Investigation of Reactive Intermediates and Inner Phase Reactions Inside Molecular Container Compounds

该项目的长期目标是将分子容器化合物应用于活性中间体的表征和催化等领域。在半碳化合物的内相中，将生成两个高应变的环烯和各种萘卡宾重排中间体，并对它们的热化学进行了研究。这些物种对有机化学中的结构理论很重要。此外，还将开发一种稳定活性中间体的新方法。这种方法涉及到半碳化合物内部的前体分子的共价键，然后从该前体生成活性中间体，从而排除其他活性物种。有了这个奖项，有机和高分子化学项目的有机动力学项目支持堪萨斯州立大学的Ralf Warmuth教授的研究。Warmuth教授正在从事一个物理有机化学领域，在该领域中，作为反应过程中的中间体的化学物种被创建和观察到。这些物种被称为活性中间体，通常寿命很短，很难直接观察到。通过在保护壳中形成这些中间体，Warmuth教授将能够延长这些难以捉摸的实体的寿命，使它们的观测更具可行性。

This project has the long term objective to apply molecular container compounds in areas such as the characterization of reactive intermediates and in catalysis. Two highly strained cyclic allenes and various intermediates in the naphthylcarbene rearrangement will be generated and spectroscopically characterized in the inner phase of hemicarcerands, and their thermochemistry will be investigated. These species are important to structural theory in organic chemistry. In addition, a new approach for the stabilization of reactive intermediates will be developed. This approach involves the covalent bonding of a precursor molecule on the inside of a hemicarcerand, whereupon generation of a reactive intermediate from this precursor takes place to the exclusion of other reactive species. Quenching of the intermediate is thus prevented.With this award, the Organic and Macromolecular Chemistry Program's Organic Dynamics Program supports the research of Professor Ralf Warmuth of Kansas State University. Professor Warmuth is pursuing an area of physical organic chemistry wherein chemical species that are implicated as intermediates in reaction processes are created and observed. These species are referred to as reactive intermediates, and are normally so short-lived that direct observation is difficult. By forming these intermediates in a protective shell, Professor Warmuth will be able to extend the lifetimes of these elusive entities, making their observation more feasible.