NONADRIDES .2. CONSTITUTIONS OF GLAUCONIC AND GLAUCANIC ACIDS
NONADRIDES .2. CONSTITUTIONS OF GLAUCONIC AND GLAUCANIC ACIDS
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DOI：
10.1039/jr9650001772
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发表时间：
1965-01-01
期刊：
影响因子：
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通讯作者：
SUTHERLAND, JK
中科院分区：
文献类型：
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作者：
BARTON, DHR;JACKMAN, LM;SUTHERLAND, JK
本文叙述了关于葡康酸（I; X= OH）的早期工作及其结构的推导。现在我们简要介绍我们对这个有趣的中环化合物的新实验工作。这些反应可大致分为热解、还原、水解和氧化。最后提到的将与绝对构型的确定相关地呈现3。在结构测定中，还原反应是迄今为止信息量最大的。本文讨论了锌粉-乙酸还原（I; X= OH）为内酯（11）和还原（I; X= OAc）为蓝桉酸（I; X= H）的反应。这种酮是由三氧化铬-丙酮氧化葡康酸制备的，虽然它不能还原回葡康酸，但从它的光谱和进一步的转化来看，毫无疑问它具有给定的结构。锌粉-乙酸还原酮得到两种Cl ~-化合物。第一个，Cl，H，06（111; R= H），含有完整的衣康酸酐单元，从其光谱[hmx 225-228 mp（E 8600）; vmx. 1830和1770厘米。1; 16-Me 8.59 7，13-乙烯基H在3-08 7处为双峰（J= 10 c./ sec.）];这些值是该单元的特征值，并且在所有含有该单元的该系列化合物中都可以找到。作为紫外模型，使用了在环己烷中的1-和2-脱氢环己烷-1，2-二羧酸酐，其A1分别为250 mp（E3500）和223（7600）。对于化合物（I11;
THE earlier work on glauconic acid (I; X= OH), and the deduction of the structure, have been described. lP2 We present now a concise account of our new experimental work on this interesting medium-ring compound. The reactions can be roughly classified as pyrolytic, reductive, hydrolytic, and oxidative. The last named will be presented 3 in connection with the determination of the absolute configuration. In the structure determination the reductive reactions were by far the most informative. The zinc dust-acetic acid reduction of (I; X= OH) to the lactone (11) and of (I; X= OAc) to glaucanic acid (I; X= H) has been discussed-l Similar reduction of the ketone (I; X, H= 0) takes yet another course. This ketone was prepared by chromium trioxide-acetone oxidation of glauconic acid, and although it could not be reduced back to glauconic acid, there is little doubt, from its spectra and further transformations, that it has the given structure. Zinc dust-acetic acid reduction of the ketone gave two Cl,-compounds. The first, Cl, H,, 06 (111; R= H), contained the intact itaconic anhydride unit, identified from its spectra [hmx 225-228 mp (E 8600); vmx. 1830 and 1770 cm.-l; 16-Me 8.59 7, 13-vinyl H as a doublet at 3-08 7 (J= 10 c./sec.)]; these values are characteristic of this unit, and are found in all compounds of this series containing it. As ultraviolet models, 1-and 2-dehydrocyclohexane-1, Zdicarboxylic acid anhydrides, having A,, 250 mp (E 3500) and 223 (7600), respectively, in cyclohexane, were used. For the compound (I11;