Potassium Fluoride → 6-(1-Ethoxy-vinyl)-nicotinonitrile

HRID 1191087Notes

Reaction equation

HRID 1191087 reaction equation
Br[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][N:3]=1.[CH2:10]([O:12][C:13]([Sn](CCCC)(CCCC)CCCC)=[CH2:14])[CH3:11].[F-].[K+]>C(#N)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH2:13]([O:12][C:10]([C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][N:3]=1)=[CH2:11])[CH3:14]

Participants

6

Reactant 3

HCID 522689Potassium FluorideHCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 50057186-Bromopyridine-3-carbonitrile

Product 1

HCID 598289076-(1-Ethoxy-vinyl)-nicotinonitrileYield 190.5%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 6342AcetonitrileSolvent

Procedure

Slurry 6-bromo-nicotinonitrile (8.0 g, 43.7 mmol), 1-ethoxyvinyl-tributylstannane (17.4 g, 48 mmol), and dichlorobis(triphenylphosphine)-palladium (1.5 g, 2.2 mmol) in acetonitrile (680 mL) at room temperature. Stir the mixture at reflux for 16 h under a nitrogen atmosphere. Cool the mixture to room temperature, add aqueous saturated potassium fluoride (100 mL), stir 30 min then filter and wash with EtOAc (200 mL). Wash the organic phase with water (250 mL). Dry the organic layer over Na2SO4, filter and concentrate in vacuo to obtain the desired intermediate (14.5 g) that was used without further purification. MS (ES+) m/z: 175 (M+H)+.

Workup

  1. customat room temperature
  2. temperatureat reflux for 16 h under a nitrogen atmosphere
  3. stirringstir 30 min
  4. filtrationthen filter
  5. washwash with EtOAc (200 mL)
  6. washWash the organic phase with water (250 mL)
  7. dry with materialDry the organic layer over Na2SO4
  8. filtrationfilter
  9. concentrationconcentrate in vacuo

Sources & evidence

ORD record
ord-915c87f2b3024d70ac469c4727470327
Source dataset
uspto-grants-2014_03
Patent number
US08680091B2

Reaction notes

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