Acetonitrile → Diethyl 2-propyl-6-vinylpyridine-3,5-dicarboxylate

HRID 531089Notes

Reaction equation

HRID 531089 reaction equation
P(Cl)(Cl)(Cl)=O.O[C:7]1[C:12]([C:13]([O:15][CH2:16][CH3:17])=[O:14])=[CH:11][C:10]([C:18]([O:20][CH2:21][CH3:22])=[O:19])=[C:9]([CH2:23][CH2:24][CH3:25])[N:8]=1.[C:26](#N)[CH3:27]>>[CH2:23]([C:9]1[C:10]([C:18]([O:20][CH2:21][CH3:22])=[O:19])=[CH:11][C:12]([C:13]([O:15][CH2:16][CH3:17])=[O:14])=[C:7]([CH:26]=[CH2:27])[N:8]=1)[CH2:24][CH3:25]

Participants

4

Reactant 3

HCID 6342AcetonitrileHCID 24813Phosphorus oxychlorideHCID 178440245HCID 178440245, compound

Product 1

HCID 117992132Diethyl 2-propyl-6-vinylpyridine-3,5-dicarboxylate

Conditions

Temperature
90 °C

Procedure

Phosphoryl trichloride (7.95 mL) was added to a solution of diethyl 2-hydroxy-6-propylpyridine-3,5-dicarboxylate (12.0 g) in acetonitrile (120 mL) at room temperature. The mixture was stirred at 90° C. under a dry atmosphere with calcium chloride tube for 3 hours. After cooling to room temperature, the mixture was quenched with aqueous saturated sodium hydrogen carbonate solution at room temperature and extracted with ethyl acetate. The organic layer was separated, washed with brine and water, dried over anhydrous magnesium sulfate and concentrated in vacuo. A mixture of the residue, triethylamine (11.8 mL), potassium trifluoro(vinyl)borate (8.51 g) and dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium dichloromethane adduct (2.42 g) in ethanol (130 mL) was stirred at 90° C. overnight under nitrogen atmosphere. After cooling to room temperature, the mixture was concentrated in vacuo. The residue was diluted with ethyl acetate and water. The organic layer was separated, washed with brine, dried over anhydrous magnesium sulfate and concentrated in vacuo. The residue was passed through a silica gel-pad (hexane/ethyl acetate) to give the title compound (10.3 g).

Workup

  1. temperatureAfter cooling to room temperature
  2. customthe mixture was quenched with aqueous saturated sodium hydrogen carbonate solution at room temperature
  3. extractionextracted with ethyl acetate
  4. customThe organic layer was separated
  5. washwashed with brine and water
  6. dry with materialdried over anhydrous magnesium sulfate
  7. concentrationconcentrated in vacuo
  8. additionA mixture of the residue, triethylamine (11.8 mL), potassium trifluoro(vinyl)borate (8.51 g) and dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium dichloromethane adduct (2.42 g) in ethanol (130 mL)
  9. stirringwas stirred at 90° C. overnight under nitrogen atmosphere
  10. temperatureAfter cooling to room temperature
  11. concentrationthe mixture was concentrated in vacuo
  12. additionThe residue was diluted with ethyl acetate and water
  13. customThe organic layer was separated
  14. washwashed with brine
  15. dry with materialdried over anhydrous magnesium sulfate
  16. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-447bdc1fbbd246c39774ff80fc9563ac
Source dataset
uspto-grants-2016_05
Patent number
US09353108B2

Reaction notes

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