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Experimental and theoretical approaches to the study of the reactivity and mechanism of the substitution of phenyl 1‐(2,4‐dinitronaphthyl) ether with anilines derivatives
Author(s) -
Moghazy Yasmen M.,
Fathalla Magda F.,
Hamada Nagwa M. M.,
Elmarassi Yasser R.,
Hamed Ezzat A.
Publication year - 2020
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.21354
Subject(s) - chemistry , sn2 reaction , aniline , substituent , reaction rate constant , ether , nucleophilic substitution , computational chemistry , medicinal chemistry , aryl , reactivity (psychology) , density functional theory , reaction mechanism , organic chemistry , catalysis , kinetics , medicine , physics , alkyl , alternative medicine , pathology , quantum mechanics
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.