Toluene → Tralopyril

HRID 1651707

反応式

HRID 1651707 の反応式
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[NH:9][C:10]([C:15]([F:18])([F:17])[F:16])=[CH:11][C:12]=2[C:13]#[N:14])=[CH:4][CH:3]=1.[Br:19]Br.C1(C)C=CC=CC=1>C(O)(=O)C>[Br:19][C:11]1[C:12]([C:13]#[N:14])=[C:8]([C:5]2[CH:4]=[CH:3][C:2]([Cl:1])=[CH:7][CH:6]=2)[NH:9][C:10]=1[C:15]([F:18])([F:16])[F:17]

参加物

5

反応物 3

HCID 1140TolueneHCID 24408Bromine2 回HCID 110001432-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile

生成物 1

HCID 183559Tralopyril

試薬・触媒・溶媒 1

HCID 176Acetic Acid溶媒3 回

実験手順

Under a nitrogen purge, a suspension or 2-(p-chlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile (1.6 g; 0.005 mol) in acetic acid (25 mL) is heated, all the material dissolving to a clear solution at about 60° C. A solution of bromine (0.8 mL; 0.015 mol) in acetic acid (10 mL) is added dropwise over 15 minutes to the refluxing solution. The solution is refluxed 6 hours then allowed to stir 18 hours at room temperature. The HPLC of the reaction mixture shows about 80% conversion to product. The mixture is heated back to reflux and more bromine (0.5 mL; 0.01 mol) in acetic acid (5 mL) is added dropwise. After refluxing another 3 hours, the aliquot shows >95% conversion to product. The reaction is cooled, and solvent removed under reduced pressure on a rotary evaporator to obtain a dark grey solid. Toluene is added to the mixture and removed under reduced pressure, but the odor of acetic acid still remains. The entire material is dissolved in hot toluene (75 mL) to a turbid solution which is treated with DARCO filter and filtered. The light pink solution deposits a white solid upon cooling to ambient. After cooling in the freezer, the solid is collected by filtration, washed with hexanes, and dried on the filter. Further drying in a vacuum oven at 45° C. provides the product (1.2 g; app. 60% theoretical); m.p. 247°-250° C.(dec.)

後処理

  1. customUnder a nitrogen purge
  2. dissolutionall the material dissolving to a clear solution at about 60° C
  3. temperatureThe solution is refluxed 6 hours
  4. temperatureThe mixture is heated back
  5. temperatureto reflux
  6. temperatureAfter refluxing another 3 hours
  7. temperatureThe reaction is cooled
  8. customsolvent removed under reduced pressure on a rotary evaporator
  9. customto obtain a dark grey solid
  10. customremoved under reduced pressure
  11. dissolutionThe entire material is dissolved in hot toluene (75 mL) to a turbid solution which
  12. additionis treated with DARCO
  13. filtrationfilter
  14. filtrationfiltered
  15. temperatureThe light pink solution deposits a white solid upon cooling to ambient
  16. temperatureAfter cooling in the freezer
  17. filtrationthe solid is collected by filtration
  18. washwashed with hexanes
  19. customdried on the filter
  20. customFurther drying in a vacuum oven at 45° C.
  21. customprovides the product (1.2 g

出典と根拠

ORDレコード
ord-c13f6e28d051403f9b37685f6bb6fe0c
出典データセット
uspto-grants-1990_05
特許番号
US04929634

関連ノート

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