Method for preparing 6,7-dehydro-17beta-hydrocarbon acyloxy nandrolone
An alkanoyloxynandrolone and dehydrogenation technology is applied in the field of preparation of pharmaceutical intermediates, which can solve the problems of difficult control, many by-products, difficult separation and purification, etc., and achieves easy reaction control, low price and simple conditions. Effect
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Embodiment 1
[0025] Dissolve 3-tris(isopropyl)silyloxy-17β-acetoxy-3,5-androstadiene (0.970 g, 2.50 mmol) in anhydrous DMF (20 ml), N 2 Stir and cool to 0 °C under protection. Slowly add (NH 4 ) 2 Ce(NO 3 ) 6 (3.06 g, 5.60 mmol), the addition was completed in about half an hour, and the reaction mass was stirred for 1 h at 0°C. After the reaction is complete, pour the reaction solution into 30 ml saturated NaHCO 3 solution, and with CH 2 Cl 2 (20 ml *3) extracted. The combined organic phases were washed with 10% hydrochloric acid solution (20 ml *3), dried over anhydrous sodium sulfate, and concentrated. Column chromatography (petroleum ether-acetone 4:1) separated and concentrated to give 17β-acetoxy-3,5-estradien-3-one: 0.726 g, light yellow solid, yield 93%, Mp: 103 ~105°C; [a] D 20 = -39 o ( c = 1.00, CHCl 3 ); MS ( m / z ): 315 [M+1] + ; IR (cm) -1 : 2970, 2945, 2911, 2859 (C 4 =C 6 ); 1732 ( O=C CH 3 );1665 (O=C 3 ) ( figure 1 ). 1 H NMR (CDCl 3 , 50...
Embodiment 2
[0027] Dissolve 3-tris(isopropyl)silyloxy-17β-acetoxy-3,5-androstadiene (2.13 g, 5.50 mmol) in anhydrous DMF (44 ml), N 2 Stir and cool to 0 °C under protection. Slowly add (NH 4 ) 2 Ce(NO 3 ) 6 (5.38 g, 11.0 mmol), the addition was completed in about half an hour, and the reaction mass was stirred at 0°C for 1 h. After the reaction is completed, the reaction solution is poured into 66 ml saturated NaHCO 3 solution, and with CH 2 Cl 2 (45 ml *3) extracted. The combined organic phases were washed with 10% hydrochloric acid solution (45 ml * 3), dried over anhydrous sodium sulfate, and concentrated. Separation and concentration by column chromatography (petroleum ether-acetone 4:1) gave 17β-acetoxy-3,5-estradien-3-one: 1.51 g, light yellow solid, yield 82%.
Embodiment 3
[0029] Dissolve 3-tris(isopropyl)silyloxy-17β-acetoxy-3,5-androstadiene (2.34 g, 6.05 mmol) in anhydrous DMF (48 ml), N 2 Stir and cool to 0 °C under protection. Slowly add Ce(NO 3 ) 4 (3.94 g, 12.1 mmol), the addition was completed in about half an hour, and the reaction mass was stirred at 0°C for 1.5 h. After the reaction is completed, the reaction solution is poured into 70 ml saturated NaHCO 3 solution, and with CH 2 Cl 2 (50 ml * 3) extract. The combined organic phases were washed with 10% hydrochloric acid solution (50 ml *3), dried over anhydrous sodium sulfate, and concentrated. Column chromatography (petroleum ether-acetone 4:1) separated and concentrated to give 17β-acetoxy-3,5-estradien-3-one: 0.64 g, light yellow solid, yield 80%.
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