Factors affecting the rates of addition of free radicals to alkenes-determination of absolute rate coefficients using the persistent aminoxyl method
Factors affecting the rates of addition of free radicals to alkenes-determination of absolute rate coefficients using the persistent aminoxyl method
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DOI：
10.1021/ja025730g
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发表时间：
2002-08-14
影响因子：
15
通讯作者：
Poole, JS
中科院分区：
文献类型：
--
作者：
Beckwith, ALJ;Poole, JS
以烷基自由基与持久性氨基氧自由基1，1，3，3-四甲基-异吲哚啉-N-氧自由基（1）的偶联速率为动力学探针，测定了烷基自由基与丙烯酸甲酯加成反应的绝对速率系数。结果进行了讨论的攻击自由基的结构和功能化的作用，另外的速率，特别是因为它们影响空间，极性和疏水因子。对测定自由基加成速率系数的其他方法的aminoxyl方法进行了评估。
The rate of coupling of alkyl radicals with the persistent aminoxyl radical 1,1,3,3-tetramethyl-isoindolin-N-oxyl (1) has been used as a kinetic probe to determine absolute rate coefficients for the addition of alkyl radicals to methyl acrylate. The results are discussed in terms of the role of the structure and functionalization of the attacking radical on the rates of addition, particularly as they affect steric, polar, and enthalpic factors. The aminoxyl method is assessed against other methods for determining free radical addition rate coefficients.