反应详情

Mercuric oxide red (0.32 g) was mixed with sulfuric acid/water (sulfuric acid, 0.4 ml; water, 6.0 ml) and let stand overnight. 17α-Ethynyl-17β-hydroxy-6,16-dimethyleneandrosta-4-en-3-one (Example 4, 5.0 g) is mixed with THF (15 ml). The mercuric sulfate solution is added the reaction heated to 41°-49° over a period of 6 hrs at which time TLC indicates the reaction is completed. Sodium carbonate (0.79 g) in water (10 ml) is added and the mixture stirred for 5 min. Celite (5 g) is added and the mixture stirred 1/2 hr at 20°-25°. The mixture is filtered through Celite (5 g), the solids washed with methanol/THF; 1/1 (2×10 ml) and once with THF (10 ml), followed by methylene chloride (10 ml). The filtrate and washings are concentrated under reduced pressure to about 35 ml, at which point crystals begin forming. Methanol (50 ml) is added and the mixture again concentrated under reduced pressure and permitted to sit overnight at 20°-25° under nitrogen atmosphere. Water (500 ml) is added, slowly at first, with stirring over a period of 15 min. The mixture is filtered, the solids washed with water (3×20 ml), and hexane (2×10 ml). The solids were dried under nitrogen to give the title compound.

1. temperatureheated to 41°-49° over a period of 6 hrs at which time TLC
2. additionCelite (5 g) is added
3. stirringthe mixture stirred 1/2 hr at 20°-25°
4. filtrationThe mixture is filtered through Celite (5 g)
5. washthe solids washed with methanol/THF
6. concentrationThe filtrate and washings are concentrated under reduced pressure to about 35 ml, at which point crystals
7. custombegin forming
8. concentrationthe mixture again concentrated under reduced pressure
9. waitto sit overnight at 20°-25° under nitrogen atmosphere
10. additionWater (500 ml) is added
11. stirringslowly at first, with stirring over a period of 15 min
12. filtrationThe mixture is filtered
13. washthe solids washed with water (3×20 ml), and hexane (2×10 ml)
14. customThe solids were dried under nitrogen