Low-Energy Electron-Induced Hydroamination Reactions between Different Amines and Olefins
Low-Energy Electron-Induced Hydroamination Reactions between Different Amines and Olefins
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DOI：
10.1021/jp501192v
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发表时间：
2014-04-03
影响因子：
3.7
通讯作者：
Swiderek, P.
中科院分区：
文献类型：
--
作者：
Boehler, E.;Bredehoeft, J. H.;Swiderek, P.
采用热脱附光谱法（TDS）研究了含烯烃和胺或氨的多层凝聚膜的电子暴露引发的反应。在所有情况下，检测到导致氨或胺加成到烯烃的C=C双键上的电子诱导的氢胺化反应。氢胺化产物产率对电子能量的依赖性进行了研究，为乙烯与氨，乙胺，二乙胺和点的混合物，在所有三种情况下，电离驱动的过程。并行反应包括形成较大的烃以及反应物的断裂，特别是胺的断裂，从而即使在不存在烯烃的情况下也获得更高取代的类似物。这些反应的机制进行了审查，并提出了一个电离驱动的烯烃二聚反应，非常类似于先前描述的加氢胺化。结果强调了电离驱动的电子诱导合成的一般概念，但也展示了反应的复杂性如何随着反应物变得更大而增加。
Thermal desorption spectrometry (TDS) was applied to investigate reactions initiated by electron exposure of multilayer condensed films containing both an olefin and an amine or ammonia. In all cases, electron-induced hydroamination reactions leading to addition of ammonia or an amine to the C=C double bond of the olefin were detected. The dependence of the hydroamination product yield on the electron energy was studied for mixtures of ethene with ammonia, ethylamine, and diethylamine and points, in all three cases, to an ionization-driven process. Concurrent reactions include the formation of larger hydrocarbons as well as fragmentation of the reactants and, in particular, of the amines so that higher substituted analogues are obtained even without the presence of an olefin. The mechanisms of these reactions are reviewed and an ionization-driven olefin dimerization is proposed that closely resembles the previously described hydroamination. The results underline the general concept of electron-induced synthesis driven by ionization but also demonstrate how the complexity of the reactions increases as the reactants become larger.