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化学学报
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化学学报 ›› 1962, Vol. 28 ›› Issue (6): 351-364. 上一篇    下一篇

论文

维生素丁的研究Ⅲ.2-取代-顺-亚环已基乙酸类化合物的合成(二)2-氧代-顺-亚环己基乙酰肼类化合物及其环化和重排

汪猷, 黄敬坚   

  1. 中国科学院有机化学研究所
  • 投稿日期:1960-12-15 发布日期:2013-06-03

STUDIES ON VITAMIN D Ⅲ. THE SYNTHESIS OF COMPOUNDS OF 2-SUBSTITUTED CIS-CYCLOHEXYLIDENEACETIC ACID TYPE (2) HYDRAZIDES OF 2-KETO-CIS-CYCLOHEXYLIDENEACETIC ACID AND THEIR CYCLIZATION AND REARRANGEMENT

WANG YU, HUANG JIGN-JAIN   

  1. Institute of Organic Chemistry, Academia Sinica
  • Received:1960-12-15 Published:2013-06-03

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本文报告2,2-双羟亚环己基乙酸内酯(Ⅱ)和2-羟基亚环己基乙酸内酯(Ⅲ)中内酯环打开的工作,尤其2-氧代-顺-亚环己基乙酰肼类化合物的制备及其环化和重排的研究结果。Ⅱ与肼作用得5,6,7,8-四氢邻二氮杂萘酮-(3)(Ⅳa),与苯肼作用则得2-氧代-顺-亚环己基乙酰苯肼(Ⅵ)。Ⅵ经热、酸或碱处理易脱水环化,并发生重排而成2-苯基-5,6,7,8-四氢邻二氮杂蓁酮-(3)(ⅩⅥa)。ⅩⅥa的结构式是根据其紫外及杠外吸收光谱和活泼氢的测定而确定。本文中提出重排的可能机理。Ⅱ与1,1-苯甲基苯肼或1,1-二甲基肼作用则分别得2-氧代-顺-亚环己基乙酰苯甲基苯肼(Ⅶ)和2-氧代-顺-亚环己基乙酰二甲基肼(Ⅷ),Ⅷ与氨基脲先形成2-氧代-顺-亚环己基乙酰氨基脲(Ⅸ),进而变成Ⅳa。而2-氧代-反-亚环己基乙酸(Ⅹ)与苯肼反应则生2-氧代-反-亚环己基乙酸苯腙(Ⅺ)。Ⅱ于甲醇中与重氮甲烷生成ⅩⅢ,再与苯肼作用获得2'-氧代-环己烷-(1'-螺-4)-4,5-双氢呲唑-3-甲酰苯肼(ⅩⅣ)。Ⅲ与S-苯甲基硫脲盐酸盐、苯甲胺和甲醇钠的甲醇溶液分别作用都未获得预期的顺烯构型产物,而得到异构化的2-氧代-环己基乙酸的S-苯甲基硫脲盐(ⅩⅩ),2-苯甲亚胺环己基乙酰苯甲胺(ⅩⅪ)和2-氧代-环己基乙酸甲酯(ⅩⅫ)。Ⅲ的开环化合物极易重排为2-氧代-环己基乙酸衍生物,而Ⅱ的开环化合物的酮基极不活泼。

Various ways for the opening of the rings of 2,2-dihydroxy-cyclohexylideneacetic acid lactone (Ⅱ) and 2-hydroxy-cyclohexylideneacetic acid lactone (Ⅲ) have been investigated. 5,6,7,8-Tetrahydrocinnolinone-(3) [Ⅳa, m.p. 188-189°, λmaxEtOH 296 mμ (ε 2410), νmax 3255(w), 3195(w), 1675(s), 1600(m), 1540(m) cm-1] was formed from Ⅱ with hydrazine, and 2-keto-cis-cyclohexylideneacetic acid phenylhydrazide [Ⅵ, m.p. 136-137°, λmaxEtOH 240mμ(ε 18,300)] from Ⅱ with phenylhydrazine. On heating only or on treatment with acid or alkali, Ⅵ underwent cyclization with a rearrangement into 2-phenyl-5,6,7,8-tetrahydrocinnolinone-(3) [ⅩⅥa, m.p. 121-122°, λmaxEtOH 315 mμ (ε 4840), λmax 1685(s), 1600(m)cm-1]. The structure of ⅩⅥa has been established by elementary analysis, UV-and IR-absorption spectra, and the determination of active hydrogen. The mechanism of the above mentioned rearrangement has been discussed.