Radical Reactions of the Azo and Azoxy Groups

有机动力学计划的这一奖项将支持这项研究 保罗·恩格尔在莱斯大学的研究研究将广泛集中于 偶氮和氧化偶氮化合物的自由基化学。的特定区域 研究将解决的是：（1）确定 α-偶氮和氧化偶氮自由基的稳定能，（2） 作为混合双官能自由基聚合的偶氮酯 引发剂，（3）二甲基环丙基原基的重排速率 自由基时钟，（4）自由基的反应， 偶氮氧基，（5）无环偶氮烷烃的醚化物，和（6） 由偶氮烷烃产生前氧杂环丁烷双自由基。 光化学和 将采用热方法来产生自由基， 调查 这项研究将促进对 衍生自偶氮和氧化偶氮的自由基的产生和稳定 化合物，并探索其在合成转化中的用途， 作为高速聚合的引发剂。

This award made in the Organic Dynamics Program will support the research of Paul Engel at Rice University. The research will focus broadly on the free radical chemistry of azo and azoxy compounds. Specific areas of research that will be addressed are :(1) determination of the stabilization energy of alpha-azo and azoxy radicals, (2) utility of azoperesters as mixed bifunctional free radical polymerization initiators, (3) rearrangement rates of the dimethylcyclopropylcarbinyl radical as applied to radical clocks,(4) free radical reactions of the azoxy group, (5) thermolysis rates of acyclic azoalkanes, and (6) generation of preoxetane biradicals from azoalkanes. Photochemical and thermal approaches will be employed to generate the free radicals under investigation. This research will advance the fundamental understanding of the generation and stabilization of free radicals derived from azo and azoxy compounds as well as explore their use in synthetic transformations and as initiators for high speed polymerizations.