(±)-13β,17α-二乙基-17β-羟基甾烷骈3,2-C吡唑及2,3-C呋咱的合成
SYNTHESIS OF (±)-13β, 17α-DIETHYL-17β-HYDROXY-GONANO 3,2-C PYRAZOLES AND 2,3-C FURAZANES
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摘要: 以(±)-13β,17α-二乙基-17β-羟基-5α-甾烷-3-酮(Ⅱ)为原料,经甲酰化、缩合反应合成了(±)-13β,17α,-二乙基-17β-羟基-5α-甾烷骈3,2-C吡唑(Ⅴ);又将甲酰化反应所得羟次甲基化合物(Ⅳ)依次转变成单肟(Ⅵ)、双肟(Ⅶ)、再坏合成(±)-13β,17α-二乙基-5α-甾烷骈2,3-C呋咱(Ⅷ)。采用类似的反应,从(Ⅱ)及(Ⅳ)的5β-异构体(Ⅲ)和(Ⅸ)分别合成了(±)-13β,17α-二乙基-17β-羟基-5β-甾烷骈3,2-C吡唑(Ⅹ)与(±)-13β,17α-二乙基-17β-羟基-5β-甾烷骈2,3-C)呋咱(ⅩⅢ)。Abstract: In Ihe presence of CH3ONa,(Ⅱ) was reacted with ethyl formate to give 2-hydroxy-methylene-steroid(Ⅳ) which was made to react with hydrazine hydrate to give the pyrazole(Ⅴ). (Ⅳ) was treated with sodium nitrite and acetic acid(or hydrochloric acid) to afford the 2-hydroxylimino-steroid(Ⅵ) which on further oxidation with hydroxylamine gave the dioxime(Ⅶ). Finally dehydration and cyclization of(Ⅶ) produced the desired furazane(Ⅷ).Using similar reaction, 5β isomer(Ⅹ) and(ⅩⅢ) were also obtained from(Ⅲ).
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