Studies in Organic Free Radical and Cation Radical Chemistry

对一种新品种的稳定性和反应性的研究 偶氮化合物产生的自由基物种将 进行。反应机制将通过使用 在包括电分析方法的各种技术中， 激光闪光光解，量热法，制备和 定量光化学和ESR。用于工程的 调查将包括：（1）评估的稳定性 氮杂烯丙基自由基及其决定因素 重组以产生二聚体;（2）确定 使用自由基时钟的环状双自由基的寿命;以及 (3)氧化的滞留机理的阐明 偶氮烷烃通过稳定的阳离子自由基盐。该项目将 包括各种新型偶氮化合物的合成， 以及速率过程的精确计算， 确定活性中间体的特性。 %%% 有机动力学计划的这笔赠款支持 保罗·S教授的工作。莱斯大学的恩格尔。 这些研究将围绕反应和固有的 产生的自由基物种的稳定性 某些化合物暴露在热或光下。 为了确定这些自由基的性质， 它们只存在十亿分之几秒， 将使用复杂的方法。通过了解 这些中间体化合物的稳定性， 设计出类似的系统， 导致更快的反应。这一点尤其重要 由于待研究的基础化合物代表一类 化学物质，已发现广泛使用在一个 各种工业应用，包括 塑料和泡沫。

An investigation of the stability and reactivity of a variety of radical species generated from azo compounds will be conducted. Reaction mechanisms will be established by the use of a variety of techniques including electroanalytical methods, laser flash photolysis, calorimetry, preparative and quantitative photochemistry, and ESR. The projects to be investigated will include: (1) assessment of the stability of azaallyl radicals and the factors which determine their recombination to yield dimers; (2) determination of the lifetimes of cyclic biradicals using a free radical clock; and (3) elucidation of the detained mechanism of the oxidation of azoalkanes by stable cation radical salts. The project will involve both the synthesis of a variety of novel azo compouunds as well as precise calculations of rate processes and the determination of the identity of reactive intermediates. %%% This grant from the Organic Dynamics Program supports the continuing work of Professor Paul S. Engel at Rice University. These studies will be center around the reactions and inherent stabilities of radical species which are generated upon exposure of certain chemical compounds to either heat or light. In order to ascertain the nature of these radical species, which exist for only a few billionths of a second, a variety of sophisticated methods will be utilized. By understanding the stability of these intermediate compounds, it will be possible to devise similar systems that will be more efficient and result in faster reactions. This is particularly important since the base compounds to be investigated represent a class of chemical substances which have found widespread use in a variety of industrial applications involving the processing of plastics and foams.