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化学学报
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化学学报 ›› 1958, Vol. 24 ›› Issue (1): 69-73,77. 上一篇    下一篇

论文

多环化合物的研究——Ⅳ. 1-氧代-2-甲基-2-甲氧羰基-7-甲氧基-1, 2, 3, 4, 9, 10-六氢化菲的又一合成法

张锦   

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

STUDIES ON POLYCYCLIC COMPOUNDS Ⅳ. A SYNTHESIS OF 1-KETO-2-METHYL-2-CARBOMETHOXY-7-METHOXY-1, 2, 3, 4, 9, 10-HEXAHYDROPHENANTHRENE FROM 6-METHOXY-α-TETRALONE

CHANG CHIN   

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

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由1-氧代-7-甲氧基-1, 2, 3, 4, 9, 10-六氢化菲经过两种不同的方法, 可以得到1-氧代-2-甲基-2-甲氧羰基-7-甲氧基-1, 2, 3, 4, 9, 10-六氢化菲.这两种方法, 一为由1-氧代-7-甲氧基-1, 2, 3, 4, 9, 10-六氢化菲, 经过乙酮酸甲酯化(glyoxalation)後, 加热及玻璃粉去羰基, 再经过甲基化;一为利用1-氧代-7-甲氧基-1, 2, 3, 4, 9, 10-六氢化菲与氨基钠在液体氨溶液中的反应, 先得到1-氧代-7-甲氧基-1, 2, 3, 4, 9, 10-六氢化菲的2-钠盐.此钠盐与乾燥过的二氧化碳在无水乙醚内反应, 可得到1-氧代-2-羧基-7-甲氧基-1, 2, 3, 4, 9, 10-六氢化菲的钠盐.此钠盐经过酸化, 酯化, 甲基化后, 即得到1-氧代-2-甲基-2-甲氧羰基-7-甲氧基-1, 2, 3, 4, 9, 10-六氢化菲.

γ-(6-Methoxy-1, 2, 3, 4-tetrahydro-1-naphthylidene)-butyric acid was prepared according to the method of Stork.This acid could be successfully cyclized to 1-keto-7-methoxy-1, 2, 3, 4, 9, 10-hexahydrophenanthrene by means of 100% orthophosphoric acid at 125-135°.The product obtained gave the characteristic iodine colored 2, 4-dinitrophenylhydrazone, m.p.253-255°.From this ketone, two routes were employed to obtain the desired 1-keto-2-methyl-2-carbomethoxy-7-methoxy-1, 2, 3, 4, 9, 10-hexahydrophenanthrene:(1)1-keto-7-methoxy-1, 2, 3, 4, 9, 10-hexahydrophenanthrene was treated with dimethyl oxalate and sodium methoxide, and methyl 1-keto-7-methoxy-1, 2, 3, 4, 9, 10-hexahydrophenanthrene-2-glyoxalate was obtained in excellent yield as orange prisms, m.p.138-138.5°.