Dimethyl Sulfoxide → 9,9-Bis[4-(2-bromotetrafluoroethoxy)phenyl]fluorene

HRID 373286

反応式

HRID 373286 の反応式
CS(C)=O.[OH:5][C:6]1[CH:11]=[CH:10][C:9]([C:12]2([C:25]3[CH:30]=[CH:29][C:28]([OH:31])=[CH:27][CH:26]=3)[C:24]3[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=3[C:18]3[C:13]2=[CH:14][CH:15]=[CH:16][CH:17]=3)=[CH:8][CH:7]=1.[OH-].[K+].Br[C:35]([F:41])([F:40])[C:36]([F:39])([F:38])[Br:37]>C1(C)C=CC=CC=1>[Br:37][C:36]([F:39])([F:38])[C:35]([F:41])([F:40])[O:5][C:6]1[CH:7]=[CH:8][C:9]([C:12]2([C:25]3[CH:26]=[CH:27][C:28]([O:31][C:35]([F:41])([F:40])[C:36]([F:39])([F:38])[Br:37])=[CH:29][CH:30]=3)[C:13]3[CH:14]=[CH:15][CH:16]=[CH:17][C:18]=3[C:19]3[C:24]2=[CH:23][CH:22]=[CH:21][CH:20]=3)=[CH:10][CH:11]=1

参加物

6

反応物 4

HCID 679Dimethyl SulfoxideHCID 14797Potassium HydroxideHCID 313011,2-Dibromo-1,1,2,2-tetrafluoroethaneHCID 767169,9-Bis(4-hydroxyphenyl)fluorene

生成物 1

HCID 189564699,9-Bis[4-(2-bromotetrafluoroethoxy)phenyl]fluorene収率 82.1%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
100 °C

実験手順

Into a 2 liter 5-necked round bottom flask fitted with a mechanical stirrer, Dean-Stark trap topped with a nitrogen padded reflux condenser and a thermocouple attached to a temperature controller, are placed DMSO (650 ml) and toluene (200 ml). While the stirrer solution is purged with nitrogen, 9,9-bis(4'-hydroxyphenyl)fluorene (200.0 g, 0.57 mole) is added to the flask. While purging with nitrogen continues, potassium hydroxide (85% pellets, 77.5 g, 1.17 mole) is added all at once, and the mixture is heated to 100° C. with constant stirring. After two hours, the temperature is increased until the solution begins to reflux (130° C.). Water is removed by azeotropic distillation for 24 hours. The Dean-Stark trap is replaced by a Soxhlet extractor containing anhydrous sodium sulfate, and the toluene is refluxed through the Soxhlet for 5 hours. A small amount of toluene (60 ml) is then removed by simple distillation. Then the reactor is cooled to 35° C. Addition of 1,2-dibromotetrafluoroethane (315 g, 1.21 mole) via dropping addition funnel is then maintained at a rate that keeps the reaction temperature at 35°-38° C. When the addition is complete, the mixture is heated at 50° C. for 8 hours, then cooling to room temperature with constant stirring. The mixture is filtered, and the precipitate is washed twice with acetone. The filtrates are combined and evaporated thoroughly. The residue from the evaporation is washed with water to remove residual potassium bromide (KBr). After the residue is air dried for 24 hours, it is purified by column chromatography (on neutral alumina, using hexane eluent) to provide as product, 9,9-bis(4'-[2"-bromotetrafluoroethoxy]phenyl)fluorene (331.4 g, 0.468 mole, 82% yield), melting point 157°-158° C.

後処理

  1. customInto a 2 liter 5-necked round bottom flask fitted with a mechanical stirrer
  2. temperaturepadded reflux condenser
  3. additionis added to the flask
  4. customWhile purging with nitrogen
  5. temperaturethe temperature is increased until the solution
  6. temperatureto reflux (130° C.)
  7. customWater is removed by azeotropic distillation for 24 hours
  8. additioncontaining anhydrous sodium sulfate
  9. temperaturethe toluene is refluxed through the Soxhlet for 5 hours
  10. customA small amount of toluene (60 ml) is then removed by simple distillation
  11. temperatureThen the reactor is cooled to 35° C
  12. additionaddition funnel
  13. temperatureis then maintained at a rate that
  14. customat 35°-38° C
  15. additionWhen the addition
  16. temperaturethe mixture is heated at 50° C. for 8 hours
  17. temperaturecooling to room temperature with constant stirring
  18. filtrationThe mixture is filtered
  19. washthe precipitate is washed twice with acetone
  20. customevaporated thoroughly
  21. customThe residue from the evaporation
  22. washis washed with water
  23. customto remove residual potassium bromide (KBr)
  24. customdried for 24 hours
  25. customit is purified by column chromatography (on neutral alumina, using hexane eluent)
  26. customto provide as product

出典と根拠

ORDレコード
ord-bf2d6e5a8b5e4689916e9dea66c7b73c
出典データセット
uspto-grants-1992_11
特許番号
US05162468

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