Previous research in our group examined the conformational variability of <i>N,N-</i>diethyl-<i>m</i>-toluamide (DEET) analogs with the desire to investigate the role of modification of the functional groups on the conformational changes induced by the partial double bond rotation. During the course of these studies, several DEET analogs, primarily those which were ortho substituted, displayed unique trapping of specific conformations predominantly due to the steric effects induced by the substitutions. While all the analogs studied thus far contained symmetric tertiary amides, either cyclic or acyclic, the current project explores the role of two different groups on the amide nitrogen. Extending the library of DEET analogs with asymmetric nitrogen arms will allow us to investigate the role of steric interactions on the various conformational states sampled by the molecules. A series of DEET analogs are synthesized with dissymmetric amines varying steric bulk and electronic factors, such as ethylmethylamine and benzylethylamine. The kinetic and thermodynamic parameters are measured using NMR spectroscopic methods, including variable temperature measurements and line shape analysis of the chemical exchange process. Potential energy surface calculations based on computational calculations are also performed to identify the configurations of the conformational sub-states.

Conformational analysis of DEET analogs with asymmetric nitrogen arms

2019 Fall National Meeting

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