A novel ternary approach to quantitatively assess the reactivity of nitroaniline regioisomers by investigation of rapid iodination kinetics using hydrodynamic voltammetry, reduction propensities from polarography, and binding affinities from molecular docking simulations

Abstract

A novel ternary approach to assess the reactivity of nitroaniline regioisomers on a quantitative scaffold has been manifested on the basis of three complementary tenets: kinetics, polarography, and molecular docking. Data from investigation of rapid iodination kinetics of nitroaniline regioisomers by hydrodynamic voltammetry in aqueous medium, reduction propensities of these regioisomers from polarography, and their binding affinities with hypoxanthine‐guanine phophoribosyltransferase (HPRT1) from molecular docking simulations lead to inferences regarding their reactivity that agree in entirety. The experimentally determined magnitudes of the specific reaction rates, energies of activation, collision frequencies, entropies of activation from kinetic studies, and reduction propensities of nitroaniline regioisomers from polarograms when complemented with in silico binding energies of these regioisomer ligands with the receptor enzyme, assess their relative reactivities in unison on a quantitative scaffold. This novel ternary approach unambiguously assesses the reactivity of the regioisomers of nitroaniline as 4‐nitroaniline > 2‐nitroaniline > 3‐nitroaniline.

Comparative quantitative kinetic study of rapid iodination of thiazole and its methyl derivatives in aqueous medium

“…These iodination reactions are faster and have a half‐life of a few seconds and hence require special techniques such as competition technique, flow technique, relaxation technique, pulse radiolysis, femtochemistry technique, and attosecond technique 19,20 . In the present work, special electroanalytical technique known as hydrodynamic voltammetry 21–24 is employed to study the kinetics of the iodination reactions of thiazole and its methyl derivatives. In the acidic medium thiazole nitrogen is protonated and forms azolium cation which is comparatively inert toward electrophilic substitution 25 .…”