反应详情

To a suspension of 20 g. (0.5 mole) of sodamide in 750 ml. of dry toluene was added dropwise 50.58 g. (0.5 mole) of 1-methyl-3-pyrrolidinol with cooling below 30° C. After stirring for 1 hour, 95.32 g. (0.5 mole) of p-toluene sulfonyl chloride in 500 ml. of dry toluene was added rapidly at a temperature below 10° C. maintained by dry ice/acetone bath. The temperature was allowed to come to room temperature and stirred for 2 hours. The reaction mixture was cooled, washed with 500 ml. of cold water and the toluene layer was dried over calcium sulfate, filtered and the dried toluene solution concentrated at reduced pressure. To 93.5 g. (0.39 mole) of N,N-dimethyl-α,α-diphenylacetamide in 500 ml. of dry toluene was added 15.6 g. (0.4 mole) of sodamide and the mixture was slowly brought to reflux with stirring. After refluxing for 3 hours, the tosylate in 250 ml. of dry toluene was added at a convenient rate to the refluxing reaction mixture which was then refluxed for 3 hours. The resulting suspension was filtered and the toluene filtrate was evaporated under water pump vacuum, leaving an oil which on cooling became semi-crystalline and was taken into 6N hydrochloric acid. The acid solution was extracted with ether, made basic with 6N sodium hydroxide and the base insoluble oil extracted with ether. The ether extracts were dried over calcium sulfate, filtered, and evaporated leaving an amber oil. The product was distilled at 175°-180° C./0.005 mm. to give 22 g. (38%) of product.

1. additionTo a suspension of 20 g
2. temperaturemaintained by dry ice/acetone bath
3. customto come to room temperature
4. stirringstirred for 2 hours
5. temperatureThe reaction mixture was cooled
6. washwashed with 500 ml
7. dry with materialof cold water and the toluene layer was dried over calcium sulfate
8. filtrationfiltered
9. concentrationthe dried toluene solution concentrated at reduced pressure
10. temperatureto reflux
11. stirringwith stirring
12. temperatureAfter refluxing for 3 hours
13. temperaturewas then refluxed for 3 hours
14. filtrationThe resulting suspension was filtered
15. customthe toluene filtrate was evaporated under water pump vacuum
16. customleaving an oil which
17. temperatureon cooling
18. extractionThe acid solution was extracted with ether
19. extractionthe base insoluble oil extracted with ether
20. dry with materialThe ether extracts were dried over calcium sulfate
21. filtrationfiltered
22. customevaporated
23. customleaving an amber oil
24. distillationThe product was distilled at 175°-180° C./0.005 mm
25. customto give 22 g