Development of Novel Qumoid Compounds by Taking Advantage of the Molccular Cavities as a Steric Protection Environment

新型碗型分子腔已被应用于合成包括高活性化合物在内的多种奎宁类化合物。合成了一种桥联杯[6]芳烃，其中1，4-苯二酚部分共价固定在杯[6]芳烃刚性锥形大环的空腔中，其结构经X-射线分析确定。循环伏安图显示：与不含杯芳烃宏码的参比化合物相比，其还原电位负移。以对叠氮苯酚为原料，在碱性条件下进行热分解反应，成功地合成了稳定的N-未取代喹啉亚胺。通过X-射线分析确定了它的晶体结构，首次提出了N-未取代喹啉亚胺的结晶学分析。结果表明，杯[6]芳烃大环能有效地保护亚胺基团。循环伏安曲线表明，与相应的对苯二酚相比，对苯二亚胺在一步中发生了两个电子的还原，而相应的对苯二酚则进行了两步还原。此外，还考察了硫代醌等其他活性喹啉物种的稳定性。

Novel bowl-type molecular cavities have been applied to synthesis of a variety of quinoid compounds including highly reactive ones. A bridged calix[6]arene, where a 1,4-benzoquinone moiety is covalently anchored in the cavity of the calix[6]arene macrocycle with a rigid cone conformation, was synthesized and its structure was determined by X-ray analysis. The cyclic voltammogram showed 'that :its reduction potential is negatively shifted in comparison with the reference compounds without the calixarene macrocode. A stable N- unsubstituted quinoneimine was successfully synthesized by thermolysis of the corresponding p-azidophenol under basic conditions. Its crystal structure was established by X-ray analysis, presenting the first example of the crystallographic analysis of an N-unsubstituted quinoneimine. It was revealed that the imine moiety is effectively protected by the calix[6]arene macrocycle. The cyclic voltammogram indicated that the quinoneimine is subject to two-electron reduction in one step in contrast to the corresponding quinone, which is reduced by two steps. Stabilization of other reactive quinoid species such as thioquinones was also investigated.