反应详情

温度

70 °C

Sodium hydride (60%, 26 mg, 0.66 mmole) was added to a solution of 101 mg. (0.33 mol) of 17-keto-4-methyl-5α-androstan-3-one (F) and 173 mg (0.66 mol) of diethyl 2-chlorobenzylphosphonate in 1.0 ml of dry DMF at room temperature. The mixture was heated at 70° C. in a nitrogen atmosphere with stirring for 110 minutes, cooled, poured into 0.5N HCl (20 ml) and extracted with methylene chloride (3×). The organic phases were combined, washed with water (3×), saturated NaCl solution and dried over magnesium sulfate. The organic phase was concentrated under reduced pressure to yield a tan, gummy solid. Flash chromatography of the crude solid was conducted on a silica gel 60×20 mm column, and eluted with 4:1 methylene chloride/acetone in 6 ml. fractions. Fractions 18-24 contained the product which were combined and evaporated to yield a white solid, mp 205°-208° C., yielding one spot on silica gel TLC using 4:1 methylene chloride/acetone. The proton NMR confirmed the assigned structure for 39.

1. customat room temperature
2. temperaturecooled
3. extractionextracted with methylene chloride (3×)
4. washwashed with water (3×), saturated NaCl solution
5. dry with materialdried over magnesium sulfate
6. concentrationThe organic phase was concentrated under reduced pressure
7. customto yield a tan, gummy solid
8. washeluted with 4:1 methylene chloride/acetone in 6 ml
9. customevaporated
10. customto yield a white solid, mp 205°-208° C.
11. customyielding one spot on silica gel TLC