Hydrochloric Acid → 5,5''-Di-tert-butyl-3-(perfluorocyclopent-1-en-1-yl)-2,2':5',2''-terthiophene

HRID 589249

反応式

HRID 589249 の反応式
Br[C:2]1[CH:6]=[C:5]([C:7]([CH3:10])([CH3:9])[CH3:8])[S:4][C:3]=1[C:11]1[S:12][C:13]([C:16]2[S:17][C:18]([C:21]([CH3:24])([CH3:23])[CH3:22])=[CH:19][CH:20]=2)=[CH:14][CH:15]=1.C(=O)=O.CC(C)=O.[Li]CCCC.[F:37][C:38]1([F:49])[C:42]([F:43])=[C:41](F)[C:40]([F:46])([F:45])[C:39]1([F:48])[F:47].Cl>C(OCC)C.CO.O>[C:7]([C:5]1[S:4][C:3]([C:11]2[S:12][C:13]([C:16]3[S:17][C:18]([C:21]([CH3:24])([CH3:23])[CH3:22])=[CH:19][CH:20]=3)=[CH:14][CH:15]=2)=[C:2]([C:41]2[C:40]([F:46])([F:45])[C:39]([F:47])([F:48])[C:38]([F:37])([F:49])[C:42]=2[F:43])[CH:6]=1)([CH3:10])([CH3:9])[CH3:8]

参加物

9

反応物 5

HCID 313Hydrochloric AcidHCID 11212PerfluorocyclopenteneHCID 18522661Acetone cardiceHCID 89479847HCID 89479847、化合物HCID 178418339Butyllithium

生成物 1

HCID 894840555,5''-Di-tert-butyl-3-(perfluorocyclopent-1-en-1-yl)-2,2':5',2''-terthiophene

試薬・触媒・溶媒 3

HCID 887Methanol溶媒HCID 962Water溶媒HCID 3283Diethyl Ether溶媒

反応条件

温度
-45 °C

実験手順

In a flame-dried, 1 L rbf, 3-bromo-5,5″-di-t-butyl-2,2′:5′,2″-terthiophene (112, 4 g, 9.10 mmol) was dissolved in anhydrous diethyl ether (400 mL) and cooled to −48° C. (dry ice/acetone). n-BuLi (2.5 M in hexanes, 1.5 mL, 3.82 mmol) was added dropwise over a period of 5 minutes. The resulting yellow solution was allowed to stir for 20 minutes, then octafluorocyclopentene (0.24 mL, 1.82 mmol) was added in one portion. The reaction mixture warmed to −45° C. The reaction mixture was allowed to mix and slowly warm to 5° C., and then was poured into water (300 mL) and mixed well, then acidified with 10% HCl (100 mL). The aqueous phase was separated and extracted with EtOAc (2×100 mL). The combined organics were washed with water (500 mL), dried over MgSO4, filtered and solvent removed by rotary evaporation. The resulting dark orange oil was redissolved in chloroform and dry-loaded onto silica gel. Flash chromatography (hexanes) afforded a yellow oil, which was sonicated in methanol, filtered and air dried to afford 113 as a bright yellow, powdery solid (3.62 g, 72%).

後処理

  1. additionto mix
  2. temperatureslowly warm to 5° C.
  3. additionmixed well
  4. customThe aqueous phase was separated
  5. extractionextracted with EtOAc (2×100 mL)
  6. washThe combined organics were washed with water (500 mL)
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. customsolvent removed by rotary evaporation
  10. dissolutionThe resulting dark orange oil was redissolved in chloroform and dry-loaded onto silica gel
  11. customFlash chromatography (hexanes) afforded a yellow oil, which
  12. filtrationfiltered
  13. customair dried

出典と根拠

ORDレコード
ord-7a2d3828dab44eb7a9c433f2b80e640f
出典データセット
uspto-grants-2016_01
特許番号
US09227986B2

関連ノート

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