Photochemistry and Strained Molecules

将对高应变联烯的合成和反应活性进行研究。拟议的研究将包括研究异丁烯的光化学、不对称的光化学过程、卡宾的光生成，以及光诱导反应产生高应变的联烯。一个主要的目标是开发产生应变双烯和三烯的通用合成方法。高应变中间体的特性和反应性将通过使用基质分离方法和瞬变光谱来检测。此外，制造高分子量环型聚合物的尝试将通过涉及应变中间体的途径进行。来自有机动力学项目的这笔赠款支持新汉普郡大学理查德·P·约翰逊教授的工作。这些研究的目标将是合成高度应变的有机分子，这些分子预计会经历各种非常不寻常的反应。通过开发合成这类物种的一般方法，应该可以生产出目前任何其他工艺都不可能产生的各种化合物。高活性的应变环物种只能存活很短的时间，因此需要专门的技术来证明它们的存在。

A study of the synthesis and reactivity of highly strained allenes will be conducted. The proposed investigation will include studies of cumulene photochemistry, asymmetric photochemical processes, photogeneration of carbenes, and photoinduced reactions to give highly strained allenes. A major objective is to develop general synthetic methods for the generation of strained dienes and trienes. The identity and reactivity of the highly strained intermediates will be detected by use of matrix isolation methods and transient spectroscopy. In addition, attempts to make high molecular weight cyclic-type polymers will be conducted via pathways involving strained intermediates. %%% This grant from the Organic dynamics Program supports the work of Professor Richard P. Johnson at the University of New Hampshire. These investigations will be aimed at the synthesis of highly strained organic molecules that are expected to undergo a variety of quite unusual reactions. By the development of general methods for the synthesis of such species, it should be possible to produce a variety of compounds which are currenty impossible to generate by any other process. The highly reactive strained ring species live for only very short periods of time and therefore specialized techniques are required to prove their existence.