Sterols. CXII. Sapogenins. XLI. The Preparation of Trillin and its Conversion to Progesterone
Sterols. CXII. Sapogenins. XLI. The Preparation of Trillin and its Conversion to Progesterone
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DOI：
10.1021/ja01869a023
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发表时间：
1940-12
影响因子：
15
通讯作者：
R. Marker;J. Krueger
中科院分区：
文献类型：
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作者：
R. Marker;J. Krueger
水解延龄草根的醇提取物已显示产生纯薯蓣皂苷元。[1]我们证明了格罗夫、詹金斯和斯普森[2]所报道的“trillarigenin”是trillin和薯蓣皂苷元的混合物。3 Trillin为薯蓣皂苷元的单糖苷。我们现在已经合成了薯蓣皂苷元的一个-四乙酰基葡萄糖苷，它与从延龄草中分离的延龄草苷的乙酸酯相同。来自两种来源的游离糖苷是相同的，因此trillin必须由通过非糖苷键连接到薯蓣皂苷元分子的3位的葡萄糖分子组成。我们还制备了从鼠尾草皂苷元中提取的糖苷。货车der Haar [4]描述了m. p.230，其通过乙酰溴葡萄糖与萨洒皂草配基在甲苯-喹啉溶液中缩合以小于2%的产率获得。本文报道的薯蓣皂苷元和萨洒皂草苷元的β-葡萄糖苷是用Zemplén法合成的，产率约为50%。以前已经证明薯蓣皂苷元在与乙酸酐一起加热时很容易转化为假皂苷元。本实验室研究的所有甾体皂甙元都是这种情况。假皂甙元在温和氧化后以良好的产率转化为A16-孕烯酮-20衍生物。由此可见，薯蓣皂苷元在C-5位有双键，是合成甾体激素的理想原料。认为在进行氧化之前，有必要用溴保护薯蓣皂苷元中的双键。在溴化反应中，相当数量的假皂甙元附着在其易受攻击的侧链上。在一个实验中，我们发现侧链氧化成A 16-烯酮-20衍生物的过程是这样的。
The hydrolysis of the alcoholic extract of the root of trillium erectum has been shown to yield pure diosgenin. 1 We have proved the previously reported “trillarigenin” of Grove, Jenkins and Thompson2 to be a mixture of trillin and dios-genin. 3 Trillin was characterized as a monoglu-coside of diosgenin. We have now synthesized an-tetraacetylglucoside of diosgenin which is identical with the acetate of trillin, isolated from trillium erectum. The free glucosides from both sources are identical, and thus trillin must be composed of a molecule of glucose joined through an-glucosidic linkage to the 3-position of the diosgenin molecule. We have also prepared the glucoside from sar-sasapogenin. Van der Haar4 has described a glu-coside of sarsasapogenin of m. p. 230 which he obtained in less than 2% yield by condens-ing acetobromoglucose with sarsasapogenin in toluene-quinoline solution. The-glucosides of diosgenin and sarsasapogenin reported in the present paper were prepared in approximately 50% yields by Zemplén’s method. 5 It has previously been shown6 that diosgenin upon heating with acetic anhydride is readily con-verted into a pseudo sapogenin. This is the case of all the steroidal sapogenins studied in this Laboratory. The pseudo sapogenins upon mild oxidation are converted into A16-pregnenone-20 derivatives in good yield. Thus it can be seen that diosgenin having a double bond at C-5 would be an ideal starting material for thesyn-thesis of the steroidal hormones. It was thought necessary to protect the double bond in pseudodiosgenin with bromine before carrying out the oxidation. In the bromination a considerable amount of the pseudo sapogenin is attackedin its vulnerable side-chain. In an experiment now re-ported we find that the oxidation of the side-chain to a A16-pregnenone-20 derivative goes so