论文部分内容阅读
本文研究了乙氧羰基甲烯对戊烷、己烷、庚烷和辛烷的插入反应。用色谱-质谱联用法分离并鉴定了插入反应得到的各种异构体,以及测定了在烷烃各位置碳原子上的插入产物的分配比。实验表明在烷烃的各个碳原子上插入产物的分配比例与从反应几率的计算所得的数值不符。文中提出的机理,即经由甲烯夺取氢原子后所生成的碳阳离子或自由基,有一部分重排而后再与乙氧羰基负离子或自由基偶合,可以解释这样的结果。
In this paper, we studied the insertion of ethoxycarbonylmethane into pentane, hexane, heptane and octane. The various isomers obtained by the insertion reaction were isolated and identified by chromatography-mass spectrometry and the partition ratio of the inserted products at the carbon atoms in each position of the alkane was determined. Experiments have shown that the distribution ratio of the inserted products on each carbon atom of the alkane does not agree with the value calculated from the reaction probability. The mechanism proposed in this paper is that carbamates or free radicals generated after the hydrogen atoms have been taken off via the methylenes are partly rearranged and then coupled with ethoxycarbonyl anions or radicals to explain such a result.