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.
