Kinetics and Mechanism of Initiated Oxidation of 4,7-Dihydro-1,3-dioxepines

Yu. G. Borisova, G. Z. Raskil’dina, N. S. Pitsyn, A. V. Sirik, E. M. Pliss
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Abstract

The initiated oxidation of 4,7-dihydro-1,3-dioxepine and 2-isopropyl-4,7-dihydro-1,3-dioxepine with molecular oxygen in the liquid phase (323 K) was studied. Microvolumetry, IR Fourier-transform spectroscopy, 1H NMR spectroscopy, potentiometry in combination with computer simulation and quantum chemical calculations were used. It was found that during the oxidation process, continuation of chains is realized due to the abstraction of a hydrogen atom by the peroxyl radical from the CH bond of the cycloolefin weakened by conjugation.

Abstract Image

4,7-二氢-1,3-二氧杂环庚烷引发氧化的动力学和机理
摘要 研究了 4,7-二氢-1,3-二氧杂环庚烷和 2-异丙基-4,7-二氢-1,3-二氧杂环庚烷与分子氧在液相(323 K)中的引发氧化。研究中使用了微量水分测定法、红外傅立叶变换光谱法、1H NMR 光谱法、电位测定法以及计算机模拟和量子化学计算。研究发现,在氧化过程中,由于过氧自由基从因共轭作用而减弱的环烯烃 CH 键中抽取了一个氢原子,链得以延续。
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