Studies on Synthesis and Properties of Cyclophanes Based on the Bridged[14]π-Annulene Units

1.桥式芳香族化合物的合成研究进展尽管目前已有大量关于桥式芳香族化合物合成的报道，但其制备路线似乎过于冗长，难以实际应用。特别是[2.2]元环蒽-二烯及其价互变异构体反式-10b，10c-二氢芘是高度应变的化合物，可能对许多试剂起反应。然而，这些玉米的化学成分非常有限。在这项工作中，我们利用叔丁基作为芳香环上的位置保护基团，开发了一种方便的制备具有双键的桥接芳香化合物的方法。在这些合成结果的基础上，我们成功地制备了由桥接b[14]π-环烯单元构成的环烷。结构与化学反应活性的关系研究了二甲苯和二氢芘的亲电取代反应，探讨了反应活性与分子菌株的关系。由于分子菌株的释放，我们观察到各种跨环反应和异构化。结构与光化学性质的关系我们研究了环芳二烯和10b，10c-二甲基-10b，10c-二氢芘的光化学性质。用x射线衍射分析研究了结构与物理性质之间的关系。基于环己烷的光化学性质，我们研究了10b，10c-二甲基-10b，10c-二氢芘的光诱导价互变异构成8,16-二甲基[2.2]-甲基环己烷-1,9-二烯。我们已经成功地构建了新的光致变色系统，并将其应用于光响应分子识别系统等先进材料。

1.The development of synthesis of the bridged aromatic copoundsAlthough there are numerious reports concerning synthesis of the bridged aromatic compounds, their preparative routes seem to be too lomg for practical purposes. Especially, the [2.2]metacyclophane-dienes and their valence tautomers trans-10b,10c-dihydropyrenes are so highly strained compounds that may be reactive towards many reagents. However, the chemistry of these cornpouns is very limited. In this work, we have developed the convenient preparation of the strained bridged aromatic compounds having the double bouns on bridged chaines using the tertbutyl function as a positional protecting group on the aromatic ring. Based on these synthetic results, we have succeeded to prepare the cyclophanes constructed by the bridged [14]π-annulene units.2.Relationship between the structures and chemical reactivityElectrophilic substitution reactions of metacyclophane-dienes and dihydropyrenes were studied in order to investigate the relationship between the reactivity and the molecular strains. We have observed a various kinds of transannular reaction and isomerizarion due to the release of the molecular strains.3.Relationship between the structures and photochemical propertiesWe have investigated the photochemical properties of cyclophane-dienes and 10b,10c-dimethyl-10b,10c-dihydropyrenes. The relationship between the structures and physical properties was also investigated by X-ray diffraction analysis.4.The development to the advanced materialsBased on the photochemical properties of cyclopanes, we have investigated the photo-induced valence tautomerization of 10b,10c-dimethyl-10b,10c-dihydropyrenes to 8,16-dimethyl[2.2]metacyclophane-1,9-dienes. We have succeeded to construct the new photocromic systems and devdoped to the application for the advanced materials, for example photo-response molecular recognition systems.