Cation Radical Explorations

有机动力学项目的这笔拨款支持了罗切斯特大学约瑟夫·P·迪诺琴佐博士的继续工作，他正在研究单个电子被移除的分子的反应。对这些活性物种的研究将提供有关酸碱反应的基本信息，并将导致合成有机化学的新方法。迪诺森佐博士将进行的实验将包括两个与阳离子自由基相关的研究。第一种是为了提供对叔胺阳离子自由基和烷基芳基阳离子自由基的动力学酸性的详细了解。可分离阳离子自由基盐的制备、表征和质子转移研究将提供动力学和热力学数据，有助于识别阳离子自由基去质子化与中性闭壳有机分子去质子化的异同。第二个研究旨在阐明具有不饱和取代基环丙烷的阳离子自由基反应的范围、机理和合成应用。

This grant from the Organic Dynamics Program supports the continuing work of Dr. Joseph P. Dinnocenzo at the University of Rochester, who is studying the reactions of molecules from which a single electron has been removed. Investigations of these reactive species will provide fundamental information on acid-base reactions and should lead to new methodology in synthetic organic chemistry. The experiments to be carried out by Dr. Dinnocenzo will comprise two related investigations of cation radicals. The first is designed to provide a detailed understanding of the kinetic acidities of tertiary amine cation radicals and alkylaromatic cation radicals. Preparation, characterization, and proton-transfer studies of isolable cation radical salts will afford kinetic and thermodynamic data that will help to identify the similarities and differences between cation radical deprotonations and those of neutral, closed-shell organic molecules. The second investigation is designed to elucidate the scope, mechanism, and synthetic applications of cation radical reactions for cyclopropanes having unsaturated substituents.