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化学学报
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化学学报 ›› 1955, Vol. 21 ›› Issue (2): 190-196. 上一篇    下一篇

论文

稠環化合物的研究I.7-甲氧基-1-氧代-2-甲基-1,2,3,4-四氢化菲和γ-溴代巴豆酸甲酯的反应;dl-同去氢雌马酮的合成及由其甲醚的降遞而制成dl-去氢雌马酮

张锦   

  1. 北京石油学院
  • 投稿日期:1955-03-16 发布日期:2013-06-04

STUDIES OF FUSED RING SYSTEMS I.REACTION OF 7-METHOXY-1-KETO-2-METHYL-1,2,3,4-TETRAHYDROPHENANTHRENE WITH METHYL γ-BROMOCROTONATE;SYNTHESIS OF DL-HOMOEQUILENIN AND DEGRADATION OF ITS METHYL ETHER INTO DL-EQUILENIN

CHANG CHIN   

  1. Peking Petroleum Institute
  • Received:1955-03-16 Published:2013-06-04

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(1)利用γ-溴代巴豆酸甲酯及7-甲氧基-1-氧代-2-甲基-1,2,3,4-四氫化菲的Reformatsky反應,催化加氫及水解後,得到γ-1-羥基-7-甲氧基-2-甲基-1,2,3,4-四氫化菲-1-丁酸。此酸可用P2O5環化,得到去氫同去氫雌馬酮-3-甲醚。此不飽和酮用5%Pd-C為觸媒,催化加氫後,得到dl-3-甲氧基同去氫雌馬酮。(2)用KOI為氧化劑,自dl-3-甲氧基同去氫雌馬酮製得β-7-甲氧基-2-甲基-2-羧基-1,2,3,4-四氫化菲-1-丙酸。按照Bachmann等氏的方法,自此酸製得dl-去氫雌馬酮。

By means of Reformatsky reaction between methyl γ-bromocrotonate and 7-methoxy-1-keto-2-methyl-1, 2, 3, 4-tetrahydrophenanthrene, methyl y-(1-hydroxy-7-methoxy-2-methyl-1, 2, 3, 4-tetrahydrophenanthrene)-1-crotonate was obtained. This compound was reduced with 5% Pd-C in absolute ethyl alcohol. The reduced ester was hydrolyzed with 2 N KOH, and. then acidified to give y-l-hydroxy-7-methoxy-2-methyl-1, 2, 3, 4-tetrahydrophenanthrene-l-butyric acid. This hydroxy acid was cyclized with F205 in benzene to the methyl ether of dehydrohomoequilenin. With 5% Pd}C as catalyst this unsaturated ketone was reduced in thiophene-free benzene to the methyl ether of dl-homoequilenin, which was demethylated to d}l-homoequilenin with 48% HBr. Its identity was established by mixed melting point with a sample prepared by Bachmann and Holmes. The methyl ether of dl-homoequilenin was satisfactorily degraded with KOI into β-7-methoxy-2-methyl-2-carboxy-1, 2, 3, 4-tetrahydrophenanthrene-l}propionic acid. The dimethyl ester prepared from this dibasic acid with diazomethane was cyclized to 16-carbmethoxy equilenin, which was readily decarboxylated and demethylated into dl-equilenin, the identity of which was established by mixed melting point with a sample prepared by Bachmann, Cole and Wilds.