Acetaldehyde → alpha-Ethylidene 3-pyridineacetonitrile

HRID 465110Notes

Reaction equation

HRID 465110 reaction equation
[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([CH2:7][C:8]#[N:9])[CH:2]=1.[CH:10](=O)[CH3:11].C(=O)([O-])[O-].[Cs+].[Cs+]>C(O)C>[CH:10](=[C:7]([C:3]1[CH:2]=[N:1][CH:6]=[CH:5][CH:4]=1)[C:8]#[N:9])[CH3:11]

Participants

5

Reactant 3

HCID 177AcetaldehydeHCID 10796Cesium carbonateHCID 809233-Pyridineacetonitrile

Product 1

HCID 54373598alpha-Ethylidene 3-pyridineacetonitrile

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
20 °C

Procedure

A mixture of 57 g of 3-pyridineacetonitrile, 23.3 g of acetaldehyde and 0.5 g of cesium carbonate were dissolved in 1 liter of ethanol. The solution was stirred at 20° C. for 30 hours, then partitioned between 2 liters of water and 1 liter of ether. The aqueous phase was extracted with three 1 liter portions of ether and then 500 ml of ethyl acetate. All organic layers were combined, dried and the solvent removed at reduced pressure giving an orange oil. This oil was purified by chromatography on silica gel, eluting with ethyl acetate:hexane (1:1), giving a pale yellow oil which was crystallized from methylene chloride-hexane, giving α-ethylidene 3-pyridineacetonitrile as white needles, mp 46°-47° C.

Workup

  1. custompartitioned between 2 liters of water and 1 liter of ether
  2. extractionThe aqueous phase was extracted with three 1 liter portions of ether
  3. customdried
  4. customthe solvent removed at reduced pressure
  5. customgiving an orange oil
  6. customThis oil was purified by chromatography on silica gel
  7. washeluting with ethyl acetate:hexane (1:1)
  8. customgiving a pale yellow oil which
  9. customwas crystallized from methylene chloride-hexane

Sources & evidence

ORD record
ord-21c40282d1d74fa590d8bd12d7c9fe03
Source dataset
uspto-grants-1985_10
Patent number
US04550166

Reaction notes

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