Cesium fluoride → 3-Allyl-1-(2-methyl-4-nitrophenyl)pyridin-2(1H)-one

HRID 85217Notes

Reaction equation

HRID 85217 reaction equation
Br[C:2]1[C:3](=[O:18])[N:4]([C:8]2[CH:13]=[CH:12][C:11]([N+:14]([O-:16])=[O:15])=[CH:10][C:9]=2[CH3:17])[CH:5]=[CH:6][CH:7]=1.[F-].[Cs+].[CH2:21](B1OC(C)(C)C(C)(C)O1)[CH:22]=[CH2:23]>C1COCC1.ClCCl.O>[CH2:23]([C:2]1[C:3](=[O:18])[N:4]([C:8]2[CH:13]=[CH:12][C:11]([N+:14]([O-:16])=[O:15])=[CH:10][C:9]=2[CH3:17])[CH:5]=[CH:6][CH:7]=1)[CH:22]=[CH2:21]

Participants

7

Reactant 3

HCID 25953Cesium fluorideHCID 27631714,4,5,5-Tetramethyl-2-(prop-2-en-1-yl)-1,3,2-dioxaborolaneHCID 594101573-Bromo-1-(2-methyl-4-nitrophenyl)pyridin-2(1H)-one

Product 1

HCID 594101353-Allyl-1-(2-methyl-4-nitrophenyl)pyridin-2(1H)-one

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

In a flask which had been dried by heating, 1.50 g (4.85 mmol) of the compound from Example 12A, 1.44 g (9.46 mmol) of caesium fluoride and 0.56 g (0.48 mmol) of tetrakis-(triphenylphosphine)palladium(0) are initially charged in 30 ml of degassed THF. A solution of 2.04 g (12.1 mmol) of 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane in 5 ml of degassed THF is added dropwise, and the mixture is heated at reflux overnight. The mixture is then diluted with dichloromethane, and water is added. After phase separation, the aqueous phase is extracted three times with dichloromethane. The combined organic phases are dried over sodium sulphate and concentrated. The product is purified by chromatography on silica gel, giving 1.18 g (62% of theory) of the title compound.

Workup

  1. customIn a flask which had been dried
  2. temperatureby heating
  3. temperaturethe mixture is heated
  4. temperatureat reflux overnight
  5. additionis added
  6. customAfter phase separation
  7. extractionthe aqueous phase is extracted three times with dichloromethane
  8. dry with materialThe combined organic phases are dried over sodium sulphate
  9. concentrationconcentrated
  10. customThe product is purified by chromatography on silica gel

Sources & evidence

ORD record
ord-60a1cc269a7945ed9a97c5cf6f05363b
Source dataset
uspto-grants-2014_09
Patent number
US08846934B2

Reaction notes

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