Molecular Discrimination in the Excited States and Its Synthetic Applications

本文对激发态的分子分辨及其在合成中的应用进行了研究，得到了以下结果.对具有两个发色团的有机分子在激发态的分子内相互作用的研究为激发态激基复合物和三链体的结构和性质提供了重要的信息.具有1-氰基萘发色团的有机分子与烯烃或呋喃发色团的分子内光环加成反应以立体选择性方式产生（2 + 2）或（4 + 4）环加合物。还研究了添加剂和溶剂效应。此外，带有烯基的萘甲酸甲酯衍生物的光反应通过分子内1，10-夺氢得到了一种新的八元酮.在手性1，4-二氰基萘衍生物和2，2 '-二甲基-1，1'-联蒽的荧光猝灭过程中，发现了手性识别现象。在激基复合物猝灭中也观察到手性歧视。研究了9，10-二氰基蒽对苯中醇与芳基烯烃通过激基复合物的分子间和分子内光加成反应的增敏作用。在手性1，4-二氰基萘衍生物或1，4-二氰基萘存在下，甲醇与手性或非手性芳基烯烃的光加成以对映或非对映选择性方式发生。

The molecular discrimination in the excited states and its synthetic applications have been studied and the following results were obtained.1. The studies on the intramolecular interaction of organic molecules having two chromophores in the excited states provide significant information regarding the structures and the properties of exciplexes and triplexes in the exciteds states.2. The intramolecular photocycloaddition of organic molecules having l-cyanonaphthalene chromophore and alkenes or furan chromophore gives (2+2) or (4+4) cycloadducts in a stereoselective manner. The additive and solvent effects are also investigated. In addition, the photoreaction of methyl naphthoate derivatives bearing alkenyl groups gives a novel 8-membered ketone via intramolecular 1,10-hydrogen abstraction.3. Chiral discrimination is observed in the fluorescence quenching of chiral 1,4-dicyanonaphthalene derivatives and 2,2' -dimethyl-1,1' -bianthryl by some chiral quenchers. Chiral discrimination is also observed in the exciplex quenching.4. Inter-and intramolecular photoaddition of alcohols to arylalkenes via exciplexes in benzene is sensitized by 9,10-dicyanoanthracene in a stereoselective manner. The photoaddition of methanol to chiral or achiral arylalkenes in the presence of chiral 1,4-dicyanonaphthalene derivatives or 1,4-dicyanonaphthalene occurs in an enantio-or diastereoselective manner.