权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Studies on Synthesis, Reaction and Functionality of the Bridged Aromatic Compounds

桥联芳香族化合物的合成、反应及功能研究

基本信息

批准号：
02640399
负责人：
YAMATO Takehiko
金额：
$ 1.34万
依托单位：
SAGA UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1990
资助国家：
日本
起止时间：
1990 至 1992
项目状态：
已结题

项目摘要

1. The development of synthesis of the bridged aromatic compounds Although there are numerous reports concerning synthesis of the bridged aromatic compounds, their preparative routes seem to be too long for practical purposes. The [2.2]meta- and [2.2]metaparacyclophanes are so highly strained compounds that may be reactive toward many reagents. However, the chemistry of these compounds is very limited since their preparation from easily available compounds are very limited. In this work, we have developed the convenient preparation of the strained bridged aromatic compounds using the tert-butyl function as a positional protecting group on aromatic ring. Furthermore, we have applied this method to the synthesis of large membered macrocyclic metacyclophanes.2. Relationship between the reactivity and structures. Electrophilic substitution reactions of medium-sized cyclophanes were studied in order to investigate the relationship between the reactivity and the molecular strain. For example, in the electrophilic aromatic substitution of 8-substituted [2.2]metaparacyclophanes the isomerization and tramsannular reaction due to the release of the molecular strain were observed. We have studied on the reactive organic intermediates, which are contained cyclophane skeleton, for example, carbenes, nitrenes, and benzaynes etc.3. The development to the advanced materials. The conformational studies of cyclophanes and the application for the advanced materials, for example photo-response materials, host compounds, and new conductive cyclophane polymers etc. were investigated. For example, the functionalized macrocyclic metacyclophanes, which we have designed in this work found to act as host compounds and have abilities of molecular recognition such as organic compounds and metal ions.The relationship between the reactivity and physical properties was also investigated by X-ray diffraction analysis.

1.桥连芳香族化合物的合成进展尽管有许多关于桥连芳香族化合物的合成的报道，但它们的制备路线似乎太长而不实用。[2.2]Meta-和[2.2]间对环芳是如此高张力的化合物，其可对许多试剂具有反应性。然而，这些化合物的化学性质非常有限，因为它们由容易获得的化合物制备的方法非常有限。在本工作中，我们开发了一种利用叔丁基官能团作为芳环上的位置保护基的应变桥联芳族化合物的方便制备方法。此外，我们还将该方法应用于大环间环芳的合成.反应性与结构的关系。研究了中型环番的亲电取代反应，探讨了反应活性与分子张力的关系。例如，在8-取代[2.2]间对环芳的亲电芳香取代反应中，观察到由于分子应变的释放而引起的异构化和跨环反应。研究了含环番骨架的反应性有机中间体，如卡宾、氮烯、苯乙炔等。向先进材料发展。综述了环蕃的构象研究及其在光响应材料、主体化合物、新型导电环蕃聚合物等新材料中的应用。例如，我们设计的功能化大环间环芳类化合物，可以作为主体化合物，对有机化合物和金属离子等具有分子识别能力，并通过X射线衍射分析研究了其反应活性与物理性能的关系。