Kinetic Study of the Reaction of N-(2,4-Dinitrophenyl)imidazole with Piperidine and n-Butylamine

Article abstract of DOI:10.1021/jo00195a020

The reaction of N-(2,4-dinitrophenyl)imidazole, 1, with piperidine and n-butylamine was studied.The reaction with piperidine is catalyzed by hydroxide ions and by the amine while the reaction with n-butylamine is weakly catalyzed by hydroxide ion.The hydrolysis of the substrate competes with the aminolysis reaction.The base catalysis in the reaction of 1 with piperidine is shown to be a consequence of rate-limiting deprotonation of the zwitterionic intermediate complex, followed by spontaneous (noncatalyzed) leaving group expulsion.On the other hand, the small rateacelaration observed in the reaction of butylamine as well as the catalysis of the hydrolysis reaction by n-butylamine and piperidine is considered of unclear origin.