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

自由基、双自由基、碳负离子、卡宾和周环反应中的动力学效应

• 批准号: 9214805
• 负责人: William Dolbier
• 金额: $ 32.64万
• 依托单位: University of Florida
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1992
• 资助国家: 美国
• 起止时间: 1992-07-15 至 1995-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9214805&HistoricalAwards=false
• 关键词: Kinetic; Effects; Radical; Diradical; Carbanion

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.

氟取代对自由基、双自由基、 将进行碳负离子、卡宾和周环反应。 通过将氟策略性地放置在衬底上， 将评价立体化学和区域化学效应。 待研究的过程包括科普重排， 电环化反应，环丙烷和乙烯基环丙烷 重排，甲基环丙烷和甲基环丁烷 重新安排调查的一个亮点将是 使用分子内环化反应来检查空间位阻， 氟的极性和立体电子反应性效应 自由基，碳负离子，卡宾， 和1，3-偶极子。 %%% 有机动力学计划的这笔赠款支持 W教授的研究R.多尔比耶在佛罗里达大学 碳氟化合物化学。将氟加入到 各种物质可以提高其效用， 具有上级性能的材料，用于各种 从耐化学性纤维 涉及在高湿度下抗水渗透的聚合物 环境.为了最大限度地发挥氟对 其所附接的衬底，必须完全 了解氟对化学反应的影响 在各种不同的条件下。的研究 Dolbier教授将提供宝贵的信息， 将有助于加快氟基 材料，并确保充分利用独特的 碳氟化合物的性质。