Theoretical study of alkaline acetylation of p-methylaniline

Autores
Caglieri, Silvana; Servetti, Gustavo Iván
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The acetylation of amines 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 and the amide bond is found to be present in a large number of pharmacologically active molecules. Acetylation of amine is a nucleophilic substitution reaction. This reaction is carried out with acetic anhydride in the presence of amine bases such as tertiary amine and pyridine. The nitrogen from the amine produces the nucleophilic attack on the carbonyl carbon of the anhydride to obtain tetrahedral intermediate, decisive step of the reaction rate. Subsequent loss of a proton will yield the amide and acetic acid as products. Computational investigation1 and an experimental work2 , agreed that this reaction takes place with the formation of a tetrahedral intermediate. A theoretical study of alkaline acetylation of p-methylaniline from the analysis of intermediate of the reaction was carried out. Geometries of all species involved in the acetylation were made and identified. All of the geometry optimizations were performed by the method at the Density Functional Theory (DFT) with B3LYP level of theory and was adopted the 6-31G* basis set. Energies of all reagents and products and the energy of activation for the reaction were calculated using the MP2- 2nd order Mo/ller–Plesset method. Following the same procedure it was identified the geometric parameters and energy of intermediate. The Figure show the optimized structure of the intermediate and the Table lists the geometric parameters, lengths and binding angles values, obtained. The calculations show 12.80 kcal/mol of activation energy.
Fil: Caglieri, Silvana. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Transferencia en Ingeniería Química Ambiental; Argentina.
Fil: Servetti, Gustavo. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Transferencia en Ingeniería Química Ambiental; Argentina.
Peer Reviewed
Materia
Alkaline acetylation
Organic synthesis
Acetic anhydride
Nivel de accesibilidad
acceso abierto
Condiciones de uso
2024-07-25T20:50:38Z
Repositorio
Repositorio Institucional Abierto (UTN)
Institución
Universidad Tecnológica Nacional
OAI Identificador
oai:ria.utn.edu.ar:20.500.12272/11171
Acceder
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network_acronym_str RIAUTN
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network_name_str Repositorio Institucional Abierto (UTN)
spelling Theoretical study of alkaline acetylation of p-methylanilineCaglieri, SilvanaServetti, Gustavo IvánAlkaline acetylationOrganic synthesisAcetic anhydrideThe acetylation of amines 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 and the amide bond is found to be present in a large number of pharmacologically active molecules. Acetylation of amine is a nucleophilic substitution reaction. This reaction is carried out with acetic anhydride in the presence of amine bases such as tertiary amine and pyridine. The nitrogen from the amine produces the nucleophilic attack on the carbonyl carbon of the anhydride to obtain tetrahedral intermediate, decisive step of the reaction rate. Subsequent loss of a proton will yield the amide and acetic acid as products. Computational investigation1 and an experimental work2 , agreed that this reaction takes place with the formation of a tetrahedral intermediate. A theoretical study of alkaline acetylation of p-methylaniline from the analysis of intermediate of the reaction was carried out. Geometries of all species involved in the acetylation were made and identified. All of the geometry optimizations were performed by the method at the Density Functional Theory (DFT) with B3LYP level of theory and was adopted the 6-31G* basis set. Energies of all reagents and products and the energy of activation for the reaction were calculated using the MP2- 2nd order Mo/ller–Plesset method. Following the same procedure it was identified the geometric parameters and energy of intermediate. The Figure show the optimized structure of the intermediate and the Table lists the geometric parameters, lengths and binding angles values, obtained. The calculations show 12.80 kcal/mol of activation energy.Fil: Caglieri, Silvana. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Transferencia en Ingeniería Química Ambiental; Argentina.Fil: Servetti, Gustavo. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Transferencia en Ingeniería Química Ambiental; Argentina.Peer Reviewed2024-07-25T20:50:38Z2024-07-25T20:50:38Z2015info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articulopdfapplication/pdfTorino Incontra Congress Center.2015http://hdl.handle.net/20.500.12272/11171-enginfo:eu-repo/semantics/openAccess2024-07-25T20:50:38Zhttp://creativecommons.org/licenses/by-nc-nd/4.0/Attribution-NonCommercial-NoDerivatives 4.0 InternacionalCaglieri , Silvana; Servetti, Gustavohttps://creativecommons.org/licenses/by-nc-sa/4.0/reponame:Repositorio Institucional Abierto (UTN)instname:Universidad Tecnológica Nacional2026-09-24T12:44:32Zoai:ria.utn.edu.ar:20.500.12272/11171instacron: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 12:44:34.119Repositorio Institucional Abierto (UTN) - Universidad Tecnológica Nacionalfalse
dc.title.none.fl_str_mv Theoretical study of alkaline acetylation of p-methylaniline
title Theoretical study of alkaline acetylation of p-methylaniline
spellingShingle Theoretical study of alkaline acetylation of p-methylaniline
Caglieri, Silvana
Alkaline acetylation
Organic synthesis
Acetic anhydride
title_short Theoretical study of alkaline acetylation of p-methylaniline
title_full Theoretical study of alkaline acetylation of p-methylaniline
title_fullStr Theoretical study of alkaline acetylation of p-methylaniline
title_full_unstemmed Theoretical study of alkaline acetylation of p-methylaniline
title_sort Theoretical study of alkaline acetylation of p-methylaniline
dc.creator.none.fl_str_mv Caglieri, Silvana
Servetti, Gustavo Iván
author Caglieri, Silvana
author_facet Caglieri, Silvana
Servetti, Gustavo Iván
author_role author
author2 Servetti, Gustavo Iván
author2_role author
dc.subject.none.fl_str_mv Alkaline acetylation
Organic synthesis
Acetic anhydride
topic Alkaline acetylation
Organic synthesis
Acetic anhydride
dc.description.none.fl_txt_mv The acetylation of amines 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 and the amide bond is found to be present in a large number of pharmacologically active molecules. Acetylation of amine is a nucleophilic substitution reaction. This reaction is carried out with acetic anhydride in the presence of amine bases such as tertiary amine and pyridine. The nitrogen from the amine produces the nucleophilic attack on the carbonyl carbon of the anhydride to obtain tetrahedral intermediate, decisive step of the reaction rate. Subsequent loss of a proton will yield the amide and acetic acid as products. Computational investigation1 and an experimental work2 , agreed that this reaction takes place with the formation of a tetrahedral intermediate. A theoretical study of alkaline acetylation of p-methylaniline from the analysis of intermediate of the reaction was carried out. Geometries of all species involved in the acetylation were made and identified. All of the geometry optimizations were performed by the method at the Density Functional Theory (DFT) with B3LYP level of theory and was adopted the 6-31G* basis set. Energies of all reagents and products and the energy of activation for the reaction were calculated using the MP2- 2nd order Mo/ller–Plesset method. Following the same procedure it was identified the geometric parameters and energy of intermediate. The Figure show the optimized structure of the intermediate and the Table lists the geometric parameters, lengths and binding angles values, obtained. The calculations show 12.80 kcal/mol of activation energy.
Fil: Caglieri, Silvana. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Transferencia en Ingeniería Química Ambiental; Argentina.
Fil: Servetti, Gustavo. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Transferencia en Ingeniería Química Ambiental; Argentina.
Peer Reviewed
description The acetylation of amines 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 and the amide bond is found to be present in a large number of pharmacologically active molecules. Acetylation of amine is a nucleophilic substitution reaction. This reaction is carried out with acetic anhydride in the presence of amine bases such as tertiary amine and pyridine. The nitrogen from the amine produces the nucleophilic attack on the carbonyl carbon of the anhydride to obtain tetrahedral intermediate, decisive step of the reaction rate. Subsequent loss of a proton will yield the amide and acetic acid as products. Computational investigation1 and an experimental work2 , agreed that this reaction takes place with the formation of a tetrahedral intermediate. A theoretical study of alkaline acetylation of p-methylaniline from the analysis of intermediate of the reaction was carried out. Geometries of all species involved in the acetylation were made and identified. All of the geometry optimizations were performed by the method at the Density Functional Theory (DFT) with B3LYP level of theory and was adopted the 6-31G* basis set. Energies of all reagents and products and the energy of activation for the reaction were calculated using the MP2- 2nd order Mo/ller–Plesset method. Following the same procedure it was identified the geometric parameters and energy of intermediate. The Figure show the optimized structure of the intermediate and the Table lists the geometric parameters, lengths and binding angles values, obtained. The calculations show 12.80 kcal/mol of activation energy.
publishDate 2015
dc.date.none.fl_str_mv 2015
2024-07-25T20:50:38Z
2024-07-25T20:50:38Z
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 Torino Incontra Congress Center.2015
http://hdl.handle.net/20.500.12272/11171
-
identifier_str_mv Torino Incontra Congress Center.2015
-
url http://hdl.handle.net/20.500.12272/11171
dc.language.none.fl_str_mv eng
language eng
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
2024-07-25T20:50:38Z
http://creativecommons.org/licenses/by-nc-nd/4.0/
Attribution-NonCommercial-NoDerivatives 4.0 Internacional
Caglieri , Silvana; Servetti, Gustavo
https://creativecommons.org/licenses/by-nc-sa/4.0/
eu_rights_str_mv openAccess
rights_invalid_str_mv 2024-07-25T20:50:38Z
http://creativecommons.org/licenses/by-nc-nd/4.0/
Attribution-NonCommercial-NoDerivatives 4.0 Internacional
Caglieri , Silvana; Servetti, Gustavo
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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