Isopropenyl acetate → 2-Fluoro-4-biphenylyl acetone

HRID 849376

Reaction equation

HRID 849376 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)=[C:4]([F:14])[CH:3]=1.C[O-].C([Sn+](CCCC)CCCC)CCC.C([O:33][C:34]([CH3:36])=[CH2:35])(=O)C.[F-].[K+]>C1(C)C=CC=CC=1>[F:14][C:4]1[CH:3]=[C:2]([CH2:35][C:34](=[O:33])[CH3:36])[CH:7]=[CH:6][C:5]=1[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1

Participants

6

Reactant 4

HCID 7916Isopropenyl acetateHCID 5210634-Bromo-2-fluoro-1,1'-biphenylHCID 522689Potassium FluorideHCID 11964040Methoxytri-n-butylstannane

Product 1

HCID 129504182-Fluoro-4-biphenylyl acetone

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

15.0 g of 4-bromo-2-fluorobiphenyl, 25.8 ml of tributyltin methoxide, 8.96 g of isopropenyl acetate and 0.47 g of dichlorobis{tri(o-tolyl)phosphine}palladium, were dissolved in 100 ml of toluene and refluxed under heating for 2 hours. The reaction solution was left to cool to room temperature, and a saturated potassium fluoride aqueous solution was added, followed by stirring for one hour. Then the solution was subjected to celite filtration and washed with ethyl acetate. The filtrate and the washing liquid were put together. Then, the organic layer was separated and washed with a saturated sodium chloride aqueous solution and then, dried over anhydrous magnesium sulfate. The drying agent was filtered off, and then, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=10/1→5/1), followed by treatment with methylene chloride-hexane, to obtain 10.6 g of the above identified compound as yellow solid.

Workup

  1. temperaturerefluxed
  2. temperatureunder heating for 2 hours
  3. waitThe reaction solution was left
  4. filtrationThen the solution was subjected to celite filtration
  5. washwashed with ethyl acetate
  6. customThen, the organic layer was separated
  7. washwashed with a saturated sodium chloride aqueous solution
  8. dry with materialdried over anhydrous magnesium sulfate
  9. filtrationThe drying agent was filtered off
  10. distillationthe solvent was distilled off under reduced pressure
  11. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate=10/1→5/1)
  12. customto obtain 10.6 g of the

Sources & evidence

ORD record
ord-5ff20dfa283b45cd9c16cda02f7dc8d9
Source dataset
uspto-grants-2000_01
Patent number
US06011174

Linked notes

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