Theoretical study of acetylation of p-methylaniline catalyzed by Ni2+ ions

A theoretical study of acetylation of p-methylaniline catalyzed by Ni2+ ions from the analysis of intermediate of the reaction was carried out. The study of acetylation of amines is of great interest by the utility of its products of reaction and is one of the most frequently used transformations...

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Autores principales: Caglieri, Silvana, Macaño, Hèctor Rubèn, Servetti, Gustavo Iván
Formato: Artículo publisherVersion
Lenguaje:Inglés
Publicado: 2024
Materias:
Acetylation of p-methylaniline
Organic synthesis
Acetic anhydride
Acceso en línea:http://hdl.handle.net/20.500.12272/11268
Aporte de:
RIA - Repositorio Institucional Abierto (UTN) de Universidad Tecnológica Nacional
id I68-R174-20.500.12272-11268
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spelling I68-R174-20.500.12272-112682024-08-07T22:19:18Z Theoretical study of acetylation of p-methylaniline catalyzed by Ni2+ ions Caglieri, Silvana Macaño, Hèctor Rubèn Servetti, Gustavo Iván Acetylation of p-methylaniline Organic synthesis Acetic anhydride A theoretical study of acetylation of p-methylaniline catalyzed by Ni2+ ions from the analysis of intermediate of the reaction was carried out. The study of acetylation of amines is of great interest by the utility of its products of reaction and is one of the most frequently used transformations in organic synthesis as it provides an efficient and inexpensive means for protecting amino groups in a multistep synthetic process. Acetylation of amine is a nucleophilic substitution reaction. This reaction can be catalyzed by Lewis acid1 , metallic ion. The reaction and the compounds studied are shown in Figure1. + + H3C O OH O O O H3C CH3 H3C NH2 Ni 2+ H3C O NH Fig. 1: General Scheme of Acetylation In reaction mechanism, the metallic ion formed a complex with the oxygen of the acetic anhydride carbonyl, facilitating the polarization of the same and the successive addition of amine at the position to form a tetrahedral intermediate, determining step of the rate of the reaction. Experimental work2 agreed that this reaction takes place with the formation of a tetrahedral intermediate. In the present theoretical work were investigated the structure and energy of the tetrahedral intermediate of the reaction catalyzed by Ni2+ ions. Geometries of all species involved in the acetylation were made and identified. All of the geometry optimizations were performed by the method at the DFT/B3LYP level of theory and was adopted the 6-31+G* basis set. Energies were calculated using the Mechanics-UFF method. Following the same procedure it was identified the geometric parameters and energy of reaction intermediate. The calculations show 61.89 kcal/mol of energy for the tetrahedral intermediate and the energy of activation for the reaction was 16.05 kcal/mol. Fil: Caglieri, Silvana. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Transferencia en Ingeniería Química Ambiental; Argentina. Fil: Macaño, Hèctor Rubèn. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Transferencia en Ingeniería Química Ambiental; Argentina. Fil: Servetti, Gustavo Ivàn. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Transferencia en Ingeniería Química Ambiental; Argentina. Peer Reviewed 2024-08-07T22:19:18Z 2024-08-07T22:19:18Z 2017 info:eu-repo/semantics/article publisherVersion 14a Conferencia Latinoamericana de Fìsico-Quìmica Orgànica.2017 / 14th Latin American Conference on Physical Organic Chemistry.2017.2017 http://hdl.handle.net/20.500.12272/11268 - eng openAccess http://creativecommons.org/licenses/by-nc-nd/4.0/ Attribution-NonCommercial-NoDerivatives 4.0 Internacional Caglieri , Silvana; Macaño, Hèctor Rubèn; Servetti, Gustavo Ivàn https://creativecommons.org/licenses/by-nc-sa/4.0/ pdf
institution Universidad Tecnológica Nacional
institution_str I-68
repository_str R-174
collection RIA - Repositorio Institucional Abierto (UTN)
language Inglés
topic Acetylation of p-methylaniline
Organic synthesis
Acetic anhydride
spellingShingle Acetylation of p-methylaniline
Organic synthesis
Acetic anhydride
Caglieri, Silvana
Macaño, Hèctor Rubèn
Servetti, Gustavo Iván
Theoretical study of acetylation of p-methylaniline catalyzed by Ni2+ ions
topic_facet Acetylation of p-methylaniline
Organic synthesis
Acetic anhydride
description A theoretical study of acetylation of p-methylaniline catalyzed by Ni2+ ions from the analysis of intermediate of the reaction was carried out. The study of acetylation of amines is of great interest by the utility of its products of reaction and is one of the most frequently used transformations in organic synthesis as it provides an efficient and inexpensive means for protecting amino groups in a multistep synthetic process. Acetylation of amine is a nucleophilic substitution reaction. This reaction can be catalyzed by Lewis acid1 , metallic ion. The reaction and the compounds studied are shown in Figure1. + + H3C O OH O O O H3C CH3 H3C NH2 Ni 2+ H3C O NH Fig. 1: General Scheme of Acetylation In reaction mechanism, the metallic ion formed a complex with the oxygen of the acetic anhydride carbonyl, facilitating the polarization of the same and the successive addition of amine at the position to form a tetrahedral intermediate, determining step of the rate of the reaction. Experimental work2 agreed that this reaction takes place with the formation of a tetrahedral intermediate. In the present theoretical work were investigated the structure and energy of the tetrahedral intermediate of the reaction catalyzed by Ni2+ ions. Geometries of all species involved in the acetylation were made and identified. All of the geometry optimizations were performed by the method at the DFT/B3LYP level of theory and was adopted the 6-31+G* basis set. Energies were calculated using the Mechanics-UFF method. Following the same procedure it was identified the geometric parameters and energy of reaction intermediate. The calculations show 61.89 kcal/mol of energy for the tetrahedral intermediate and the energy of activation for the reaction was 16.05 kcal/mol.
format Artículo
publisherVersion
author Caglieri, Silvana
Macaño, Hèctor Rubèn
Servetti, Gustavo Iván
author_facet Caglieri, Silvana
Macaño, Hèctor Rubèn
Servetti, Gustavo Iván
author_sort Caglieri, Silvana
title Theoretical study of acetylation of p-methylaniline catalyzed by Ni2+ ions
title_short Theoretical study of acetylation of p-methylaniline catalyzed by Ni2+ ions
title_full Theoretical study of acetylation of p-methylaniline catalyzed by Ni2+ ions
title_fullStr Theoretical study of acetylation of p-methylaniline catalyzed by Ni2+ ions
title_full_unstemmed Theoretical study of acetylation of p-methylaniline catalyzed by Ni2+ ions
title_sort theoretical study of acetylation of p-methylaniline catalyzed by ni2+ ions
publishDate 2024
url http://hdl.handle.net/20.500.12272/11268
work_keys_str_mv AT caglierisilvana theoreticalstudyofacetylationofpmethylanilinecatalyzedbyni2ions
AT macanohectorruben theoreticalstudyofacetylationofpmethylanilinecatalyzedbyni2ions
AT servettigustavoivan theoreticalstudyofacetylationofpmethylanilinecatalyzedbyni2ions
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