Captodative Radicals, Diradicals, and Their Peroxides

在有机动力学计划的更新奖是在 支持泰德·科赫博士的研究， 博尔德的科罗拉多。该研究将集中在captodative 自由基通过以下因素的综合作用而稳定 给电子和吸电子基团。 这种效果 氨基和羧基取代基应是最大的。 的 研究将进一步探索2-氧代吗啉基自由基 其取代基在刚性环中， 电子互动 这些自由基存在于 平衡与他们的二聚体在溶液中，并作为温和的功能 在各种溶剂中的单电子还原剂 包括水。 根据烷基的位置， 自由基化学计量地还原分子氧， 过氧化氢或形成可分离的过氧化物。 本研究的长期目标是设计、制备 和使用俘获性自由基。 具体目标是 设计、合成和表征新的 2-氧代吗啉基自由基和双自由基， 氧可逆地形成有用的过氧化物或用作 用于大分子结构的交联剂。 热 并且所得过氧化物的光化学反应性将是 确立了习 氧化还原活性和捕获稳定化 2-氧代吗啉基作为结构的函数， 中将确定。 具有增强的氧化还原的新结构 活动将被设计和合成。

This renewal award in the Organic Dynamics Program is in support of the research of Dr. Tad Koch at the University of Colorado at Boulder. The research will focus on captodative radicals which are stabilized through the combined effect of electron-donating and electron-withdrawing groups. This effect should be maximum with amino and carboxy substituents. The research will explore further the 2-oxomorpholinyl free radical whose substituents are in a rigid ring which maximizes the electronic interaction. These free radicals exist in equilibrium with their dimers in solution and function as mild one-electron reducing agents in a wide variety of solvents including water. Depending upon the placement of alkyl groups, the radicals reduce stoichiometrically molecular oxygen to hydrogen peroxide or form isolable peroxides. The long range goal of the research is the design, preparation and use of captodative radicals. The specific objectives are the design, synthesis and characterization of new 2-oxomorpholinyl radicals and diradicals which will either bind oxygen reversibly, form useful peroxides or serve as crosslinking agents for macromolecular structures. The thermal and photochemical reactivity of the resulting peroxides will be established. The redox activity and captodative stabilization of 2-oxomorpholinyl radicals as a function of structure and medium will be determined. New structures with enhanced redox activity will be designed and synthesized.