate
  8. washwashed with water
  9. dry with materialdried over anhydrous magnesium sulfate
  10. distillationDistilling off the solvent from the dried solution

Sources & evidence

ORD record
ord-25163be0943c4cbdb88efe76659a6131
Source dataset
uspto-grants-1991_02
Patent number
US04996210

Reaction notes

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