Date of Award
Doctor of Philosophy
Dr. Donald C. Berndt
Dr. Stephen Friedman
Dr. Robert Harmon
Dr. Robert Nagler
The reaction of 2-naphthoyl azide with primary and secondary amines in protic and aprotic solvents follows second-order kinetics. The effect of increasing solvent polarity is shown to increase the rate of reaction. For amines of similar basicity, the rate of reaction decreases with increasing steric hindrance on the amine. The changes in free energy and entropy of activation for n-butylamine and cyclohexylamine are in accord with steric requirements of amines. For amines of similar steric hindrance, the rate of reaction increases with increasing amine basicity. The mechanism of addition-elimination involving the formation of a tetrahedral intermediate is consistent with the data obtained. The rate-determining step in this reaction is postulated on the basis of amine and azide ion basicities, and the possibility of anchimeric-type assistance by the azide group in the expulsion of the amine from the tetrahedral intermediate. The absence of general base catalysis in this reaction is explained in terms of a fast proton transfer from the protonated amide intermediate to a solvent or an amine molecule which occurs after the rate-determining step. Qualitative evaluation of the total steric and electronic effects on the rate of this reaction indicates that the former factor is predominant. The combination of high basicity and small steric hindrance on the amine results in a dramatic enhancement in rate of reaction as demonstrated by pyrrolidine.
Faburada, Abraham L., "Kinetics and Mechanism of Acylation of Amines with 2-Naphthoyl Azide" (1983). Dissertations. 2423.
Fifth Advisor: Dr. Jochanan Stenesh