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

1.桥联芳香族化合物的合成进展虽然关于桥联芳香族化合物的合成有许多报道，但它们的制备路线似乎过于冗长，不利于实际应用。尤其是[2.2]异构体反式-10b，10c-二氢戊二烯是高度紧张的化合物，可能与多种试剂发生反应。然而，这些玉米粒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环上的位置保护基团，方便地制备了具有桥链上双键的应变桥联芳香族化合物。在这些合成结果的基础上，我们成功地制备了桥联的[14]π-轮烯单元构成的环芳烃。2.结构与化学反应的关系研究了偏环芳烃-二烯和二氢戊二烯的亲电取代反应，以探讨反应活性与分子应变的关系。我们观察到了由于分子应变的释放而发生的各种跨环反应和异构化反应。3.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-二氢戊二烯的光化学性质。基于环戊烷的光化学性质，我们研究了10b，10c-二甲基-10b，10c-二氢戊二烯的光诱导价异构化为8，16-二甲基[2.2]偏环-1，9-二烯。我们已经成功地构建了新的光致变色系统，并将其应用于先进材料，例如光响应分子识别系统。

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.