Reactions of Atomic Carbon and Related High Energy Intermediates

有机化学和高分子化学项目的这笔赠款支持菲利普·舍夫林教授在原子碳化学和相关的高能有机反应中间体方面的研究。因为原子碳具有形成键的巨大热力学驱动力，所以它是一种多用途的试剂，用于制备精选的、高活性的物种，如卡宾。因此，这项工作既可以作为一种新的高能化学碎片的制备方法，也可以用于理解其他碎片中的成键和反应力。一般来说，设计实验是为了准备和阐明单价碳中间体的化学。Shevlin博士最近的工作表明，弧形碳原子与四氟甲烷反应生成CF，观察到CF与烯烃反应生成氟环丙基。这一有趣的物种与其他底物如双烯和芳香族化合物反应的产物将在接下来的工作中确定。另外还设计了一些实验来研究其他卤代甲烷和母体物种CH的化学性质。其他研究是围绕碳原子反应中作为中间体产生的新型卡宾的持续研究而建立的。将研究碳原子与氰化物的反应，目标是生成氰基或异氰卡宾。将对氨基甲烷的化学进行研究，以确定它是否经历类似于羟甲基与羰基的亲核加成，然后进行氢化物转移的反应。最后，设计了研究溶液中原子碳与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.