Mechanisms of Nucleophilic Substitution at the Carbon- Nitrogen Double Bond

这笔来自有机动力学项目的拨款支持了德克萨斯女子大学的詹姆斯·E·约翰逊教授的工作。将探讨立体电子效应在碳-氮双键亲核取代反应中的作用。将合成亚胺的几何异构体，测量它们与氧和氮亲核试剂的反应速度，并确定产物的结构。将进行的具体研究包括：(1)环羟基异辛酸酯和羟甲基氯化物上的亲核取代；(2)正丙基O-甲基乙氧基甲醛的Z和E异构体上的甲氧基离子取代；(3)羟甲基氯的Z和E异构体中的胺取代，以及(4)羟甲苯磺酸酯和/或羟甲基溴的Z和E异构体的水解。将测量原子在空间中排列不同的几种底物的反应速度。反应活性和产物结构的不同将使人们能够评估非键电子对反应过程的影响。这项研究的结果将有助于更好地理解含有氮原子的有机化合物的反应。

This grant from the Organic Dynamics Program supports the work of Professor James E. Johnson at Texas Woman's University. The role of stereoelectronic effects in nucleophilic substitution reactions at the carbon-nitrogen double bond will be explored. Geometric isomers of imines will be synthesized, the rates of their reactions with oxygen and nitrogen nucleophiles will be measured, and the structures of the products will be determined. The specific studies that will be undertaken include: (1) nucleophilic substitution on cyclic hydroximates and hydroximoyl chlorides; (2) methoxide ion substitution on the Z and E isomers of n-propyl O-methylethoxy formohydroximate; (3) amine substitution in the Z and E isomers of hydroximoyl chlorides, and (4) hydrolysis of the Z and E isomers of a hydroximoyl tosylate and/or a hydroximoyl bromide. %%% The rates of reaction of several substrates that different in the arrangement of their atoms in space will be measured. Differences in reactivity and in the structures of the products will allow assessment of the effect of nonbonding electrons on the course of the reaction. The results of this study will contribute to an improved understanding of reactions of organic compounds which contain nitrogen atoms.