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化学学报
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化学学报 ›› 1955, Vol. 21 ›› Issue (3): 315-319. 上一篇    下一篇

论文

稠環化合物的研究Ⅲ.1-氧代-2-甲基-7-甲氧基-1, 2, 3, 4, 9, 10, 11, 12-入氢化菲与γ-溴代巴豆酸甲酯的REFORMATSKY反应

张锦   

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

STUDIES ON FUSED RING SYSTEMS Ⅲ. REFORMATSKY REACTIONO OF 1-KETO-2-METHYL-7-METHOXY-1, 2, 3, 4, 9, 10, 11, 12-OCTAHYDROPHENANTHRENE WITH METHYL γ-BROMOCROTONATE

CHANG CHIN   

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

PDF

474

由1-氧代-2-甲基-7-甲氧基-1,2,3,4,9,10,11,12-八氫化菲及γ-溴代巴豆酸甲酯,利用Reformatsky反應,得到γ-1-羥基-2-甲基-7-甲氧基-1,2,3,4,9,10,11,12-八氫化菲-1-巴豆酸甲酯.此化合物經過催速氫化及水解後,得到γ-1-羥基-2-甲基-7-甲氧基-1,2,3,4,9,10,11,12-八氫化菲-1-丁酸,產量極佳.

1-Keto-2-methyl-7-methoxy-1, 2, 3, 4, 9, 10, 11, 12-0ctahydrophenanthrene,, whose BC ring has the same configuration as dl-strone's, was readily obtained from Miescher's ketoester A by alkali hydrolysis.By means of the Reformatsky reaction this ketone reacted with methyl y-bromocrotonate, forming methyl y-l-hydroxy-2-methyl-7-methoxy-1, 2, 3, 4, 9, 10, 11, 2-octahydrophenanthrene-l-crotonate.This unsaturated ester, after being hydrogenated in the presence of 5% Pd-C, was hydrolyzed with dilute KOH in CH30H solution, giving the sodium salt of the hydroxy acid.Upon acidification of the sodium salt solution,Y-1-hydroxy-2-methyl-7-methoxy-1, 2, 3, 4, 9, 10, 11, 2-octahydrophenanthrene-1-butyric acid was obtained with excellent yield.This acid was recrystallized from benzene, melring at 168-169°.Preliminary experiments on the cyclization of this hydroxy acid indicated the formation of a ketone.