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Generation and Application of Radicals and Polyradicals

自由基和多自由基的产生和应用

基本信息

批准号：
05453031
负责人：
OKADA Keiji
金额：
$ 4.1万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1993
资助国家：
日本
起止时间：
1993 至 1994
项目状态：
已结题

项目摘要

This project established 1) a new and efficient radical generation method which is applicable to organic synthesis (investigation A), 2) a new route to trimethylenemethane diradical from [3] dendralene (investigation B), and 3) a methodology utilizing pyridinyl radicals as spin building blocks for high spin organic compounds (investigation C).In the investigation A,a very efficient and mild radical generation method was realized by utilizing Nacyloxyphthalimides which can be readily prepared from various carboxylic acid in high yields. The reaction proceeds in the presence of colored radical scavenger in aqueous solvent with visible light excitation at room temperature and the reaction is readily applied to reductive decarboxylation, decarboxylative phenylselenenylation, and decarboxylative phenyltellurenylation. The quantum yields of theses reactions are usually over unity and readily available right sources such as projector lamp, halogen lamp, and sunlight can be used. Since phenylselenenyl group is known to be converted to various functional groups, this method clearly widens the scope of synthetic methods starting from carboxylic acids.In the investigation B,a novel photochemical reaction of [3] dendralene derivative leading to trimethylenemethane diradical intermediate was found. The intermediate was successfully trapped by molecular oxygen or in the flash photolysis experiment.4,4'-(m-Phenylene) bis (1-menthyl-2,6-diphenylpyridinyl) diradical and its analogues were prepared and their spin-multiplicities in the ground states were investigated by means of ESR in the investigation C.

本课题建立了1）一种新的、高效的适用于有机合成的自由基生成方法（研究A）; 2）从[3] dendralene得到三亚甲基甲烷双自由基的新途径（研究B），和3）利用吡啶基自由基作为高自旋有机化合物的自旋结构单元的方法在研究A中，通过利用N酰氧基邻苯二甲酰亚胺实现了非常有效和温和的自由基产生方法，所述N酰氧基邻苯二甲酰亚胺可以容易地由各种羧酸以高产率制备。该反应在有色自由基清除剂存在下在水溶剂中在室温下用可见光激发进行，并且该反应容易地应用于还原脱羧、脱羧苯基硒化和脱羧苯基碲化。这些反应的量子产率通常超过1，并且可以使用容易获得的合适光源，如投影灯、卤素灯和太阳光。由于已知苯基硒基可转化为各种官能团，因此该方法明显拓宽了从羧酸开始的合成方法的范围。在研究B中，发现了[3] dendralene衍生物导致三亚甲基甲烷双自由基中间体的新型光化学反应。该中间体被分子氧或闪光光解实验成功捕获。4，本文合成了4 ′-（间苯撑）双（1-薄荷基-2，6-二苯基吡啶基）自由基及其类似物，用ESR研究了它们的基态自旋多重性。