KINETICS OF OLEFIN OXIDATION
KINETICS OF OLEFIN OXIDATION
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DOI：
10.1039/qr9490300001
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发表时间：
1949-01-01
期刊：
影响因子：
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通讯作者：
BOLLAND, JL
中科院分区：
文献类型：
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作者：
BOLLAND, JL
在自由基独立存在的二十年里，可以用自由基中间体来解释的有机化学反应的数量不断增加。在缺乏基于严格的反应动力学分析的结论的情况下，对这种反应机理中所包含的基本自由基过程的鉴定主要是基于对最终反应产物的定性鉴定得出的许可证据。动力学方法在应用上的滞后，部分是因为它们本质上更费力，部分是因为经常侵入二次反应，使得对主要反应的完全定量处理变得极其困难。然而，近年来，在建立定量的自由基化学方面取得了实质性的进展。因此，每种类型的自由基在它将参与的反应中表现出一定的特异性；同样，一系列自由基参与给定的一般化学反应的容易程度可以表现出明显的差异。应用反应动力学来确定支配反应的基本原理。因此，一般来说，自由基的反应性可以分解为两部分。首先，有必要确定各种化学反应中可能发生的涉及自由基的基元反应；其次，在确定了特定自由基反应的发生后，应跟踪自由基和非自由基反应物的化学结构变化对反应效率的影响。例如，已被最仔细地识别的自由基反应是在乙烯基聚合中发生的传播过程：
IN the twenty years that have elapsed since the independent existence of free radicals was established, the number of organic chemical reactions explicable in terms of free-radical intermediates has multiplied continuously. In the absence of conclusions based on rigorous reaction-kinetic analyses, identification of the elementary free-radical processes contained in such reaction mechanisms has been based largely on permissive evidence derived from the qualitative identification of final reaction products. This lag in the application of kinetic methods arises partly from their intrinsically more laborious nature and partly because intrusion of secondary reactions frequently renders a completely quantitative treatment of the main reaction extremely difficult. In recent years, however, substantial progress has been made towards establishing free-radical chemistry on a quantitative basis.Thus each type of free radical shows a certain specificity in the reactions in which it will take part; again, the ease with which a series of radicals participate in a given general chemical reaction can show distinct variation. The application of reaction kinetics to determine the basic principles governing the. reactivity of radicals in general may therefore be resolved into two parts. I n the first place, it is necessary to identify the elementary reactions involving free radicals, which may occur in a wide variety of chemical reactions; secondly, having established the occurrence of a particular radical reaction, the influence on reaction efficiency resulting from alteration in the chemical structure of the radical and non-radical reactants should be followed. For example, a radical reaction which has been most carefully identified is the propagation process occurring in vinyl polymerisations: