反应详情

16β-Methylandrosta-1,4,9(11)-triene-3,17-dione (IB, U.S. Pat. No. 3,010,958, 20 g) is added in THF (60 ml) to the lithium acetylide at -40°. When the reaction is complete, acetone (24 ml) is added. The mixture is warmed while bubbling nitrogen thru the slurry to remove excess acetylene. Water (25 ml) is slowly added. Water (105 ml) is then added more quickly creating two phases which are separated. The aqueous phase is washed with THF (50 ml); the organic phases (pH is 9) are combined, washed with aqueous sulfuric acid and concentrated to 350 ml. Heptane (200 ml) is added, the mixture heated to 80° and held for 30 min. The mixture is cooled slowly to 30° and then to 18° for one hr. The mixture is filtered, the solid washed with heptane (20 ml) and then dried under reduced pressure with heat to give the title compound.

1. temperatureThe mixture is warmed
2. customwhile bubbling nitrogen
3. customto remove excess acetylene
4. additionWater (25 ml) is slowly added
5. additionWater (105 ml) is then added more quickly
6. customare separated
7. washThe aqueous phase is washed with THF (50 ml)
8. washwashed with aqueous sulfuric acid
9. concentrationconcentrated to 350 ml
10. additionHeptane (200 ml) is added
11. temperaturethe mixture heated to 80°
12. temperatureThe mixture is cooled slowly to 30°
13. waitto 18° for one hr
14. filtrationThe mixture is filtered
15. washthe solid washed with heptane (20 ml)
16. customdried under reduced pressure
17. temperaturewith heat