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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.

我们开发了一种光学纯螺烯，1，12-二甲基苯并[c]菲-5，8-二羧酸的多克合成，这使我们能够进行分子中螺旋度的化学研究。本文研究了含螺烯的大环化合物的合成及性质.采用双向法合成了含1 ~ 10个螺烯单元的环酰胺类化合物。通过光谱分析比较了它们的结构，发现在小于五聚体的化合物中存在“环效应”。较大的化合物被证明具有灵活的结构。合成了含3 ~ 6个螺烯的环炔。发现三聚体在有机溶剂中自聚集。该化合物仅形成二聚体，在检查的浓度范围内未观察到较高的聚集。螺烯部分的手性对聚集行为起着重要的作用.采用一锅法合成了含三个和四个螺烯的环状酸酐.研究了螺烯二甲酸酯的区域选择性多硝化反应，并开发了在对称位置进行官能化的方法.研究了四硝基螺烯与芘的电荷转移络合反应。并将其晶体结构与外消旋体进行了比较。研究了缺电子螺烯和富电子螺烯的手性识别作用。相同构型的螺烯形成更稳定的配合物。