Kinetic Effects in Radical, Diradical, Carbanion, Carbene, and Pericyclic Reactions

氟取代对自由基、二自由基、碳离子、碳烯和周环反应的影响。通过在衬底上战略性地放置氟，将评估其动力学、立体化学和区域化学效应。要研究的过程包括Cope重排、电环反应、环丙烷和乙烯基环丙烷重排、甲基环丙烷和甲基环丁烷重排。本研究的重点将是利用分子内环化反应来检验氟取代基对自由基、碳离子、碳烯和1,3偶极子反应的立体、极性和立体电子反应性影响。来自有机动力学计划的这笔赠款支持佛罗里达大学W. R. Dolbier教授对碳氟化合物化学的研究。将氟掺入各种物质中可以增强其效用，并提供具有优异性能的材料，用于各种不同的应用，从耐化学纤维到在高湿度环境中抵抗水渗透的聚合物。为了最大限度地发挥氟对所附着底物的影响，有必要充分了解氟在各种不同条件下对化学反应的影响。Dolbier教授的研究将提供宝贵的信息，这将有助于加速氟基材料的发展，并确保充分利用氟碳化合物的独特特性。

The effect of fluorine substitution on radical, diradical, carbanion, carbene, and pericyclic reactions will be conducted. By strategic placement of fluorine on a substrate, the kinetic, stereochemical, and regiochemical effects will be evaluated. Processes to be investigated include Cope rearrangements, electrocyclic reactions, cyclopropane and vinylcyclopropane rearrangements, and methylcyclopropane and methylcyclobutane rearrangements. A highlight of the investigation will be the use of intramolecular cyclization reactions to examine steric, polar, and stereoelectronic reactivity effects of fluorine substituents on reactions of radicals, carbanions, carbenes, and 1,3-dipoles. %%% This grant from the Organic Dynamics Program supports the studies of Professor W. R. Dolbier at the University of Florida on fluorocarbon chemistry. The incorporation of fluorine into a variety of substances can enhance their utility and provide materials with superior properties for use in a variety of different applications ranging from chemically resistant fibers to polymers which resist penetration of water in high humidity environments. In order to maximize the impact of fluorine on the substrate to which it is attached, it is necessary to fully understand the effect that fluorine has on chemical reactions under a variety of different conditions. The studies of Professor Dolbier will provide invaluable information which will help accelerate the development of fluorine based materials and insure that full advantage is taken of the unique properties of fluorocarbons.