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Generation of methylene by the liquid phase oxidation of isobutene with nitrous oxide
Tetrahedron ( IF 2.1 ) Pub Date : 2018-05-17 , DOI: 10.1016/j.tet.2018.05.022
Sergey Semikolenov , Dmitry Ivanov , Dmitry Babushkin , Sergey Malykhin , Alexander Kharitonov , Konstantin Dubkov

The application of nitrous oxide as an alternative oxidant provides new opportunities for selective oxidation of olefins. Here, we studied for the first time the thermal oxidation of isobutene with N2O in the liquid phase. The study revealed that the oxidation proceeds via 1,3-dipolar cycloaddition of N2O to the CC bond by two routes forming unstable 4,5-dihydro-[1,2,3]-oxadiazole intermediates. The main route (the contribution of 91%) includes the addition of the N2O oxygen to the second carbon atom in olefin. In this case, the oxadiazole decomposes with the CC bond cleavage yielding acetone, methylene (:CH2), and N2. The methylene then readily reacts with isobutene and benzene (solvent). The minor route involves the addition of the N2O oxygen to the first carbon atom and the oxadiazole decomposition with a hydrogen shift leading to isobutanal and N2.

The main distinctive feature of the studied reaction is the formation of methylene in high yield.



中文翻译:

通过异丁烯与一氧化二氮的液相氧化生成亚甲基

一氧化二氮作为替代氧化剂的应用为烯烃的选择性氧化提供了新的机会。在这里,我们首次研究了异丁烯与液相中N 2 O的热氧化。研究表明,氧化是通过N 2 O的1,3-偶极环加成反应通过两条途径形成的不稳定的4,5-二氢-[1,2,3]-恶二唑中间体发生的。主要途径(贡献率为91%)包括将N 2 O氧添加到烯烃中的第二个碳原子上。在这种情况下,恶二唑通过C C键断裂而分解,生成丙酮,亚甲基(:CH 2)和N 2。然后,亚甲基容易与异丁烯和苯(溶剂)反应。较小的途径包括将N 2 O氧添加到第一个碳原子上,并通过氢位移导致异丁醛和N 2的恶二唑分解。

所研究的反应的主要特征是高产率地形成亚甲基。

更新日期:2018-05-17
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