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化学学报
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化学学报 ›› 1958, Vol. 24 ›› Issue (1): 73-78. 上一篇    下一篇

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Ⅴ. β-(2-甲基-7-甲氧基-1, 2, 3, 4, 9, 10, 11, 12-八氢化-1-亚菲基)-丙酸的合成

张锦   

  1. 北京石油学院
  • 投稿日期:1957-08-17 发布日期:2013-06-03

Ⅴ. SYNTHESIS OF β-(2-METHYL-7-METHOXY-1, 2, 3, 4, 9, 10, 11, 12-OCTAHYDRO-1-PHENANTHRYLIDENE)-PROPIONIC ACID

CHANG CHIN   

  1. Peking Petroleum Institute
  • Received:1957-08-17 Published:2013-06-03

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由1-氧代-2-甲基7-甲氧基-1, 2, 3, 4, 9, 10, 11, 12-八氢化菲及溴代乙酸甲酯的Re-formatsky反应, 得到1-羟基-2-甲基-7-甲氧基-1, 2, 3, 4, 9, 10, 11, 12-八氢化菲-1-乙酸甲酯.由此羟基酯与二硫亚砜及吡啶的反应后, 得(2-甲基-7-甲氧基1, 2, 3, 4, 9, 10, 11, 12-八氢化-1-亚菲基)-乙酸甲酯.此酯经过水解后, 得到相对应的酸, 此酸酰氯经过Arndt-Eistert在甲醇内的反应, 得到β-(2-甲基-7-甲氧基-1, 2, 3, 4, 9, 10, 11, 12-八氢化-1-亚菲基)-丙酸甲醇.此酯经过水解后, 得到相对应的酸.

The d iastereoisomeric 1-keto-2-methyl-7-methoxy-1, 2, 3, 4, 9, 10, 11, 12-octahy-drophenantlrene with m.p.116-117°, whose B/C ring has the same configuration as that of dl-estrone's, was readily obtained from Miescher's keto ester(A)by alkali hydrolysis.By means of the Reformatsky reaction between this ketone and methyl bromoacetate, methyl 1-hydroxy-2-methyl-7-methoxy-1, 2, 3, 4, 9, 10, 11, 12-octahydrophenanthrene-1-acetate was obtained.This hydroxy ester could be readily dehydrated to the unsaturated ester by means of thionyl chloride and pyridine.This ester, upon hydrolysis with methanolic potassium hydroxide, gave the potassium salt which, upon acidification with hydrochloric acid, yielded the unsaturated acid, (2-methyl-7-methoxy-1, 2, 3, 4, 9, 10, 11, 12-octahydro-1-phenanthrylidene)-acetic acid in excellent yield, m.p.193.5-195°.