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化学学报
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化学学报 ›› 1965, Vol. 31 ›› Issue (2): 165-170. 上一篇    下一篇

论文

Kishner-Wolff改良法——X.数种C20羰基甾体化合物的还原

黄鸣龙, 陈兆容, 周维善   

  1. 中国科学院有机化学研究所
  • 投稿日期:1964-06-19 发布日期:2013-06-03

MODIFIED KISHNER-WOLFF REDUCTION Ⅹ. REDUCTION OF SEVERAL 20-KETOSTEROIDS

HUANG-MINLON, CHEN CHAO-YUNG, CHOW WEI-ZAN   

  1. Institute of Organic Chemistry, Academia Sinica
  • Received:1964-06-19 Published:2013-06-03

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在螺旋内酯甾的结构与疗效关系研究中,我们准备用17α-羟基-17β-醛基化合物(Ⅰ)为原料以合成具反式构型的螺旋内酯甾(Ⅱ).Ⅰ系未知体.为证明其结构曾用改良的Kishner-Wolff还原法处理.Ⅰ还原后得一混合物,经氧化铝层析获得化合物(Ⅲ)及(Ⅳ),其纯品得率分别为13%及45%,两者均为已知体.Ⅳ经Oppenauer氧化成17β-甲基异睾丸素(Ⅴ);Ⅲ经微量臭氧氧化生成甲醛,因而得到进一步的证明.α-酮醇在用改良的Kishner-Wolff法还原时,α位置的羟基往往易被除去,而现在含α-羟基的醛基化合物(Ⅰ)经还原则主要生成羟基保留之物(Ⅳ).

In contrast with the general observation that the modified Kishner-Wolff reduction of an a-ketol leads essentially to the elimination of the hydroxy group,the reduction of 17 β-aldehydo-l7α-hydroxy compound(Ⅰ) yields mainly Ⅳ with retention of the hydroxy group,whereas reduction of Ⅵ gives Ⅶ as the principal product.The major product obtained by the same reduction of the a,β-unsaturated ketone(Ⅹ) has been found to be the sidechain saturated compound(ⅩⅠ) instead of the expected compound(Ⅶ).