Abstract:
The kinetics of reactions of 1-chloro-2,4-dinitrobenzene with aniline and several substituted aromatic amines, B, in toluene shows a quadratic dependence of the second-order rate constant, kA, on [B], which is preserved even in the presence of increasing amounts of dimethylaniline, while the reaction with N-methylaniline shows a linear dependence of kA vs [B]. All these results are interpreted by the "dimer nucleophile" mechanism, and confirmed by the effects of a non-nucleophilic hydrogen bond acceptor tertiary amine which show the relevance of the structure of the nucleophile and the role of mixed aggregates in defining the mechanisms of aromatic nucleophilic substitutions with amines in aprotic solvents.
Registro:
| Documento: |
Artículo
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| Título: | Effects of the nucleophile structure on the mechanisms of reaction of 1-chloro-2,4-dinitrobenzene with aromatic amines in aprotic solvents |
| Autor: | Nudelman, N.S.; Alvaro, C.E.S.; Savini, M.; Nicotra, V.; Yankelevich, J. |
| Filiación: | Depto. de Quimica Organica, Fac. de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Buenos Aires, Argentina
Departamento de Quimica, Facultad de Ingeniería, Universidad Nacional del Comahue, Neuquén, Argentina
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| Palabras clave: | Amine aggregation states; Aprotic solvents; Aromatic nucleophilic substitutions; Dimer nucleophile mechanism; Nucleophile structure; Reaction kinetics; Reaction mechanism |
| Año: | 1999
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| Volumen: | 64
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| Número: | 1
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| Página de inicio: | 1583
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| Página de fin: | 1593
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| Título revista: | Collection of Czechoslovak Chemical Communications
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| Título revista abreviado: | Collect. Czech. Chem. Commun.
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| ISSN: | 00100765
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| CODEN: | CCCCA
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| Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00100765_v64_n1_p1583_Nudelman |
Referencias:
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- Forlani, L., (1996) The Chemistry of Amino, Nitroso, Nitro and Related Groups, , (S. Patai, Ed.), Chap. 10. Wiley, Chichester
- Durantini, E., Zingaretti, L., Anunziata, J.D., Silber, J.J., (1992) J. Phys. Org. Chem., 5, p. 557. , and references therein
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- Reichardt, C.F., (1988) Solvents and Solvent Effects in Organic Chemistry, 2nd Ed., , VCH, Weinheim
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- Forlani, L., (1982) Gazz. Chim. Ital., 112, p. 205
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Citas:
---------- APA ----------
Nudelman, N.S., Alvaro, C.E.S., Savini, M., Nicotra, V. & Yankelevich, J.
(1999)
. Effects of the nucleophile structure on the mechanisms of reaction of 1-chloro-2,4-dinitrobenzene with aromatic amines in aprotic solvents. Collection of Czechoslovak Chemical Communications, 64(1), 1583-1593.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00100765_v64_n1_p1583_Nudelman [ ]
---------- CHICAGO ----------
Nudelman, N.S., Alvaro, C.E.S., Savini, M., Nicotra, V., Yankelevich, J.
"Effects of the nucleophile structure on the mechanisms of reaction of 1-chloro-2,4-dinitrobenzene with aromatic amines in aprotic solvents"
. Collection of Czechoslovak Chemical Communications 64, no. 1
(1999) : 1583-1593.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00100765_v64_n1_p1583_Nudelman [ ]
---------- MLA ----------
Nudelman, N.S., Alvaro, C.E.S., Savini, M., Nicotra, V., Yankelevich, J.
"Effects of the nucleophile structure on the mechanisms of reaction of 1-chloro-2,4-dinitrobenzene with aromatic amines in aprotic solvents"
. Collection of Czechoslovak Chemical Communications, vol. 64, no. 1, 1999, pp. 1583-1593.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00100765_v64_n1_p1583_Nudelman [ ]
---------- VANCOUVER ----------
Nudelman, N.S., Alvaro, C.E.S., Savini, M., Nicotra, V., Yankelevich, J. Effects of the nucleophile structure on the mechanisms of reaction of 1-chloro-2,4-dinitrobenzene with aromatic amines in aprotic solvents. Collect. Czech. Chem. Commun. 1999;64(1):1583-1593.
Available from: https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00100765_v64_n1_p1583_Nudelman [ ]
