Styrene → 2-Styrylnicotinic acid methyl ester

HRID 989908Notes

Reaction equation

HRID 989908 reaction equation
[CH3:1][O:2][C:3](=[O:11])[C:4]1[CH:9]=[CH:8][CH:7]=[N:6][C:5]=1Cl.[CH2:12]=[CH:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.C([O-])(=O)C.[Na+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:1][O:2][C:3](=[O:11])[C:4]1[CH:9]=[CH:8][CH:7]=[N:6][C:5]=1[CH:12]=[CH:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

7

Reactant 4

HCID 7501StyreneHCID 11776TriphenylphosphineHCID 517045Sodium AcetateHCID 819931Methyl 2-chloronicotinate

Product 1

HCID 536734442-Styrylnicotinic acid methyl esterYield 82.1%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Procedure

To a solution of the ester 18 (48.8 g, 0.28 mol) in DMF (450 mL) was added styrene (165 mL, 1.42 mol), palladium acetate (6.5 g, 30 mmol), sodium acetate (47 g, 0.57 mol) and triphenyl phosphine (30 g, 0.11 mol). The mixture was heated under reflux for 22 h. The palladium-catalyst was removed by filtration through a Celite pad. The filtrate was concentrated under reduced pressure, and the residue was dissolved in a minimum amount of ethyl acetate. To the above solution was added hexane. After removal of the precipitate by filtration, the filtrate was concentrated. The resulting crude material was purified by FCC (1:1 v/v ethyl acetate-hexane) to afford the ester 19 (55.0 g, 81%) as a light yellow oil:

Workup

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for 22 h
  3. customThe palladium-catalyst was removed by filtration through a Celite pad
  4. concentrationThe filtrate was concentrated under reduced pressure
  5. dissolutionthe residue was dissolved in a minimum amount of ethyl acetate
  6. additionTo the above solution was added hexane
  7. customAfter removal of the precipitate
  8. filtrationby filtration
  9. concentrationthe filtrate was concentrated
  10. customThe resulting crude material was purified by FCC (1:1 v/v ethyl acetate-hexane)

Sources & evidence

ORD record
ord-ddaf48dd610a4e8bb78cf349de9b5448
Source dataset
uspto-grants-2002_10
Patent number
US06458816B1

Reaction notes

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