The kinetics of the reaction of phenyl 2,4,6-trinitrophenyl ether with aniline in methanol, acetonitrile, tetrahydrofuran, ethyl acetate, and benzene

Abstract

The kinetics of the reaction of phenyl 2,4,6-trinitrophenyl ether with aniline have been investigated as a function of the amine concentration in methanol, acetonitrile, tetrahydrofuran, ethyl acetate, and benzene. Base catalysis was observed in all the solvents. The second-order rate constant k_A shows a linear correlation with the aniline concentration except in benzene where the linearity is with the square of the aniline concentration. The k₃^B/k₂ ratios for the solvents provide information on the mechanism of the uncatalysed decomposition of the intermediate formed in nucleophilic aromatic substitution. A mechanism is proposed for the base-catalysed pathway in solvents of low dielectric constant and basicity.