The effect of a hydrogen bond acceptor catalyst on the dimer mechanism in aromatic nucleophilic substitution

The reaction of 2,6-dinitroanisole with cyclohexylamine in toluene-dimethyl sulphoxide (DMSO) mixtures was studied at several amine concentrations. In pure toluene and toluene-DMSO mixtures of low DMSO content (≤ 1%) third-order kinetics with respect to the amine are observed. These results are inte...

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Autor principal: Palleros, Daniel Ricardo
Publicado: 1985
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1472779X_v_n4_p479_Palleros
http://hdl.handle.net/20.500.12110/paper_1472779X_v_n4_p479_Palleros
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id paper:paper_1472779X_v_n4_p479_Palleros
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spelling paper:paper_1472779X_v_n4_p479_Palleros2025-07-30T18:53:10Z The effect of a hydrogen bond acceptor catalyst on the dimer mechanism in aromatic nucleophilic substitution Palleros, Daniel Ricardo The reaction of 2,6-dinitroanisole with cyclohexylamine in toluene-dimethyl sulphoxide (DMSO) mixtures was studied at several amine concentrations. In pure toluene and toluene-DMSO mixtures of low DMSO content (≤ 1%) third-order kinetics with respect to the amine are observed. These results are interpreted as a consequence of the aggregation of the nucleophile (dimer) in low-polarity solvents. Association of DMSO with the amine ('mixed dimer') in a solute-solvent hydrogen-bond interaction can be responsible for the observed catalytic effect of DMSO. At higher DMSO contents behaviour typical for amine catalysis was found which is related to considerable additional stabilization of the intermediate complex through solvation by DMSO. Fil:Palleros, D.R. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 1985 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1472779X_v_n4_p479_Palleros http://hdl.handle.net/20.500.12110/paper_1472779X_v_n4_p479_Palleros
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 reaction of 2,6-dinitroanisole with cyclohexylamine in toluene-dimethyl sulphoxide (DMSO) mixtures was studied at several amine concentrations. In pure toluene and toluene-DMSO mixtures of low DMSO content (≤ 1%) third-order kinetics with respect to the amine are observed. These results are interpreted as a consequence of the aggregation of the nucleophile (dimer) in low-polarity solvents. Association of DMSO with the amine ('mixed dimer') in a solute-solvent hydrogen-bond interaction can be responsible for the observed catalytic effect of DMSO. At higher DMSO contents behaviour typical for amine catalysis was found which is related to considerable additional stabilization of the intermediate complex through solvation by DMSO.
author Palleros, Daniel Ricardo
spellingShingle Palleros, Daniel Ricardo
The effect of a hydrogen bond acceptor catalyst on the dimer mechanism in aromatic nucleophilic substitution
author_facet Palleros, Daniel Ricardo
author_sort Palleros, Daniel Ricardo
title The effect of a hydrogen bond acceptor catalyst on the dimer mechanism in aromatic nucleophilic substitution
title_short The effect of a hydrogen bond acceptor catalyst on the dimer mechanism in aromatic nucleophilic substitution
title_full The effect of a hydrogen bond acceptor catalyst on the dimer mechanism in aromatic nucleophilic substitution
title_fullStr The effect of a hydrogen bond acceptor catalyst on the dimer mechanism in aromatic nucleophilic substitution
title_full_unstemmed The effect of a hydrogen bond acceptor catalyst on the dimer mechanism in aromatic nucleophilic substitution
title_sort effect of a hydrogen bond acceptor catalyst on the dimer mechanism in aromatic nucleophilic substitution
publishDate 1985
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1472779X_v_n4_p479_Palleros
http://hdl.handle.net/20.500.12110/paper_1472779X_v_n4_p479_Palleros
work_keys_str_mv AT pallerosdanielricardo theeffectofahydrogenbondacceptorcatalystonthedimermechanisminaromaticnucleophilicsubstitution
AT pallerosdanielricardo effectofahydrogenbondacceptorcatalystonthedimermechanisminaromaticnucleophilicsubstitution
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