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

HRID 966402ノート

反応式

HRID 966402 の反応式
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

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒

実験手順

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+).

後処理

  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)

出典と根拠

ORDレコード
ord-2dfe21d739ea4474b1720c8d33b0d597
出典データセット
uspto-grants-2005_10
特許番号
US06951938B2

反応ノート

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