Kinetic studies on the electrophilic chlorination of certain aryl ethers in solution using 1-chlorobenzotriazole

Extensive kinetic investigations have been carried out on the electrophilic chlorination of nine aryl ethes in acetic acid solution by 1-chlorobenzotrizole. The total order of the reaction, order in substrate and order id 1-chlorobenzotriazole are determined. the stoichiometry of 1-chloroberizotriazole-4-bromoanisole reaction is found to be 1 : 1. The activation energies are determined for these reactions and explained on the basis of the structure of substrate molecules. The product analysis has been carried out under kinetic concentrations using H-1 NMR spectrum. The influence of perchloric acid and benzotriazole added on the rate of the reactions are studied. The activation energy values are correlated with total electron density at the reaction site and the ionization energies of the molecules computed by MOPAC calculation at PM3 level. Based on the kinetic results a suitable mechanism has been proposed.