Reactions of aniline derivatives in dimethyl sulfoxide with phenyl 1‐(2,4‐dinitronaphthyl) ether yield aryl 1‐(2,4‐dinitronaphthyl) amine, which results in substitution of the phenoxy groups at the naphthyl ipso carbon atom. Rate constants were measured spectrophotometrically, and reaction proton transfer was rate limiting. The values of the rate coefficients indicate a rate‐limiting proton transfer mechanism with significant substituent effects. The calculated activation parameters were of regular variation with substituents in 4‐ and 3‐position in the aniline nucleophile, and the reaction proceeded through a common mechanism. Hammett's reaction constant showed that the reaction rate constants depend on the electron density of the nitrogen atom of aniline derivative, whereas the coefficient value obtained from the Brönsted relation indicated that the reaction was significantly associative and quite zwitterion like. Computational studies of the substitution were carried out based on density functional theory, and theoretical to the experimental agreement was achieved.

Reactions of aryl 1-(2,4-dinitronaphthyl) ethers with piperidine in dimethyl sulfoxide at 25oC resulted in substitution of the aryloxy group at the ipso carbon atom. The reaction was measured spectrophotochemically and the kinetic studies suggested that the titled reaction is accurately third order. The mechanism is began by fast nucleophilic attack of piperidine on C1 to form zwitterion intermediate (I) followed by deprotonation of zwitterion intermediate (I) to the Meisenheimer ion (II) in a slow step, that is, SB catalysis. The regular variation of activation parameters suggested that the reaction proceeded through a common mechanism. The Hammett equation using reaction constant σo values and Brønsted coefficient value showed that the reaction is poorly dependent on aryloxy substituent and the reaction was significantly associative and Meisenheimer intermediate-like. The mechanism of piperidinolysis has been theoretically investigated using density functional theory method using B3LYP/6-311G(d,p) computational level. The combination between experimental and computational studies predicts what mechanism is followed either through uncatalyzed or catalyzed reaction pathways, that is, SB and SB-GA. The global parameters of the reactants, the proposed activated complexes, and the local Fukui function analysis explained that C1 carbon atom is the most electrophilic center of ether. Also, kinetics and theoretical calculation of activation energies indicated that the mechanism of the piperidinolysis passed through a two-step mechanism and the proton transfer process was the rate determining step.