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

HRID 1719540Notes

Reaction equation

HRID 1719540 reaction equation
[H-].[Na+].[CH2:3]([N:7]1[CH:12]=[CH:11][C:10]([CH2:13][CH2:14][C:15]([O:17][CH2:18][CH3:19])=[O:16])=[CH:9][C:8]1=[O:20])[CH2:4][CH2:5][CH3:6].[CH:21](OCC)=[O:22]>C(COC)OC>[CH:21]([CH:14]([CH2:13][C:10]1[CH:11]=[CH:12][N:7]([CH2:3][CH2:4][CH2:5][CH3:6])[C:8](=[O:20])[CH:9]=1)[C:15]([O:17][CH2:18][CH3:19])=[O:16])=[O:22]

Participants

5

Reactant 3

HCID 8025Ethyl formateHCID 24758Sodium hydrideHCID 20267135HCID 20267135, compound

Product 1

HCID 20267147ethyl alpha-formyl-beta-(N-n-butyl-2-oxo-4-pyridyl)propionateYield 84.8%

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent

Procedure

To a stirred suspension of 50% sodium hydride in oil (13.89 g) in dimethoxyethane (100 ml) at -2° C., was added dropwise over 90 minutes, a mixture of ethyl β-(N-n-butyl-2-oxo-4-pyridyl)propionate (58.19 g) and ethyl formate (25.73 g), the reaction temperature being maintained below 5° C. The reaction mixture was then allowed to warm to room temperature overnight, poured on to ice and extracted successively into petroleum ether (40°-60°) (150 ml) and diethyl ether (3×100 ml). The combined organic extracts were washed with water (40 ml); and the aqueous layer and aqueous washings were taken to pH 5 with glacial acetic acid. A brown oil came out of solution which was extracted into ethyl acetate (3×150 ml). The combined ethyl acetate extracts were washed with water (2×30 ml), dried over MgSO4 and evaporated under reduced pressure. The residue was washed with petroleum ether (40°-60°) and dried in vacuo to afford as a pale brown solid, ethyl α-formyl-β-(N-n-butyl-2-oxo-4-pyridyl)propionate (54.84 g).

Workup

  1. additionwas added dropwise over 90 minutes
  2. temperaturethe reaction temperature being maintained below 5° C
  3. additionpoured on to ice
  4. extractionextracted successively into petroleum ether (40°-60°) (150 ml) and diethyl ether (3×100 ml)
  5. washThe combined organic extracts were washed with water (40 ml)
  6. extractionwas extracted into ethyl acetate (3×150 ml)
  7. washThe combined ethyl acetate extracts were washed with water (2×30 ml)
  8. dry with materialdried over MgSO4
  9. customevaporated under reduced pressure
  10. washThe residue was washed with petroleum ether (40°-60°)
  11. customdried in vacuo

Sources & evidence

ORD record
ord-9e934e2fc8574146956ea2cd27511539
Source dataset
uspto-grants-1985_09
Patent number
US04540699

Reaction notes

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