反应详情

A solution of 12.12 g (50 mM) of 7,11-dicyano-4,9-dimethyl-4,9-diazatricyclo[6.2.2.02,7 ]dodec-11-ene in 150 ml of dried THF is cooled in dry ice-acetone and treated with 26 ml of 1.67 molar (43.5 mM) phenyl lithium in benzene over a 15 minute period. The reaction mixture is allowed to stir at room temperature overnight and then treated with 50 ml of 2.5 N hydrochloric acid. The layers are separated and the tetrahydrofuranbenzene layer is extracted with 20 ml of 1 N hydrochloric acid. The combined product-containing hydrochloric acid layers are washed with methylene chloride and allowed to sit at room temperature for 2 hours. After making alkaline with 5 ml of 50% sodium hydroxide solution the product is extracted into a total of 125 ml of methylene chloride which after drying over MgSO4, and concentration yields 11.35 g of a crude product. By chromatography over silica gel 11-benzoyl-7-cyano-4,9-dimethyl-4,9 -diazatricyclo[6.2.2.02,7 ]dodec-11-ene is isolated analytically pure in an overall yield of 16%, m.p. 120°-139° C., NMR and IR spectrum are in accord with the structure.

1. customThe layers are separated
2. extractionthe tetrahydrofuranbenzene layer is extracted with 20 ml of 1 N hydrochloric acid
3. additionThe combined product-containing hydrochloric acid layers
4. washare washed with methylene chloride
5. waitto sit at room temperature for 2 hours
6. extractionis extracted into a total of 125 ml of methylene chloride which
7. dry with materialafter drying over MgSO4, and concentration
8. customyields 11.35 g of a crude product
9. customBy chromatography over silica gel 11-benzoyl-7-cyano-4,9-dimethyl-4,9 -diazatricyclo[6.2.2.02,7 ]dodec-11-ene is isolated analytically pure in an overall yield of 16%, m.p. 120°-139° C., NMR and IR spectrum