Phenyl-3-pyridinylmethanone → 3-Phenyl-3-pyridin-3-yl-acrylonitrile

HRID 886812Notes

Reaction equation

HRID 886812 reaction equation
[C:1]([C:9]1[CH:10]=[N:11][CH:12]=[CH:13][CH:14]=1)(=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(OP([CH2:23][C:24]#[N:25])(=O)OCC)C.CC[O-].[Na+].[H-].[Na+].[NH4+].[Cl-]>C(O)C>[C:2]1([C:1]([C:9]2[CH:10]=[N:11][CH:12]=[CH:13][CH:14]=2)=[CH:23][C:24]#[N:25])[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 5

HCID 21540Phenyl-3-pyridinylmethanoneHCID 24758Sodium hydride2×HCID 25517Ammonium ChlorideHCID 75676Diethyl (cyanomethyl)phosphonateHCID 2723922Sodium ethoxide

Product 1

HCID 666023873-Phenyl-3-pyridin-3-yl-acrylonitrileYield 96%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

1 g (5.46 mmol, 1 eq) of 3-benzoylpyridine is dissolved in 30 ml of ethanol under Ar. 1.16 mL (7.10 mmol, 1.3 eq) of diethylcyanomethylphosphonate and 965 mg (14.1 mmol, 2.6 eq) of NaOEt are added. The mixture is stirred for 1 hour at room temperature. 108 mg (2.73 mmol, 0.5 eq) of 60% NaH in oil are added and the mixture is heated to 70-80° C. for 1 hour. A further 138 mg (3.49 mmol, 0.64 eq) of NaH are added and the mixture is heated for 40 min at 70-80° C. An NH4Cl solution is added, then the EtOH is concentrated. The basic aqueous phase is extracted with AcOEt and the organic phase is washed with brine, dried, filtered and concentrated. The oil obtained is subjected to chromatography over alumina (eluant: heptane/AcOEt: 7/1). A mixture of two stereoisomers is obtained (oil, m=1.076 g, yield=96%).

Workup

  1. temperaturethe mixture is heated to 70-80° C. for 1 hour
  2. temperaturethe mixture is heated for 40 min at 70-80° C
  3. concentrationthe EtOH is concentrated
  4. extractionThe basic aqueous phase is extracted with AcOEt
  5. washthe organic phase is washed with brine
  6. customdried
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe oil obtained
  10. additionA mixture of two stereoisomers
  11. customis obtained (oil, m=1.076 g, yield=96%)

Sources & evidence

ORD record
ord-006ef43d28dc4125b2851293240954f8
Source dataset
uspto-grants-2012_08
Patent number
US08247412B2

Reaction notes

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