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

Autores
Caglieri, Silvana; Macaño, Hèctor Rubèn; Servetti, Gustavo Iván
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
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
Materia
Acetylation of p-methylaniline
Organic synthesis
Acetic anhydride
Nivel de accesibilidad
acceso abierto
Condiciones de uso
2024-08-07T22:19:18Z
Repositorio
Repositorio Institucional Abierto (UTN)
Institución
Universidad Tecnológica Nacional
OAI Identificador
oai:ria.utn.edu.ar:20.500.12272/11268
Acceder
id RIAUTN_d42bd6cc85bb94951e07da9f9515f309
oai_identifier_str oai:ria.utn.edu.ar:20.500.12272/11268
network_acronym_str RIAUTN
repository_id_str a
network_name_str Repositorio Institucional Abierto (UTN)
spelling Theoretical study of acetylation of p-methylaniline catalyzed by Ni2+ ionsCaglieri, SilvanaMacaño, Hèctor RubènServetti, Gustavo IvánAcetylation of p-methylanilineOrganic synthesisAcetic anhydrideA 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 Reviewed2024-08-07T22:19:18Z2024-08-07T22:19:18Z2017info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articulopdfapplication/pdf14a Conferencia Latinoamericana de Fìsico-Quìmica Orgànica.2017 / 14th Latin American Conference on Physical Organic Chemistry.2017.2017http://hdl.handle.net/20.500.12272/11268-enginfo:eu-repo/semantics/openAccess2024-08-07T22:19:18Zhttp://creativecommons.org/licenses/by-nc-nd/4.0/Attribution-NonCommercial-NoDerivatives 4.0 InternacionalCaglieri , Silvana; Macaño, Hèctor Rubèn; Servetti, Gustavo Ivànhttps://creativecommons.org/licenses/by-nc-sa/4.0/reponame:Repositorio Institucional Abierto (UTN)instname:Universidad Tecnológica Nacional2026-09-24T12:47:38Zoai:ria.utn.edu.ar:20.500.12272/11268instacron:UTNInstitucionalhttp://ria.utn.edu.ar/Universidad públicaNo correspondehttp://ria.utn.edu.ar/oaigestionria@rec.utn.edu.ar; fsuarez@rec.utn.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:a2026-09-24 12:47:40.459Repositorio Institucional Abierto (UTN) - Universidad Tecnológica Nacionalfalse
dc.title.none.fl_str_mv Theoretical study of acetylation of p-methylaniline catalyzed by Ni2+ ions
title Theoretical study of acetylation of p-methylaniline catalyzed by Ni2+ ions
spellingShingle Theoretical study of acetylation of p-methylaniline catalyzed by Ni2+ ions
Caglieri, Silvana
Acetylation of p-methylaniline
Organic synthesis
Acetic anhydride
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
dc.creator.none.fl_str_mv Caglieri, Silvana
Macaño, Hèctor Rubèn
Servetti, Gustavo Iván
author Caglieri, Silvana
author_facet Caglieri, Silvana
Macaño, Hèctor Rubèn
Servetti, Gustavo Iván
author_role author
author2 Macaño, Hèctor Rubèn
Servetti, Gustavo Iván
author2_role author
author
dc.subject.none.fl_str_mv Acetylation of p-methylaniline
Organic synthesis
Acetic anhydride
topic Acetylation of p-methylaniline
Organic synthesis
Acetic anhydride
dc.description.none.fl_txt_mv 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
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.
publishDate 2017
dc.date.none.fl_str_mv 2017
2024-08-07T22:19:18Z
2024-08-07T22:19:18Z
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv 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
-
identifier_str_mv 14a Conferencia Latinoamericana de Fìsico-Quìmica Orgànica.2017 / 14th Latin American Conference on Physical Organic Chemistry.2017.2017
-
url http://hdl.handle.net/20.500.12272/11268
dc.language.none.fl_str_mv eng
language eng
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
2024-08-07T22:19:18Z
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/
eu_rights_str_mv openAccess
rights_invalid_str_mv 2024-08-07T22:19:18Z
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/
dc.format.none.fl_str_mv pdf
application/pdf
dc.source.none.fl_str_mv reponame:Repositorio Institucional Abierto (UTN)
instname:Universidad Tecnológica Nacional
reponame_str Repositorio Institucional Abierto (UTN)
collection Repositorio Institucional Abierto (UTN)
instname_str Universidad Tecnológica Nacional
repository.name.fl_str_mv Repositorio Institucional Abierto (UTN) - Universidad Tecnológica Nacional
repository.mail.fl_str_mv gestionria@rec.utn.edu.ar; fsuarez@rec.utn.edu.ar
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