Reaction of 2,4-Dinitrochlorobenzene with Aromatic Amines in Toluene Effect of Nucleophile Structure 英文参考文献.docVIP

401 Molecules 2000, 5 Reaction of 2,4-Dinitrochlorobenzene with Aromatic Amines in Toluene: Effect of Nucleophile Structure C.E.S. Alvaro1, M.C. Savini1, V. Nicotra1, J. S. Yankelevich1 and N. S. Nudelman2 1Dpto. de Química, Facultad de Ingeniería, Universidad Nacional del Comahue. Buenos Aires 1400. (8300) Neuquén, Argentina E-mail: salvaro @uncoma.edu.ar 2Dpto. de Química Orgánica. Facultad de Ciencias Exactas y Naturales. Pabellón II, 3°p, Ciudad Uni- versitaria. U.B.A., Argentina E-mail: nudelman@qo.fcen.uba.ar Abstract: The kinetics of the reaction of 2,4-dinitrochlorobenzene (DNClB) with aniline and substituted anilines such as p-anisidine, p-toluidine and N-methylaniline have been studied in toluene. Except for N-methylaniline the reactions have shown a third order in amine rate dependence which is consistent with aggregates of the amine acting as the nu- cleophile. On the other hand, the reaction of DNClB with N-methylaniline under the same conditions shows a linear dependence of the second order rate coefficient, kA, vs [amine], which is consistent with the previous mechanism. Introduction Previous research carried out in our laboratory on aromatic nucleophile substitutions (SNAr) of 2,4- dinitrochlorobenzene in aprotic solvent [1,2] have shown formation of aniline dimers acting as nucleo- phile, formation of molecular complexes substrate-nucleophile and substrate-product reaction, forma- tion of mixed aggregates aniline-HBA additive and specific effects solvent on SNAr mechanism. In order to investigate the relevance of nucleophile structure in defining the mechanism of SNAr with amines in aprotic solvent, kinetic studies of the reaction of DNClB with aniline, p-anisidine, p- toluidine, 2,4-dimethylaniline and N-methylaniline in toluene at 40°C have been carried out. Experimental Aniline, p-toluidine, 2,4-dimethylaniline and N-methylaniline were distilled over zinc powder and then over sod