Free Radical and Photochemistry of Organophosphorus Systems

9319419 Bentrude新的自由基和光化学反应的三-和 五配位磷分子将被研究， 注意力集中于反应机理和合成 应用.反应将包括使用 作为自由基捕获剂的有机磷分子 以及由三配位磷衍生物通过单电子 转移光化学研究将包括 亚磷酸烯丙酯三酯的光重排和亚磷酸苄酯的光Abruzov重排。问题 烯丙基重排中的1，3-双自由基中间体， 单重态或三重态激发态的光-阿布鲁佐夫 将探索重组。 %有机动力学计划的这一赠款支持 Wesley G.教授的继续工作。本特鲁德在 犹他州大学。分子的新反应， 磷原子与三个或四个其他原子或基团 附件将予以研究。这些基团将含有碳， 氢、氧和其他原子。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。关注 将给出这些反应的详细步骤， 合成应用这项工作提供了潜在的影响 在抗肿瘤和抗病毒剂、燃料 添加剂、杀虫剂和关键的生化中间体。 ***

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. ***