反应详情

To a solution of 60.0 g. of α-(m-trifluoromethylphenyl)-4-morpholineacetonitrile in 200 ml. of tetrahydrofuran is added 10 ml. of 30% potassium hydroxide in ethanol, followed by the rapid addition of 22.0 ml. of methacrylonitrile (exothermic). The mixture is stirred at room temperature overnight and the solvent is removed. To the residue is added 200 ml. of acetic acid and 20 ml. of water and this mixture is refluxed for 2 hours. The solvent is removed in vacuo and 200 ml. of 6 N hydrochloric acid is added to the residue. This mixture is refluxed for 18 hours, cooled and extracted with dichloromethane. The dichloromethane extract is passed through a column of hydrous magnesium silicate. The eluate is concentrated in vacuo and crystallized from dichloromethane-hexane giving 55 g. of off-white crystals. These crystals are dissolved in dichloromethane and extracted with saturated sodium bicarbonate solution. The aqueous extract is acidified with hydrochloric acid and extracted with dichloromethane. This organic extract is passed through hydrous magnesium silicate and the eluate is concentrated. The residue is crystallized from dichloromethane-hexane, giving 39 g. of the desired product as off-white crystals m.p. 90°-91° C.

1. customthe solvent is removed
2. additionTo the residue is added 200 ml
3. temperatureof water and this mixture is refluxed for 2 hours
4. customThe solvent is removed in vacuo and 200 ml
5. additionof 6 N hydrochloric acid is added to the residue
6. temperatureThis mixture is refluxed for 18 hours
7. temperaturecooled
8. extractionextracted with dichloromethane
9. extractionThe dichloromethane extract
10. concentrationThe eluate is concentrated in vacuo
11. customcrystallized from dichloromethane-hexane giving 55 g
12. dissolutionThese crystals are dissolved in dichloromethane
13. extractionextracted with saturated sodium bicarbonate solution
14. extractionThe aqueous extract
15. extractionextracted with dichloromethane
16. extractionThis organic extract
17. concentrationthe eluate is concentrated
18. customThe residue is crystallized from dichloromethane-hexane
19. customgiving 39 g