反应详情

6-Methylene-16-phenylsulfonylmethylpregna-4,16-diene-3,20-dione (IX, Preparation 6, 2.0 g) is placed in a 30-ml vial under nitrogen. Toluene (20 ml), methanol (2.89 ml), TEA (0.181 ml) and trimethylphosphite 1.02 ml) are added. After 1 hr at 20°-25°, the sealed vial was plunged into a hot oil bath with a bath temperature of 90° which is stirred at 90° for 4 hrs, at which time TLC shows the reaction to be essentially complete. The reaction mixture is transferred to a separatory funnel and water (10 ml) is added. Ethyl acetate (10 ml) is added to the organic mixture, which is washed with water (2×10 ml). The aqueous portion is back extracted with toluene/ethyl acetate: 1/1. After the phases are separated, the organic phase is filtered through sodium sulfate and the filtrate is concentrated under reduced pressure to a volume of about 8 ml. This concentrate is permitted to sit at 20°-25° for approximately 1/2 hr. The resulting crystals are washed down into a flask with toluene (2 ml) and cooled to 5° for 2 hrs, then to -20° for 48 hrs. The crystals were collected with toluene (-20°), then with hexane three times and dried under nitrogen to yield the title compound.

1. customthe sealed vial was plunged into a hot oil bath with a bath
2. customthe reaction
3. customThe reaction mixture is transferred to a separatory funnel
4. washis washed with water (2×10 ml)
5. extractionThe aqueous portion is back extracted with toluene/ethyl acetate
6. customAfter the phases are separated
7. filtrationthe organic phase is filtered through sodium sulfate
8. concentrationthe filtrate is concentrated under reduced pressure to a volume of about 8 ml
9. waitto sit at 20°-25° for approximately 1/2 hr
10. washThe resulting crystals are washed down into a flask with toluene (2 ml)
11. temperaturecooled to 5° for 2 hrs
12. waitto -20° for 48 hrs
13. customThe crystals were collected with toluene (-20°)
14. dry with materialwith hexane three times and dried under nitrogen