Tributylvinyltin → Ethyl 4-fluoro-3-vinylbenzoate

HRID 401790노트

반응식

HRID 401790 반응식
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]

참가 물질

6

반응물 3

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

생성물 1

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

시약·촉매·용매 2

HCID 6102075Dichlorobis(triphenylphosphine)palladium촉매HCID 312751,4-Dioxane용매

실험 절차

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 (100 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%).

후처리

  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

출처 및 근거

ORD 기록
ord-b9cc37c5b4994d0f9be8fb9cdfeaef3e
출처 데이터셋
uspto-grants-2014_06
특허 번호
US08741934B2

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