Ethyl formate → ethyl alpha-formyl-beta-(N-benzyl-2-oxo-4-pyridyl)propionate

HRID 1719546Notes

Reaction equation

HRID 1719546 reaction equation
[H-].[Na+].[CH2:3]([N:10]1[CH:15]=[CH:14][C:13]([CH2:16][CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19])=[CH:12][C:11]1=[O:23])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[CH2:24]([O:26]C=O)C>C(COC)OC>[CH:24]([CH:17]([CH2:16][C:13]1[CH:14]=[CH:15][N:10]([CH2:3][C:4]2[CH:5]=[CH:6][CH:7]=[CH:8][CH:9]=2)[C:11](=[O:23])[CH:12]=1)[C:18]([O:20][CH2:21][CH3:22])=[O:19])=[O:26]

Participants

5

Reactant 3

HCID 8025Ethyl formateHCID 24758Sodium hydrideHCID 20267143ethyl beta-(N-benzyl-2-oxo-4-pyridyl)propionate

Product 1

HCID 20267152ethyl alpha-formyl-beta-(N-benzyl-2-oxo-4-pyridyl)propionateYield 67.7%

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a cooled (0° C.), stirred suspension of 50% sodium hydride in oil (6.37 g) in dimethoxyethane (80 ml) was added dropwise over 25 minutes a mixture of ethyl β-(N-benzyl-2-oxo-4-pyridyl)propionate (30.29 g) and ethylformate (11.80 g), whilst maintaining the reaction temperature between 5°-8° C. The reaction mixture was allowed to warm slowly to room temperature overnight and then was poured on to ice. A brown solution formed which was extracted successively with petroleum ether (40°-60° C.) (60 ml) and diethyl ether (70 ml). The combined organic extracts were washed with water. The combined aqueous layer and aqueous washings were taken to pH 5 with glacial acetic acid. The solution was cooled whereupon a solid appeared which was collected by filtration, washed with water, washed with ethyl acetate and dried in vacuo to yield ethyl α-formyl-β-(N-benzyl-2-oxo-4-pyridyl)propionate (22.52 g), m.p. 140°-143° C.

Workup

  1. additionwas added dropwise over 25 minutes
  2. temperaturewhilst maintaining the reaction temperature between 5°-8° C
  3. temperatureto warm slowly to room temperature overnight
  4. additionwas poured on to ice
  5. customA brown solution formed which
  6. extractionwas extracted successively with petroleum ether (40°-60° C.) (60 ml) and diethyl ether (70 ml)
  7. washThe combined organic extracts were washed with water
  8. temperatureThe solution was cooled whereupon a solid
  9. filtrationwas collected by filtration
  10. washwashed with water
  11. washwashed with ethyl acetate
  12. customdried in vacuo

Sources & evidence

ORD record
ord-9d861502b2d44d47842997b39d4eab6b
Source dataset
uspto-grants-1985_09
Patent number
US04540699

Reaction notes

Loading…