Electron paramagnetic resonance study of the reactions of the spin trap 3, 5-dibromo-4-nitrosobenzenesulfonate
Electron paramagnetic resonance study of the reactions of the spin trap 3, 5-dibromo-4-nitrosobenzenesulfonate
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自旋陷阱3, 5-二溴-4-亚硝基苯磺酸盐反应的电子顺磁共振研究
DOI：
10.1139/v88-189
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发表时间：
1988
期刊：
影响因子：
--
通讯作者：
J. S. Robertson
中科院分区：
文献类型：
--
作者：
Peter G. Smith;J. S. Robertson
利用基于TiCl3的快速混合、连续流动技术和涉及对称脂肪族偶氮化合物热分解的静态样品研究，我们在25℃的水溶液中用电子顺磁共振表征了3，5-二溴-4-亚硝基苯磺酸盐1的22个自旋加合物。这些自旋加合物，所有的氮氧化物，都表现出中等范围的a-N和β-CH质子分裂常数，我们从空间效应和电子效应的角度进行了讨论。与这些研究相关的空白实验表明，1的水溶液在光和热作用下不产生自由基。此外，我们还研究了1的水溶液在25°C下的静态电子顺磁共振，这些水溶液既有单独存在，也有几种丙烯酸单体和甲基丙烯酸单体的存在，以及在有光和无光的情况下。只有当含有甲基丙烯酸类单体时，这些溶液才会产生自由基，即氮氧化物，光的存在对反应没有影响。
Using rapid-mixing, continuous-flow TiCl3-based techniques and also by means of static-sample studies involving the thermal decomposition of symmetric aliphatic azo compounds, we have characterized by electron paramagnetic resonance 22 spin adducts of 3,5-dibromo-4-nitrosobenzenesulphonate, 1, in aqueous solution at 25 °C. These spin adducts, all nitroxides, exhibit a moderately wide range of a-nitrogen and β-CH proton splitting constants, which we discuss in terms of steric and electronic effects. In connection with these studies, blank experiments showed that aqueous solutions of 1 gave no radicals when exposed to light and heat. In addition, we have studied by electron paramagnetic resonance at 25 °C static samples of aqueous solutions of 1 both by itself and in the presence of each of several acrylic and methacrylic monomers and in both the presence and absence of light. These solutions yielded radicals, namely, nitroxides, only when containing methacrylic monomers, the presence of light having no eff...