反应详情

9α-Hydroxyandrostenedione (20.00 g.) is dissolved in methylene chloride (150 ml.) and cooled to -19°. Chlorosulfonic acid (10 ml.) is added while maintaining the temperature at less than or equal to -9°. After only a few minutes the reaction is shown to be nearly complete as measured by TLC. Additional chlorosulfonic acid (1 ml.) is added. Water (50 ml.) is added to the reaction mixture with the temperature rising from -18° to -1°. The phases are separated and the aqueous phase is extracted with methylene chloride (125 ml.). The organic phase is washed with aqueous sodium bicarbonate solution (10%, 50 ml.). The aqueous phases are combined and back extracted with methylene chloride. The organic phases are combined and concentrated under vacuum to approximately 80 ml. at a temperature of about 20°-23°. Heptane (100 ml.) is added and the mixture stirred for approximately 4 minute at approximately 19°. The mixture is concentrated under vacuum to approximately 100 ml. at a temperature of about 25°-30°. Heptane (50 ml.) is again added and the mixture again concentrated to approximately 100 ml. The mixture is cooled to 25° and stirred for 15 minutes, filtered, and the crystalline material washed with heptane (25 ml.) and dried under vacuum at 50° to give androsta-4,9(11)-diene-3,17-dione, 17.96 g. (89.8% weight yield, 95.3 % chemical yield); m.p. 197.5°-203.5°; [α]D +220° (chloroform); UV (methanol)λmax =240 nm (ε=16,200).

1. temperaturecooled to -19°
2. temperaturewhile maintaining the temperature at less than or equal to -9°
3. waitAfter only a few minutes the reaction is shown
4. customrising from -18° to -1°
5. customThe phases are separated
6. extractionthe aqueous phase is extracted with methylene chloride (125 ml.)
7. washThe organic phase is washed with aqueous sodium bicarbonate solution (10%, 50 ml.)
8. extractionback extracted with methylene chloride
9. concentrationconcentrated under vacuum to approximately 80 ml
10. customat a temperature of about 20°-23°
11. additionHeptane (100 ml.) is added
12. concentrationThe mixture is concentrated under vacuum to approximately 100 ml
13. customat a temperature of about 25°-30°
14. additionHeptane (50 ml.) is again added
15. concentrationthe mixture again concentrated to approximately 100 ml
16. temperatureThe mixture is cooled to 25°
17. stirringstirred for 15 minutes
18. filtrationfiltered
19. washthe crystalline material washed with heptane (25 ml.)
20. customdried under vacuum at 50°