Reaction of 2,4-dinitrochlorobenzene with aniline. Solvent effects and molecular complex formation

The kinetics of the reaction of aniline with 2,4-dinitrochlorobenzene (2,4-DNC1B) were studied in several benzene-n-hexane mixtures at 40 °C in the presence of variable amounts of aniline. A linear dependence of the second-order rate coefficients, kA, with [B] is observed, with a null intercept. Tak...

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Autores principales: Nudelman, N.S., Savini, M., Alvaro, C.E.S., Nicotra, V., Yankelevich, J.
Formato: JOUR
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_03009580_v_n8_p1627_Nudelman
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spelling todo:paper_03009580_v_n8_p1627_Nudelman2023-10-03T15:18:07Z Reaction of 2,4-dinitrochlorobenzene with aniline. Solvent effects and molecular complex formation Nudelman, N.S. Savini, M. Alvaro, C.E.S. Nicotra, V. Yankelevich, J. The kinetics of the reaction of aniline with 2,4-dinitrochlorobenzene (2,4-DNC1B) were studied in several benzene-n-hexane mixtures at 40 °C in the presence of variable amounts of aniline. A linear dependence of the second-order rate coefficients, kA, with [B] is observed, with a null intercept. Taking into account the non-polar character of the solvent, and the excellent nucleofugacity of chlorine, this kinetic behaviour is interpreted as evidence of the aggregation of aniline, the hydrogen-bonded dimer acting as the nucleophile. Consistent with this interpretation, when the solvent is changed to THF, a good hydrogen-bond acceptor (HBA), the kA is no longer dependent on [B]. Electron donor-acceptor (EDA) molecular complexes of 2,4-DNC1B with benzene and with aniline, and also between aniline and the product, were clearly recognized and the stability constants of each one of these complexes were determined. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_03009580_v_n8_p1627_Nudelman
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description The kinetics of the reaction of aniline with 2,4-dinitrochlorobenzene (2,4-DNC1B) were studied in several benzene-n-hexane mixtures at 40 °C in the presence of variable amounts of aniline. A linear dependence of the second-order rate coefficients, kA, with [B] is observed, with a null intercept. Taking into account the non-polar character of the solvent, and the excellent nucleofugacity of chlorine, this kinetic behaviour is interpreted as evidence of the aggregation of aniline, the hydrogen-bonded dimer acting as the nucleophile. Consistent with this interpretation, when the solvent is changed to THF, a good hydrogen-bond acceptor (HBA), the kA is no longer dependent on [B]. Electron donor-acceptor (EDA) molecular complexes of 2,4-DNC1B with benzene and with aniline, and also between aniline and the product, were clearly recognized and the stability constants of each one of these complexes were determined.
format JOUR
author Nudelman, N.S.
Savini, M.
Alvaro, C.E.S.
Nicotra, V.
Yankelevich, J.
spellingShingle Nudelman, N.S.
Savini, M.
Alvaro, C.E.S.
Nicotra, V.
Yankelevich, J.
Reaction of 2,4-dinitrochlorobenzene with aniline. Solvent effects and molecular complex formation
author_facet Nudelman, N.S.
Savini, M.
Alvaro, C.E.S.
Nicotra, V.
Yankelevich, J.
author_sort Nudelman, N.S.
title Reaction of 2,4-dinitrochlorobenzene with aniline. Solvent effects and molecular complex formation
title_short Reaction of 2,4-dinitrochlorobenzene with aniline. Solvent effects and molecular complex formation
title_full Reaction of 2,4-dinitrochlorobenzene with aniline. Solvent effects and molecular complex formation
title_fullStr Reaction of 2,4-dinitrochlorobenzene with aniline. Solvent effects and molecular complex formation
title_full_unstemmed Reaction of 2,4-dinitrochlorobenzene with aniline. Solvent effects and molecular complex formation
title_sort reaction of 2,4-dinitrochlorobenzene with aniline. solvent effects and molecular complex formation
url http://hdl.handle.net/20.500.12110/paper_03009580_v_n8_p1627_Nudelman
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