Sodium hydride → HCID 54096519, compound

HRID 975164Notes

Reaction equation

HRID 975164 reaction equation
[C:1]([CH2:3]P(=O)(OCC)OCC)#[N:2].[H-].[Na+].O=[C:15]1[C:21]2[CH:22]=[CH:23][CH:24]=[CH:25][C:20]=2[CH2:19][O:18][C:17]2[CH:26]=[C:27]([C:30]([O:32][CH2:33][CH3:34])=[O:31])[CH:28]=[CH:29][C:16]1=2>C1COCC1.C(OCC)(=O)C>[CH2:33]([O:32][C:30]([C:27]1[CH:28]=[CH:29][C:16]2[C:15](=[CH:3][C:1]#[N:2])[C:21]3[CH:22]=[CH:23][CH:24]=[CH:25][C:20]=3[CH2:19][O:18][C:17]=2[CH:26]=1)=[O:31])[CH3:34]

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 75676Diethyl (cyanomethyl)phosphonateHCID 19970862HCID 19970862, compound

Product 1

HCID 54096519HCID 54096519, compoundYield 58%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

Diethyl (cyanomethyl)phosphonate (52 ml) was dissolved in 200 ml of THF, and 12.8 g of sodium hydride (60% oily) was added to the solution under ice cooling, followed by stirring for one hour. To the mixture was added 200 ml of a solution of 17.3 g of ethyl 11-oxo-6,11-dihydrodibenz[b,e]oxepin-3-carboxylate in THF, and the mixture was heated under reflux for 3 hours. After cooling, ice chips were added to the reaction mixture, and the mixture was then diluted with ethyl acetate. The organic layer was washed with a saturated aqueous solution of sodium chloride and dried over anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography [eluent: hexane/ethyl acetate (2/1)] to give 11.5 g (58%) of the product as a colorless oily substance.

Workup

  1. temperaturethe mixture was heated
  2. temperatureunder reflux for 3 hours
  3. temperatureAfter cooling
  4. additionice chips were added to the reaction mixture
  5. washThe organic layer was washed with a saturated aqueous solution of sodium chloride
  6. dry with materialdried over anhydrous magnesium sulfate
  7. distillationAfter the solvent was distilled off under reduced pressure
  8. customthe residue was purified by silica gel column chromatography [eluent: hexane/ethyl acetate (2/1)]

Sources & evidence

ORD record
ord-32279345ce23437fa6b33fa28ce2cf50
Source dataset
uspto-grants-1997_03
Patent number
US05607955

Reaction notes

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