Free Radical and Photochemical Reactions of OrganophosphorusSystems

有机磷系统的自由基和光化学反应

• 批准号: 8703485
• 负责人: Wesley Bentrude
• 金额: $ 20.45万
• 依托单位: University of Utah
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1987
• 资助国家: 美国
• 起止时间: 1987-06-01 至 1990-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8703485&HistoricalAwards=false
• 关键词: Free; Radical; Photochemical; Reactions; OrganophosphorusSystems

This grant in the Organic and Macromolecular Chemistry Program supports research by Prof. W. Bentrude, which aims at elucidating mechanisms in chemical reactions of organophosphorus systems with free radicals as reaction intermediates. This work is important for two reasons: (1) It will provide understanding of the step- by-step processes by which certain phosphorus-containing organic molecules react to generate unpaired-electron-intermediates (free radicals) when excited by light absorption and other energizing events; and (2) many of these reactions may be used as synthetic methods for preparation of sensitive compounds. Studies of both free radical and photochemical reactions of organophosphorus molecules are planned. Both new investigations and new aspects of reactions discovered in the previous grant period will be pursued. A major theme is the design and investigation of reaction systems in which true biradicals or biradical-like electronic excited states react with tricovalent phosphorus in intra- or intermolecular processes. Mechanistic, exploratory new-reaction, and synthetic aspects of these systems are to be examined. Reactants included in this work are photoexcited alkenes, alkynes, allenes, carbonyls, and thiocarbonyls, along with biradicals from Norrish Type I photocleavage reactions and the photolyses of azo compounds. In addition, new reactions in which intact phosphoranyl radicals are trapped will be studied. The mechanistic aspects and synthetic applications of the intramolecular photo-Arbuzov reaction of benzyl phosphites, newly discovered in Bentrude's laboratory, will be explored. Also to be thoroughly studied is the photosolvolysis of benzyl phosphites in the presence of alcohols. Its mechanism and generality using other chromophores and leaving groups will be assessed.

有机和高分子化学项目的这笔资助支持 W. Bentrude 教授的研究，该研究旨在阐明以自由基作为反应中间体的有机磷系统的化学反应机制。 这项工作之所以重要，有两个原因：（1）它将提供对某些含磷有机分子在受到光吸收和其他供能事件激发时反应生成不成对电子中间体（自由基）的逐步过程的理解； (2)许多这些反应可以用作制备敏感化合物的合成方法。 计划对有机磷分子的自由基反应和光化学反应进行研究。 将继续进行新的调查和上一个资助期间发现的反应的新方面。 一个主要主题是反应系统的设计和研究，其中真正的双自由基或类双自由基电子激发态与三价磷在分子内或分子间过程中发生反应。 这些系统的机理、探索性新反应和合成方面都有待研究。 这项工作中包括的反应物包括光激发的烯烃、炔烃、丙二烯、羰基和硫代羰基，以及来自 Norrish I 型光裂解反应和偶氮化合物光解的双自由基。 此外，还将研究捕获完整正膦基自由基的新反应。 本特鲁德实验室新发现的亚磷酸苄酯的分子内光阿尔布佐夫反应的机理和合成应用将被探索。 还需要深入研究亚磷酸苄酯在醇存在下的光溶剂解作用。 将评估其使用其他发色团和离去基团的机制和通用性。