Electrochemical Study of the SN2 Reaction of 1-p-Toluenesulfonyl-2,4-dinitronaphthalene with Hydroxide Ions at the Nitrobenzene-Water Interface

Abstract

The rate of the interfacial nucleophilic reaction of 1-p-toluenesulfonyl-2,4-dinitronaphthalene (TSDNN) with OH -ions at the polarized nitrobenzene (NB)-water (W) interface was studied using a polarographic technique. The TSDNN partitioned into the aqueous phase underwent a displacement of the p-toluenesulfonyl moiety with OH -. The transfer of one of the products, 2,4-dinitronaphthalate (DNN -), from the W phase to the NB phase was monitored as the current across the interface. The rate constant of the reaction of TSDNN with OH -in the aqueous phase was estimated to be 1.03±0.23 dm 3 mol -1 s -1 at 25˚C, which is ten-times higher than the rate constant of the displacement of 2,4-dinitrofluorobenzene with OH -in the aqueous phase, 1.01±0.13×10 -1 dm 3 mol -1 s -1 . The contribution from the reactions in the NB phase and at the interface to the formation of DNN -seems to be negligible, suggesting the absence of an interfacial facilitation of the reaction.

Two-Phase Azo-Coupling Reactions Driven by Phase-Boundary Potential Across the Liquid|Liquid Interface

“…Moreover, mass transport, heterogeneous charge transfer, adsorption, and chemical reactions can be rigorously studied under the control of potential difference across the interface. S N aryl reactions have been studied successfully using voltammetric techniques , at the nitrobenzene|W interface where the charge transfer of products across the interface takes place after the homogeneous chemical reactions. The present study is concerned with the azo-coupling reactions at the polarized 1,2-dichloroethane (DCE)|W interface.…”

Effect of ligand protonation on the facilitated ion transfer reactions across oil/water interfaces. IV. Buffer solution effect

“…This methodology allows calculating the pH and the buffer capacity as a function of the distance of the interface. This information is useful to identify the spatial region where optimal conditions can be met to promote chemical reactions depending on the presence of j or HO À [56][57][58][59]. b H þ ð0; tÞ ¼…”

Kinetic Analysis of a Two‐Phase EC Mechanism with Concomitant Lateral Processes

“…The two-phase azo-coupling reaction [8], nucleophilic substitution [9,10], among other processes, are examples of more complex organic reactions induced by a potential difference applied to a liquid-liquid interface that have been studied to understand different mechanisms of catalysis. Potential sweep and potential step measurements were mainly used for the analysis.…”