Base-dependent kinetics of Smiles rearrangement of N-[2-(p-nitrophenoxy)ethyl]ethylenediamine in aqueous solution; intramolecular catalysis of an intramolecular SNAr reaction

Abstract

Intramolecular displacement of alkoxide ion by the secondary amino group of N-[2-(p-nitrophenoxy)ethyl]ethylenediamine in water is uncatalysed by general bases, but is characterised by a pH-insensitives rate plateau and specific-base-catalysed approach to a rate limit at high pH; the rate plateau at [OH^–] 0.1–0.01M is a consequence of the dominant catalytic effect of the neighbouring amino group in promoting rate-determining deprotonation of the spiro-Meisenheimer intermediate.