Hydrochloric Acid → 4-(4-(2-Fluoroethyl)cyclohexyl)-1-(2-(4-trifluoromethoxyphenyl)ethyl)-1-cyclohexene

HRID 1941030ノート

反応式

HRID 1941030 の反応式
[F:1][C:2]([F:14])([F:13])[O:3][C:4]1[CH:9]=[CH:8][C:7]([CH2:10][CH2:11]Br)=[CH:6][CH:5]=1.[F:15][CH2:16][CH2:17][CH:18]1[CH2:23][CH2:22][CH:21]([CH:24]2[CH2:29][CH2:28][C:27](=O)[CH2:26][CH2:25]2)[CH2:20][CH2:19]1.Cl>CCOCC>[F:15][CH2:16][CH2:17][CH:18]1[CH2:19][CH2:20][CH:21]([CH:24]2[CH2:29][CH2:28][C:27]([CH2:11][CH2:10][C:7]3[CH:8]=[CH:9][C:4]([O:3][C:2]([F:14])([F:13])[F:1])=[CH:5][CH:6]=3)=[CH:26][CH2:25]2)[CH2:22][CH2:23]1

参加物

5

反応物 3

HCID 313Hydrochloric AcidHCID 153901221-(2-Bromoethyl)-4-(trifluoromethoxy)benzeneHCID 214594604-(4-(2-Fluoroethyl)cyclohexyl)cyclohexanone

生成物 1

HCID 214594534-(4-(2-Fluoroethyl)cyclohexyl)-1-(2-(4-trifluoromethoxyphenyl)ethyl)-1-cyclohexene収率 46.4%

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒2 回

反応条件

温度
0 °C

実験手順

A Grignard reagent prepared from the above 2-(4-trifluoromethoxyphenyl)bromoethane (7.0 g, 30.3 mmol) and dried Mg (0.74 g, 30.4 mmol) in an ether solvent (40 ml) was cooled down to 0° C., followed by dropwise adding thereto a 30 ml ether solution of 4-(4-(2-fluoroethyl)cyclohexyl)cyclohexanone (2.2 g, 9.7 mmol) prepared at the third step, stirring the mixture at 0° C. for 3 hours, adding 6N HCl to the reaction solution, extracting the resulting product with toluene, washing the extraction solution successively with a saturated aqueous solution of sodium bicarbonate and water, drying over magnesium sulfate, distilling off the solvent, adding toluene (100 ml) and Amberlist (500 mg) to the resulting yellow oily substance, refluxing the mixture for 4 hours, while removing water formed by the reaction by means of Dean-Stark, filtering off Amberlist, distilling off the solvent, purifying the residue according to column chromatography treatment using toluene as a developing solvent, on silica gel, to isolate 4-(4-(2-fluoroethyl)cyclohexyl)-1-(2-(4-trifluoromethoxyphenyl)ethyl)-1-cyclohexene (1.8 g, 4.5 mmol), hydrogenating this product (1.2 g, 3.0 mmol) in the presence of 5% Pd/C catalyst (0.12 g) in ethanol solution, filtering off the catalyst, distilling off the solvent under reduced pressure, and recrystallizing the residue, to isolate only trans-form of colorless 1-(2-(4-(4-(2-fluoroethyl)-cyclohexyl)cyclohexyl)ethyl-4-trifluoromethoxybenzene (0.37 g, 0.90 mmol) exhibiting smectic phase. The yield of this product from 4-(4-(2-fluoroethyl)chclohexyl)cyclohexanone was 9.3%.

後処理

  1. additionby dropwise adding
  2. extractionextracting the resulting product with toluene
  3. washwashing the extraction solution successively with a saturated aqueous solution of sodium bicarbonate and water
  4. dry with materialdrying over magnesium sulfate
  5. distillationdistilling off the solvent
  6. additionadding toluene (100 ml) and Amberlist (500 mg) to the resulting yellow oily substance
  7. temperaturerefluxing the mixture for 4 hours
  8. customwhile removing water
  9. customformed by the reaction by means of Dean-Stark
  10. filtrationfiltering off Amberlist
  11. distillationdistilling off the solvent
  12. custompurifying the residue

出典と根拠

ORDレコード
ord-7d89458af1124df9a1edd0007d9e4d3d
出典データセット
uspto-grants-1997_12
特許番号
US05702641

反応ノート

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