Radical Reactions of the Azo and Azoxy Groups

这个有机动力学项目的奖项将支持莱斯大学保罗·恩格尔的研究。研究将广泛地集中在偶氮和偶氧化合物的自由基化学上。具体的研究领域是：(1)确定α -偶氮和偶氮自由基的稳定能量，(2)偶氮过酯作为混合双功能自由基聚合引发剂的用途，(3)应用于自由基时钟的二甲基环丙基羰基重排速率，(4)偶氮基自由基反应，(5)无环偶氮烷烃的热裂解速率，以及(6)偶氮烷烃生成预氧烷双自由基。光化学和热方法将被用来产生自由基的研究。这项研究将促进对偶氮和偶氮基化合物自由基的生成和稳定的基本理解，并探索它们在合成转化和作为高速聚合引发剂的应用。

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.