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Perfluorocyclopentene → 3-(Perfluorocyclopent-1-en-1-yl)-2-phenyl-5-(4-vinylphenyl)thiophene

HRID 589237
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HRID 589237 반응식
Br[C:2]1[CH:6]=[C:5]([C:7]2[CH:12]=[CH:11][C:10]([CH:13]=[CH2:14])=[CH:9][CH:8]=2)[S:4][C:3]=1[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.[Li]CCCC.[F:26][C:27]1([F:38])[C:31]([F:32])=[C:30](F)[C:29]([F:35])([F:34])[C:28]1([F:37])[F:36]>CCOCC>[F:32][C:31]1[C:27]([F:26])([F:38])[C:28]([F:36])([F:37])[C:29]([F:34])([F:35])[C:30]=1[C:2]1[CH:6]=[C:5]([C:7]2[CH:12]=[CH:11][C:10]([CH:13]=[CH2:14])=[CH:9][CH:8]=2)[S:4][C:3]=1[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1
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참가 물질

5

반응물 3

HCID 11212PerfluorocyclopenteneHCID 894798823-Bromo-2-phenyl-5-(4-vinylphenyl)thiopheneHCID 178418339Butyllithium

생성물 1

HCID 894839013-(Perfluorocyclopent-1-en-1-yl)-2-phenyl-5-(4-vinylphenyl)thiophene수율 67.1%

시약·촉매·용매 1

HCID 3283Diethyl Ether용매

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온도
-70 °C

실험 절차

Compound 31 (6.41 g, 18.8 mmol) was dissolved in 500 mL anhydrous Et2O and cooled to −25° C. n-BuLi (2.5 M in hexane, 9.8 mL, 24.4 mmol) was added dropwise over 45 min. Lithiation was determined to be complete by TLC after the addition of approximately 7 mL. The lithiated species precipitated from solution. Octafluorocyclopentene (5.18 mL, 37.6 mmol) was added and the reaction mixture stirred at −70° C. for 1.5 hours before warming slowly to −20° C. over 30 min, to 0° C. for 30 minutes then to room temperature for 1 hour. The reaction mixture was quenched with water and extracted with EtOAc (3×100 mL). The combined organic fractions were washed with brine, dried over MgSO4 and concentrated under vacuum. Purification by column chromatography afforded 32 (5.73 g, 67% yield). 1H NMR (600 MHz, CDCl3) δ 7.59 (d, J=8.3, 2H), 7.46 (d, J=8.2, 2H), 7.45-7.35 (m, 6H), 6.74 (dd, J=17.6, 10.9, 1H), 5.81 (d, J=17.6, 1H), 5.31 (d, J=10.9, 1H).

후처리

  1. additionwas added dropwise over 45 min
  2. additionafter the addition of approximately 7 mL
  3. customThe lithiated species precipitated from solution
  4. temperaturebefore warming slowly to −20° C. over 30 min, to 0° C. for 30 minutes
  5. waitto room temperature for 1 hour
  6. customThe reaction mixture was quenched with water
  7. extractionextracted with EtOAc (3×100 mL)
  8. washThe combined organic fractions were washed with brine
  9. dry with materialdried over MgSO4
  10. concentrationconcentrated under vacuum
  11. customPurification by column chromatography

출처 및 근거

ORD 기록
ord-e77b0da5cc154d8788e7570bd21e7147
출처 데이터셋
uspto-grants-2016_01
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US09227986B2

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