Solvent effects on aromatic nucleophilic substitutions. Part 3.1 The kinetics of the reaction of 2,4-dinitrochlorobenzene with piperidine in aprotic solvents

The kinetics of the reaction between 2,4-dinitrochlorobenzene and piperidine were studied in nitromethane, NN-dimethylformamide, ethyl acetate, dioxane, and 1,1,1 -trichloroethane at 15, 25, and 40 °C. This reaction was chosen as the simplest example of aromatic nucleophilic substitution. Different...

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Publicado: 1984
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1472779X_v_n7_p1133_Mancini
http://hdl.handle.net/20.500.12110/paper_1472779X_v_n7_p1133_Mancini
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling paper:paper_1472779X_v_n7_p1133_Mancini2025-07-30T18:53:12Z Solvent effects on aromatic nucleophilic substitutions. Part 3.1 The kinetics of the reaction of 2,4-dinitrochlorobenzene with piperidine in aprotic solvents The kinetics of the reaction between 2,4-dinitrochlorobenzene and piperidine were studied in nitromethane, NN-dimethylformamide, ethyl acetate, dioxane, and 1,1,1 -trichloroethane at 15, 25, and 40 °C. This reaction was chosen as the simplest example of aromatic nucleophilic substitution. Different correlations of the second-order rate coefficients KA with several solvent parameters were examined for this and earlier work combining 13 aprotic solvents in all with a range of 43 units in the dielectric constants (ε) in the series. It was found that the ET(30) parameter is the most useful available measure of the solvent influence in the present reaction if hydrogen-bond donor (HBD) solvents are excluded; the deviation from linearity of these solvents is explained as arising from the highly exposed strong negative charge on Dimroth's betaine which gives a high ET value to HBD solvents. Conversely, the correlation is remarkably successful for the hydrogen-bond acceptor (HBA) solvents since the positive charge in the present reaction is buried similarly to that in the model solute, and the amine hydrogen of the zwitterionic intermediate, ZH, is strongly involved in an intramolecular hydrogen bond. Aliphatic, aromatic, and polychlorinated aliphatic solvents are all well correlated. 1984 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1472779X_v_n7_p1133_Mancini http://hdl.handle.net/20.500.12110/paper_1472779X_v_n7_p1133_Mancini
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 between 2,4-dinitrochlorobenzene and piperidine were studied in nitromethane, NN-dimethylformamide, ethyl acetate, dioxane, and 1,1,1 -trichloroethane at 15, 25, and 40 °C. This reaction was chosen as the simplest example of aromatic nucleophilic substitution. Different correlations of the second-order rate coefficients KA with several solvent parameters were examined for this and earlier work combining 13 aprotic solvents in all with a range of 43 units in the dielectric constants (ε) in the series. It was found that the ET(30) parameter is the most useful available measure of the solvent influence in the present reaction if hydrogen-bond donor (HBD) solvents are excluded; the deviation from linearity of these solvents is explained as arising from the highly exposed strong negative charge on Dimroth's betaine which gives a high ET value to HBD solvents. Conversely, the correlation is remarkably successful for the hydrogen-bond acceptor (HBA) solvents since the positive charge in the present reaction is buried similarly to that in the model solute, and the amine hydrogen of the zwitterionic intermediate, ZH, is strongly involved in an intramolecular hydrogen bond. Aliphatic, aromatic, and polychlorinated aliphatic solvents are all well correlated.
title Solvent effects on aromatic nucleophilic substitutions. Part 3.1 The kinetics of the reaction of 2,4-dinitrochlorobenzene with piperidine in aprotic solvents
spellingShingle Solvent effects on aromatic nucleophilic substitutions. Part 3.1 The kinetics of the reaction of 2,4-dinitrochlorobenzene with piperidine in aprotic solvents
title_short Solvent effects on aromatic nucleophilic substitutions. Part 3.1 The kinetics of the reaction of 2,4-dinitrochlorobenzene with piperidine in aprotic solvents
title_full Solvent effects on aromatic nucleophilic substitutions. Part 3.1 The kinetics of the reaction of 2,4-dinitrochlorobenzene with piperidine in aprotic solvents
title_fullStr Solvent effects on aromatic nucleophilic substitutions. Part 3.1 The kinetics of the reaction of 2,4-dinitrochlorobenzene with piperidine in aprotic solvents
title_full_unstemmed Solvent effects on aromatic nucleophilic substitutions. Part 3.1 The kinetics of the reaction of 2,4-dinitrochlorobenzene with piperidine in aprotic solvents
title_sort solvent effects on aromatic nucleophilic substitutions. part 3.1 the kinetics of the reaction of 2,4-dinitrochlorobenzene with piperidine in aprotic solvents
publishDate 1984
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_1472779X_v_n7_p1133_Mancini
http://hdl.handle.net/20.500.12110/paper_1472779X_v_n7_p1133_Mancini
_version_ 1840325704545206272

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