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

1.桥连芳香族化合物的合成研究进展尽管有关桥连芳香族化合物的合成报道很多，但其制备路线似乎太长，难以实用。特别是，[2.2]间环芳二烯和它们的价互变异构体反式-10b，10 c-二氢芘是如此高度紧张的化合物，其可以对许多试剂反应。然而，这些化合物的化学性质非常有限。在这项工作中，我们已经开发了方便的制备应变桥连的芳香族化合物具有双键的桥连链使用叔丁基功能作为位置保护基团的芳香环。在此基础上，我们成功地合成了由桥连的[14]π-轮烯单元构成的环番。2.结构与化学反应活性的关系研究了间环番二烯和二氢芘的亲电取代反应，探讨了反应活性与分子张力的关系。3.结构与光化学性质的关系我们研究了环番二烯和10 b，10 c-二甲基-10 b，10 c-二氢芘的光化学性质。4.新型材料的开发基于环烷烃的光化学性质，我们研究了10 b，10 c-二甲基-10b，10 c-二氢芘的光诱导价态互变异构反应生成8，16-二甲基[2.2]间环蕃-1，9-二烯。我们成功地构建了新型的光致变色体系，并将其应用于先进材料，如光响应分子识别体系。

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.