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本文对光敏剂二苯甲酮存在下,重氮乙酸乙酯光解所产生的乙氧羰基甲烯对已烷的插入反应进行了研究,并与无光敏剂时的插入反应进行了比较.发现光敏剂的存在不影响插入产物性质和它们的分配比例.同时,发现作为三线态猝灭剂的氧的存在对这些反应也没有影响.这些实验结果表明,对己烷的插入反应是由单线态的乙氧羰基甲烯进行的.对在二苯甲酮存在下已烷被空气光氧化的产物进行了仔细的分离和鉴定.结果表明,得到的是2-位和3-位已基自由基偶联和氧化的产物,因此看来,伯位的已基自由基在进行偶联和氧化反应之前先要转位成热力学上比较稳定的仲位自由基。
In the presence of photosensitizer benzophenone, the insertion reaction of ethoxycarbonylmethane produced by photodegradation of ethyl diazoacetate with hexane was studied and compared with the insertion reaction without photosensitizer. The presence of the photosensitizers did not affect the nature of the inserted products and their partition ratio, and at the same time, the presence of oxygen as a triplet quencher was found to have no effect on these reactions. These experimental results show that the insertion of hexane into the mixture is caused by the singlet state Of ethoxycarbonylmethanes.Products of photo-oxidation of hexane with air in the presence of benzophenone were carefully isolated and identified.The results showed that the radical free radicals at 2-position and 3-position were obtained Coupled and oxidized products, it appears that the primary radical already radiates into a more thermodynamically stable secondary radical before proceeding with coupling and oxidation reactions.