The synthesis and relative acidity of substituted diphenylamines

Abstract

Synthetic work a study has been made of the scope and limitations of various methods of preparation of substituted diphenylamine. The study has led to extensions of the Chapman and Smiles rearrangements and a number of diphenylamines not previously prepared have been obtained. Relative Acidities of Substituted Diphenylamines the reaction between isopropoxides in alcoholic solution and substituted diphenylamines has been investigated spectrophoto-metrically. Variations in the apparent equilibrium constant may be explained by ion pair formation. A value of the ion pair dissociation constant has been determined which is of the expected order. The suggestion of ion pair dissociation in dilute solution is further supported by the study of the reaction of lithium, sodium and potassium isopropoxides with nitrodiphenylamines. A P value for proton removal for 4-nitrodiphenylamines has been found and an estimate of transmission of substituent effects through groups can be made.