Reactions of Atomic Carbon and Related High Energy Intermediates

这项有机和大分子化学项目的拨款支持Philip Shevlin教授对原子碳化学和相关高能有机反应中间体的研究。因为碳原子对键的形成具有很大的热力学驱动力，所以它是一种多用途的试剂，可用于制备某些高活性物质，如碳烯。因此，这项工作既可以作为一些新的高能化学碎片的制备方法，也可以用于理解其他化学碎片的成键力和反应力。一般来说，实验的目的是制备和阐明单价碳中间体的化学性质。舍夫林博士最近的研究表明，电弧生成的碳原子与四氟甲烷反应会生成CF，而CF与烯烃反应会生成氟环丙基自由基。这一有趣的物种与其他底物如二烯和芳香族化合物的反应产物将在接下来的工作中进行鉴定。其他实验旨在研究其他卤甲基和母体物质CH的化学性质。其他研究是围绕在C原子反应中作为中间体产生的新型碳烯的持续研究而建立的。碳原子与腈的反应将以形成氰基或异氰基羰基为目的进行研究。将研究氨基乙烯的化学性质，以确定它是否经历了类似于羟基亚甲基对羰基的亲核加成反应，然后是氢转移。最后，计划了研究原子碳与溶液中非挥发性底物反应的实验。

This grant in the Organic and Macromolecular Chemistry Program supports research by Prof. Philip Shevlin on the chemistry of atomic carbon and related high-energy organic reaction intermediates. Because atomic carbon possesses a large thermodynamic driving force for bond formation, it is a versatilereagent for preparation of selected, highly reactive species suchas carbenes. Thus, this work is useful both as a preparation method for some new high-energy chemical fragments, and for understanding the bonding and reactivity forces in others. In general, experiments are designed to prepare and elucidate thechemistry of monovalent carbon intermediates. Dr. Shevlin's recent work has shown that reaction of arc-generated carbon atomswith tetraflouromethane results in the formation of CF, which is observed to react with alkenes to generate flourocyclopropyl radicals. The products of the reaction of this interesting species with other substrates such as dienes and aromatic compounds will be identified in the coming work. Additional experiments are designed to investigate the chemistry of the other halomethynes and the parent species, CH. Other studies arebuilt around continuing investigations of novel carbenes generated as intermediates in C atom reactions. The reaction of carbon atoms with nitriles will be investigated with the goal of forming cyano- or isocyanocarbenes. The chemistry of aminomethylene will be investigated to determine if it undergoes reactions similar to the nucleophilic addition of hydroxymethylene to carbonyls, followed by hydrogent transfer. Lastly, experiments designed to investigate the reaction of atomic carbon with nonvolatile substrates in solution are planned.