Cyclopentadiene → 5-Fluoro-1,4-dihydro-1,4-methano-naphthalene

HRID 966402노트

반응식

HRID 966402 반응식
F[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([F:8])[C:3]=1I.[CH:10]1[CH2:14][CH:13]=[CH:12][CH:11]=1.[Li]CCCC>CCOCC>[F:8][C:4]1[CH:5]=[CH:6][CH:7]=[C:2]2[C:3]=1[CH:14]1[CH2:13][CH:12]2[CH:11]=[CH:10]1

참가 물질

5

반응물 3

HCID 7612CyclopentadieneHCID 27827381,3-Difluoro-2-iodobenzeneHCID 178418339Butyllithium

생성물 1

HCID 1437965-Fluoro-1,4-dihydro-1,4-methano-naphthalene

시약·촉매·용매 1

HCID 3283Diethyl Ether용매

실험 절차

A solution of 2,6-difluoroiodobenzene (5.0 g, 20.8 mmol) and cyclopentadiene (2.07 g, 31.3 mmol) was stirred at 0° C. in P. ether (70 mL, 40-60° C.) under N2 and treated with n-BuLi (8.74 mL, 2.5M in hexanes, 21.8 mmol) dropwise over 10 minutes. The reaction was quenched after 15 minutes by addition of aqueous 1N HCl solution and the product was extracted with hexanes (3×50 mL). The combined organic layer was washed with H2O (50 mL), saturated aqueous NaCl solution (50 mL), dried (MgSO4), filtered and evaporated Chromatography on Silica gel provided product as an oil (1.5 g, 45%) (TLC hexanes Rf 0.55). 1H NMR (400 MHz, CDCl3) δ 7 08 (ddd, J=7 0, 1.0, 0.8 Hz, 1H), 6.96 (ddd, J=8.5, 8.3, 7 0 Hz, 1H), 6.86 (br s, 2H), 6.72 (ddd, J=8.5, 8.3, 0.8 Hz, 1H), 4.25 (br s, 1 H), 3.98 (br s, 1H), 2.36 (ddd, J=7.2, 1.7, 1.7 Hz, 1H), 2.30 (ddd, J=7 2, 1.7, 1.5 Hz, 1H). GCMS m/e 160 (M+).

후처리

  1. customThe reaction was quenched after 15 minutes by addition of aqueous 1N HCl solution
  2. extractionthe product was extracted with hexanes (3×50 mL)
  3. washThe combined organic layer was washed with H2O (50 mL), saturated aqueous NaCl solution (50 mL)
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. customevaporated Chromatography on Silica gel provided product as an oil (1.5 g, 45%) (TLC hexanes Rf 0.55)

출처 및 근거

ORD 기록
ord-2dfe21d739ea4474b1720c8d33b0d597
출처 데이터셋
uspto-grants-2005_10
특허 번호
US06951938B2

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