(8S,9R,10S,11S,13S,14S)-17-乙酰基-9-氟-11-羟基-10,13-二甲基-2,6,7,8,11,12,14,15-八氢-1H-环戊烷[a]菲-3-酮

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 8.5 ml of dry pyridine in 220 ml of dry dichloromethane is added 5.1 g of chromium trioxide in small portions. When all the solid has dissolved, 25 g of dry Celite is added followed (with stirring) by a solution of 3.0 g of 9-fluoro-11β-hydroxypregna-4,16-diene-3,20-dione. The mixture is then stirred at room temperature for 30 minutes, filtered and the solids are washed with a small amount of dichloromethane. The filtrate and the washings are combined, washed with 5% hydrochloric acid, a dilute sodium bicarbonate solution and water, dried and evaporated to afford the product as a solid. One crystallization from acetone-hexane gives 2.65 g of the title compound, melting point 208°-211°C. When all the solid has dissolved 25 g of dry Celite is added filtered the solids are washed with a small amount of dichloromethane washed with 5% hydrochloric acid a dilute sodium bicarbonate solution and water, dried evaporated

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 8.5 ml of dry pyridine in 220 ml of dry dichloromethane is added 5.1 g of chromium trioxide in small portions. When all the solid has dissolved, 25 g of dry Celite is added followed (with stirring) by a solution of 3.0 g of 9-fluoro-11β-hydroxypregna-4,16-diene-3,20-dione. The mixture is then stirred at room temperature for 30 minutes, filtered and the solids are washed with a small amount of dichloromethane. The filtrate and the washings are combined, washed with 5% hydrochloric acid, a dilute sodium bicarbonate solution and water, dried and evaporated to afford the product as a solid. One crystallization from acetone-hexane gives 2.65 g of the title compound, melting point 208°-211°C. When all the solid has dissolved 25 g of dry Celite is added filtered the solids are washed with a small amount of dichloromethane washed with 5% hydrochloric acid a dilute sodium bicarbonate solution and water, dried evaporated

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 8.5 ml of dry pyridine in 220 ml of dry dichloromethane is added 5.1 g of chromium trioxide in small portions. When all the solid has dissolved, 25 g of dry Celite is added followed (with stirring) by a solution of 3.0 g of 9-fluoro-11β-hydroxypregna-4,16-diene-3,20-dione. The mixture is then stirred at room temperature for 30 minutes, filtered and the solids are washed with a small amount of dichloromethane. The filtrate and the washings are combined, washed with 5% hydrochloric acid, a dilute sodium bicarbonate solution and water, dried and evaporated to afford the product as a solid. One crystallization from acetone-hexane gives 2.65 g of the title compound, melting point 208°-211°C. When all the solid has dissolved 25 g of dry Celite is added filtered the solids are washed with a small amount of dichloromethane washed with 5% hydrochloric acid a dilute sodium bicarbonate solution and water, dried evaporated

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 1-Phenyl-1-tetrahydropyranyloxyacetonitrile (1.3 g.) is added to a suspension of 57% sodium hydride-paraffin (275 mg.) in dry dimethylsulfoxide (20 ml.) in a nitrogen atmosphere. The mixture is stirred at room temperature for 90 minutes to yield a homogeneous solution of the anion. To the anion is added a solution of 9-fluoro-11β-hydroxypregna-4,16-diene-3,20-dione (1.04 g.) in dry dimethylsulfoxide. After 30 minutes, the mixture is poured into water and extracted with ethyl acetate. The extracts are combined, washed with water, dried over magnesium sulfate and evaporated to afford 2.55g. of a gum. This is dissolved in methanol (25 ml.), conc. hydrochloric acid (2 drops) is added and the solution is maintained in a bath at 55°-60°C for 5.0 hours. The methanol is evaporated in vacuo, the residue is dissolved in ethyl acetate, washed with a diluted sodium bicarbonate solution and water, dried over magnesium sulfate and evaporated to afford the crude product as a gum. This is absorbed on a dry column of silica gel (40 g.) and the column is eluted successively with chloroform, ethyl acetate-chloroform (1:9) and ethyl acetate. Crystallization of the material (1.1 g.) eluted with ethyl acetate-chloroform from acetone-hexane affords the analytical specimen (690 mg.), melting point 250° -252°C, dec. to yield a homogeneous solution of the anion After 30 minutes extracted with ethyl acetate washed with water dried over magnesium sulfate evaporated to afford 2.55g the solution is maintained in a bath at 55°-60°C for 5.0 hours The methanol is evaporated in vacuo the residue is dissolved in ethyl acetate washed with a diluted sodium bicarbonate solution and water dried over magnesium sulfate evaporated

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 8.5 ml of dry pyridine in 220 ml of dry dichloromethane is added 5.1 g of chromium trioxide in small portions. When all the solid has dissolved, 25 g of dry Celite is added followed (with stirring) by a solution of 3.0 g of 9-fluoro-11β-hydroxypregna-4,16-diene-3,20-dione. The mixture is then stirred at room temperature for 30 minutes, filtered and the solids are washed with a small amount of dichloromethane. The filtrate and the washings are combined, washed with 5% hydrochloric acid, a dilute sodium bicarbonate solution and water, dried and evaporated to afford the product as a solid. One crystallization from acetone-hexane gives 2.65 g of the title compound, melting point 208°-211°C. When all the solid has dissolved 25 g of dry Celite is added filtered the solids are washed with a small amount of dichloromethane washed with 5% hydrochloric acid a dilute sodium bicarbonate solution and water, dried evaporated