Free Radical and Photochemistry of Organophosphorus Systems

9319419本课程将研究三配位和五配位磷分子的新自由基和光化学反应，重点关注反应机理和合成应用。这些反应将包括使用有机磷分子作为自由基捕捉剂，以及通过单电子转移由三配位磷衍生物产生阳离子自由基的化学。光化学研究将包括亚磷酸烯丙基三酯的光重排和亚磷酸苄酯的光-阿布鲁佐夫重排。将探讨烯丙基重排中的1，3-双自由基中间体和光-阿布鲁佐夫重排中的单、三重态激发态问题。%有机动力学项目的这笔拨款支持犹他大学韦斯利·G·本特鲁德教授的继续工作。将研究含磷原子的分子与三个或四个其他原子或基团连接的新反应。这些基团将包含碳、氢、氧和其他原子。这些反应将包括捕获碳自由基(例如，碳与其他三个原子成键，并拥有一个非键电子)和紫外光诱导的反应。将注意这些反应和合成应用中的详细步骤。这项工作在抗肿瘤和抗病毒药物、燃料添加剂、杀虫剂和关键生化中间体等领域提供了潜在的影响。***

9319419 Bentrude New free radical and photochemical reactions of tri- and penta-coordinate phosphorous molecules will be studied with attention directed to reaction mechanisms and synthetic applications. The reactions will include the use of organophosphorous molecules as free radical trapping agents and the chemistry of cation radicals produced from tri- coordinate phosphorous derivatives by single-electron transfer. Photochemical studies will include photorearrangements of allyl phosphite triesters and photo- Abruzov rearrangements of benzyl phosphites. Questions of 1,3-biradical intermediates in the allylic rearrangement and of singlet or triplet excited states in the photo-Abruzov rearrangement will be explored. %%% This grant from the Organic Dynamics Program supports the continuing work of Professor Wesley G. Bentrude at the University of Utah. New reactions of molecules containing phosphorous atoms with three and four other atoms or groups attached will be studied. The groups will contain carbon, hydrogen, oxygen, and other atoms. The reactions will include trapping of carbon free radicals (e.g., carbon bonding to three other atoms and possessing one non-bonded electron) and ultraviolet-light induced reactions. Attention will be given to the detailed steps in these reactions and synthetic applications. This work provides potential impact in areas such as antitumor and antiviral agents, fuel additives, pesticides, and key biochemical intermediates. ***