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首页> 外文期刊>Bulletin of the Chemical Society of Japan >Lead(IV) Oxide-mediated Oxidation of Azulen-2-ols to Form 1,1-Coupled Dimers and Hexacyclic Cage-Dimers.
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Lead(IV) Oxide-mediated Oxidation of Azulen-2-ols to Form 1,1-Coupled Dimers and Hexacyclic Cage-Dimers.

机译:铅(IV)氧化介导的Azulen-2-ols氧化形成1,1-偶合二聚体和六环笼式二聚体。

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摘要

The lead(IV) oxide oxidation of various azulen-2-ol derivatives in acetic aid generates azulenoxy radicals via one-electron oxidation. The intermediates end up yielding recombined dimers, [1,1'-biazulene]-2,2'-(1H,1'H)-dimers, as common type o fproducts. In addition to these, hexacyclic cage dimers were obtained from 5-substituted azulen-2-ol derivatives. From dimethyl 2-hydroxyazulene-1, 3-dicarboxylate, a hydroxyazulene having no substitutent on the seven-membered ring was isolated a pair of dimethyl 2-hydroxy-4-[1,3-di(methoxyarbonyl)-2-oxo-1,2-dihydroazulenyl]azulene-1,3-dicarboxylate, but neither a cage dimer nor a 1,6-coupled dimer. The full structures of the dimers have been firmly established by an extensive X-ray crystallographic analysis and ~(13)C NMR spectra comparisons of the key derivatives. Concerning the mechanism of the formation of the cage dimers, a [5+5] #pi# cycloaddition followed by recombination of the resultant biallyl system is suggested.
机译:乙酸助剂中各种azulen-2-ol衍生物的氧化铅(IV)氧化通过单电子氧化生成azulenoxy自由基。中间体最终产生重组的二聚体,[1,1'-二氮杂] -2,2'-(1H,1'H)-二聚体,为常见的产物。除这些之外,六环笼二聚体由5-取代的Azulen-2-ol衍生物获得。从2-羟基azulene-1二甲基3-二羧酸酯中,分离出七元环上没有取代基的羟基azulene,即一对二甲基2-羟基-4- [1,3-二(甲氧基亚芳基)-2-oxo-1 ,1,3-二羧酸的2,2-二氢杂氮烯基] azulene,但既不是笼型二聚体也不是1,6-偶联的二聚体。通过广泛的X射线晶体学分析和关键衍生物的〜(13)C NMR光谱比较,已牢固地建立了二聚体的完整结构。关于笼型二聚体的形成机理,提出了[5 + 5]#pi#环加成,然后重组所得的双烯丙基系统。

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