Tributylvinyltin → Ethyl 4-fluoro-3-vinylbenzoate

HRID 1808211Notes

Reaction equation

HRID 1808211 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:10]=[CH:11][C:12]=1[F:13])[C:5]([O:7][CH2:8][CH3:9])=[O:6].[CH3:14][CH2:15]CC[Sn](C=C)(CCCC)CCCC.[F-].[K+]>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[F:13][C:12]1[CH:11]=[CH:10][C:4]([C:5]([O:7][CH2:8][CH3:9])=[O:6])=[CH:3][C:2]=1[CH:14]=[CH2:15]

Participants

6

Reactant 3

HCID 81998TributylvinyltinHCID 522689Potassium FluorideHCID 24770261Ethyl 3-bromo-4-fluorobenzoate

Product 1

HCID 46941363Ethyl 4-fluoro-3-vinylbenzoateYield 87%

Reagents, catalysts & solvents 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 312751,4-DioxaneSolvent

Procedure

A mixture of compound ethyl 3-bromo-4-fluorobenzoate (Preparation 53, 81 g, 328.8 mmol, 1 eq) and bis(triphenylphosphine)palladium (II) chloride (7 g, 9.9 mmol, 0.03 eq) in dioxane (600 mL) was charged with nitrogen. Tin vinyltributyl (115 g, 361.6 mmol, 1.10 eq) was added and the mixture was heated to reflux overnight. The mixture was filtrated and the filtrate was concentrated in vacuum. The residue was dissolved in ether (2 L) and water (1 L). Then potassium fluoride (10 g, 1.7 mol, 5.17 eq) was added to the mixture and much of solid precipitated. The mixture was filtrated and the filtrate was separated. The aqueous phase was extracted with ether (200 mL×2). The combined organic phases were washed with brine, dried over sodium sulfate and concentrated in vacuo to give a residue. The residue was purified by chromatography (petroleum ether) to title compound as a colorless oil (55.8 g, 286 mmol, 87%).

Workup

  1. additionwas charged with nitrogen
  2. temperaturethe mixture was heated
  3. temperatureto reflux overnight
  4. filtrationThe mixture was filtrated
  5. concentrationthe filtrate was concentrated in vacuum
  6. dissolutionThe residue was dissolved in ether (2 L)
  7. customprecipitated
  8. filtrationThe mixture was filtrated
  9. customthe filtrate was separated
  10. extractionThe aqueous phase was extracted with ether (200 mL×2)
  11. washThe combined organic phases were washed with brine
  12. dry with materialdried over sodium sulfate
  13. concentrationconcentrated in vacuo
  14. customto give a residue

Sources & evidence

ORD record
ord-efcf117a2b7449049912b332ae2ec50c
Source dataset
uspto-grants-2013_01
Patent number
US08357711B2

Reaction notes

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