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 |
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| Authors: | Yasmen M Moghazy Magda F Fathalla Nagwa M M Hamada Yasser R Elmarassi Ezzat A Hamed |
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| Institution: | 1. Chemistry and Physics Department, Faculty of Education, Alexandria University, Alexandria, Egypt;2. Chemistry Department, Faculty of Science, Alexandria University, Alexandria, Egypt;3. Chemistry Department, Faculty of Science, Alexandria University, Alexandria, Egypt
Basic Science Department, Imam Abdulrahman Bin Faisal University (Dammam University), Dammam, Kingdom of Saudi Arabia |
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| Abstract: | 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. |
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