Chemistry of Optically Active Helicenes

光学活性螺旋烯的化学

基本信息

批准号：
11470466
负责人：
YAMAGUCHI Masahiko
金额：
$ 9.66万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B).
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11470466/
关键词：
helicene cyclic amides cyclic alkynes cyclic anhydrides LB films CT complex aggregation chiral recognition LB膜環状酸無水和物 Sonogashira反応

项目摘要

We developed a multigram synthesis of an optically pure helicene, 1, 12-dimethylbenzo [c] phenanthrene-5, 8-dicarboxylic acid, which enabled us to conduct studies on the chemistry of helicity in the molecules. The present study deals with the synthesis and properties of macrocyclic compounds containg the helicene.1. Cycloamides containing one to ten helicene units were synthesized by a two-directional method. Their structures were compared spectroscopically, and "ring effect" was observed in the compounds smaller than the pentamer. The larger compounds turned out to possess flexible structures.2. Cycloalkynes contining three to six helicenes were synthesized. The trimer was found to self-aggregate in organic solvents. The compound formed only dimer, and higher-aggregation was not observed in the concentration range examined. The chirality at the helicene moiety played an important role in the aggregation behaviors.3. Cyclic anhydrides containing three and four helicenes were synthesized by a one-pot method.4. Regioselective polynitration of the helicenedicarboxylate was examined, and methods to functionalize at the symmetrical positions were developed.5. The charge-transfer (CT) complexation of a tetranitrohelicene with pyrene was examined. The crystal structure of the optically active helicene was compared with the racemic derivative. Chiral recognition in the CT-complexation was also studied using the electron-deficient helicene and an elecron-rich helicene. The same configuration of the helicenes formed more stable complex.

我们开发了光学纯的螺旋烯，1，12-二甲基苯苯二苯乙烯-5、8-二羧酸的多gram合成，这使我们能够对分子中的螺旋性化学进行研究。本研究涉及甲壳虫构成大环化合物的合成和特性。1。含有一到十个旋晶单元的环氧胺通过二向方法合成。通过光谱比较它们的结构，并在小于五聚体的化合物中观察到“环效应”。较大的化合物证明具有柔性结构。2。合成了三到六架Helicenes的环虫。发现三聚体在有机溶剂中自我聚集。化合物仅形成二聚体，并且在检查的浓度范围内未观察到更高的聚集。旋晶部分的手性在聚集行为中起着重要作用。3。通过一锅方法合成了含有三个和四个螺旋烯的循环酸酐4。检查了旋齿二羧酸盐的区域选择性多元，并开发了在对称位置上官能化的方法。5。检查了四硝基甲烯与pyrene的电荷转移（CT）络合。将光学活性的螺旋烯的晶体结构与外围衍生物进行了比较。还使用电子缺陷式的螺旋烯和富Elecron的螺旋烯研究了CT复合物中的手性识别。相同的架配置形成更稳定的复合物。