用于16α-羟化酶的16α-3H雄激素和雌激素底物的合成。

Synthesis of 16 alpha-3H androgen and estrogen substrates for 16 alpha-hydroxylase.

作者信息

Cantineau R, Kremers P, De Graeve J, Cornelis A, Laszlo P, Gielen J E, Lambotte R

出版信息

Steroids. 1981 Feb;37(2):177-94. doi: 10.1016/s0039-128x(81)80016-5.

Abstract

The synthesis of 16 alpha-3H androgens and estrogens is described. 1-(3H)-Acetic acid in the presence of zinc dust reacts with 16 alpha-bromo-17-ketosteroids to produce 16 alpha-3H-17-ketosteroids. This chemical reaction was used to prepare 16 alpha-3H-dehydroepiandrosterone (I) and 16 alpha-3H-estrone acetate (XI) from 16 alpha-bromo-dehydroepiandrosterone (X) and from 16 alpha-bromo-estrone acetate (XII), respectively. Using appropriate microbiological techniques, it was possible to convert these radiolabelled substrates into 16 alpha-3H-androstenedione (II) and 16 alpha-3H-estradiol-17 beta (VII). 16 alpha-3H-Estrone (VI) was obtained by the chemical hydrolysis of 16 alpha-3H-estrone acetate. The label distribution as determined by microbiological 16 alpha-hydroxylations indicated a specific labelling of 77% for androgens and 65% for estrogens in the 16 alpha position. These substrates can be used for measuring the 16 alpha hydroxylase activity, an important step in the biosynthesis of estriol (VIII) and estetrol (IX).

摘要

描述了16α-³H雄激素和雌激素的合成。1-(³H)-乙酸在锌粉存在下与16α-溴-17-酮类固醇反应生成16α-³H-17-酮类固醇。该化学反应分别用于从16α-溴脱氢表雄酮(X)和16α-溴雌酮乙酸酯(XII)制备16α-³H-脱氢表雄酮(I)和16α-³H-雌酮乙酸酯(XI)。使用适当的微生物技术，可以将这些放射性标记的底物转化为16α-³H-雄烯二酮(II)和16α-³H-雌二醇-17β(VII)。16α-³H-雌酮(VI)通过16α-³H-雌酮乙酸酯的化学水解获得。通过微生物16α-羟基化测定的标记分布表明，雄激素在16α位的特异性标记为77%，雌激素为65%。这些底物可用于测量16α-羟化酶活性，这是雌三醇(VIII)和雌四醇(IX)生物合成中的重要一步。