Tetrabutylammonium Fluoride → (E)-tert-butyl 2-fluoro-4-(3,3,3-trifluoroprop-1-enyl)benzoate

HRID 2102925노트

반응식

HRID 2102925 반응식
CCCC[N+](CCCC)(CCCC)CCCC.[F-].[F:19][C:20]1[CH:32]=[C:31]([CH:33]=O)[CH:30]=[CH:29][C:21]=1[C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23].[F:35][C:36]([F:53])([F:52])[CH2:37]P(=O)(C1C=CC=CC=1)C1C=CC=CC=1>C1COCC1>[F:19][C:20]1[CH:32]=[C:31](/[CH:33]=[CH:37]/[C:36]([F:53])([F:52])[F:35])[CH:30]=[CH:29][C:21]=1[C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23]

참가 물질

5

반응물 3

HCID 2724141Tetrabutylammonium FluorideHCID 11323568Diphenyl(2,2,2-trifluoroethyl)phosphine oxideHCID 86607392tert-Butyl 2-fluoro-4-formylbenzoate

생성물 1

HCID 68704410(E)-tert-butyl 2-fluoro-4-(3,3,3-trifluoroprop-1-enyl)benzoate수율 64.7%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

실험 절차

Molecular sieves 4 Å (powder, 24 g) was added to a 1 M solution of TBAF in THF (30 mL, 30 mmol), and the mixture was stirred at room-temperature overnight under an argon atmosphere. To the mixture were added a solution of tert-butyl 2-fluoro-4-formylbenzoate (750 mg, 0.0033 mol) and 2,2,2-trifluoroethyldiphenylphosphine oxide (1.9 g, 0.0067 mol) in THF (30 mL). After the mixture was stirred for 2 h it was filtered. The filtrate was concentrated under vacuum and water (120 mL) was added. The mixture was extracted with AcOEt and the organic extract was washed with brine, dried (Na2SO4), and concentrated under vacuum. The residue was purified by column chromatography on silica gel using AcOEt-hexane (0-15%) as eluent to give (E)-tert-butyl 2-fluoro-4-(3,3,3-trifluoroprop-1-enyl)benzoate as a colorless oil (620 mg, 64%), followed by (Z)-tert-butyl 2-fluoro-4-(3,3,3-trifluoroprop-1-enyl)benzoate as a colorless oil (80 mg, 8%).

후처리

  1. stirringAfter the mixture was stirred for 2 h it
  2. filtrationwas filtered
  3. concentrationThe filtrate was concentrated under vacuum and water (120 mL)
  4. additionwas added
  5. extractionThe mixture was extracted with AcOEt
  6. extractionthe organic extract
  7. washwas washed with brine
  8. dry with materialdried (Na2SO4)
  9. concentrationconcentrated under vacuum
  10. customThe residue was purified by column chromatography on silica gel

출처 및 근거

ORD 기록
ord-9261dd154d3447f2b110596b1bd14ae4
출처 데이터셋
uspto-grants-2009_08
특허 번호
US07576099B2

반응 노트

불러오는 중…