Mechanistic and Exploratory Organic Photochemistry

机理和探索性有机光化学

• 批准号: 8801796
• 负责人: Howard Zimmerman
• 金额: $ 107.11万
• 依托单位: University of Wisconsin-Madison
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1988
• 资助国家: 美国
• 起止时间: 1988-03-01 至 1993-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8801796&HistoricalAwards=false
• 关键词: Mechanistic; Exploratory; Organic; Photochemistry

Our overall aim is to study photochemical mechanisms and to develop new photochemical mechanistic methodology. Among the specific problems to be investigated are the following: (1) A study of some allene rearrangements which appear parallel to ( ) ketone counterparts ( ), (2) a search for the mirror image process, where a ( ) excited is involved, (3) completion of the synthesis and study of bugatriyne, a bicyclic Mobius type of molecule with three acetylenic bridges, (4) synthesis and study of the hexa-yne relative of bugatriyne, (5) use of chiral quenchers to determine whether species along the reaction coordinate are subject to energy transfer, (6) continuation of our efforts on solid state photochemistry and means of controlling the solid state medium, (7) investigation of hypersurfaces for many of the reactions we have studied, including a comparison of the theoretical methods, (8) continuing our energy transfer studies using the rod-like molecules we have synthesized to ascertain if we really do have sigma exciton transfer, (9) utilization of bond-oriented basis set orbitals in SCF_CI calculations to give results meaningful to organic chemical studies, (10) testing of our ( ) treatment to our quantum mechanical results to assess energy localization and diffusion during photochemical reaction, (11) exploration of the "Mechanism C" triplet rearrangement of vinylcyclopropenes to determine regioselectivity and to uncover the mechanisms of the diradical ring expansions, (12) determination of the mechanism of rearrangement of the acylcyclopropenes as well as imine and thione relatives, (13) investigation of the generality and sources of "Exchange Integral Control" of reaction multiplicity, (14) development of new photochemical concepts.

我们的总体目标是研究光化学机制并 发展新的光化学机理方法学。 中 具体问题如下：（1）A 研究一些似乎平行于 （）酮对应物（），（2）寻找镜像 过程，其中涉及（）激发，（3）完成 双环Mobius型丁三炔合成与研究 （4）含三个炔键分子的合成， 丁三炔的六炔类化合物的研究（5）手性化合物的应用 猝灭剂，以确定是否物种沿着反应 坐标经受能量转移，（6）连续 我们在固态光化学方面的努力和手段 控制固态介质，（7）研究 我们研究过的许多反应的超曲面， 包括理论方法的比较，（8） 继续我们的能量转移研究， 来确定我们是否真的有 σ激子转移，（9）利用键取向基 在SCF_CI计算中设置轨道以给出有意义的结果 有机化学研究，（10）测试我们的（）治疗 我们的量子力学结果来评估能量局域化 光化学反应过程中的扩散;（11）探测 的“机制C”三重重排， 乙烯基环丙烯，以确定区域选择性， 双自由基环扩张的机制，（12） 重排机制的确定 酰基环丙烯类以及亚胺类和环丙烯类相关物，（13） 对“交换”概念的一般性和来源的考察 反应多重性的“整体控制”;（14）发展 新的光化学概念