Solvent effect on the aniline acetylation: Theoretical study

Autores
Caglieri, Silvana
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 and 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 investigation and an experimental work, agreed that this reaction takes place with the formation of a tetrahedral intermediate. A theoretical study of aniline acetylation in several solvents 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 DFT - Density Functional Theory 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- 2 nd order Mo/ller–Plesset method. Following the same procedure it was identified the geometric parameters and energy of intermediate. The nature of solvent has an important effect on the reaction. In order to investigate the solvent effect on the aniline acetylation, both aprotic solvents such as: acetonitrile and acetone and protic solvents such as: methanol and ethanol were used. The effect of the solvent was performed with IEFPCM o PCM (Polarizable Continuum Model) method. Values of activation energy are reported in Table. Acetonitrile (aprotic solvent with the highest dielectric constant showed in the table) reveals to be the best solvent in term of activity for the reaction. This behavior could be associated with greater stability of the intermediate of the reaction.
Fil: Caglieri, Silvana. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Transferencia en Ingeniería Química Ambiental; Argentina.
Peer Reviewed
Materia
Acetylation of amines
Organic synthesis
Nucleophilic substitution
Nivel de accesibilidad
acceso abierto
Condiciones de uso
2024-07-25T21:06:57Z
Repositorio
Repositorio Institucional Abierto (UTN)
Institución
Universidad Tecnológica Nacional
OAI Identificador
oai:ria.utn.edu.ar:20.500.12272/11173
Acceder
id RIAUTN_6a0763e2b102e866bff6f50632fc42ad
oai_identifier_str oai:ria.utn.edu.ar:20.500.12272/11173
network_acronym_str RIAUTN
repository_id_str a
network_name_str Repositorio Institucional Abierto (UTN)
spelling Solvent effect on the aniline acetylation: Theoretical studyCaglieri, SilvanaAcetylation of aminesOrganic synthesisNucleophilic substitutionThe 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 and 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 investigation and an experimental work, agreed that this reaction takes place with the formation of a tetrahedral intermediate. A theoretical study of aniline acetylation in several solvents 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 DFT - Density Functional Theory 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- 2 nd order Mo/ller–Plesset method. Following the same procedure it was identified the geometric parameters and energy of intermediate. The nature of solvent has an important effect on the reaction. In order to investigate the solvent effect on the aniline acetylation, both aprotic solvents such as: acetonitrile and acetone and protic solvents such as: methanol and ethanol were used. The effect of the solvent was performed with IEFPCM o PCM (Polarizable Continuum Model) method. Values of activation energy are reported in Table. Acetonitrile (aprotic solvent with the highest dielectric constant showed in the table) reveals to be the best solvent in term of activity for the reaction. This behavior could be associated with greater stability of the intermediate of the reaction.Fil: Caglieri, Silvana. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Transferencia en Ingeniería Química Ambiental; Argentina.Peer Reviewed2024-07-25T21:06:57Z2024-07-25T21:06:57Z2015info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articulopdfapplication/pdf13a Conferencia Latinoamericana de Físico-Química Orgánica / 13th Latin American Conference on Physical Organic Chemistryhttp://hdl.handle.net/20.500.12272/11173-enginfo:eu-repo/semantics/openAccess2024-07-25T21:06:57Zhttp://creativecommons.org/licenses/by-nc-nd/4.0/Attribution-NonCommercial-NoDerivatives 4.0 InternacionalCaglieri , Silvanahttps://creativecommons.org/licenses/by-nc-sa/4.0/reponame:Repositorio Institucional Abierto (UTN)instname:Universidad Tecnológica Nacional2026-09-24T12:44:54Zoai:ria.utn.edu.ar:20.500.12272/11173instacron: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 12:44:54.632Repositorio Institucional Abierto (UTN) - Universidad Tecnológica Nacionalfalse
dc.title.none.fl_str_mv Solvent effect on the aniline acetylation: Theoretical study
title Solvent effect on the aniline acetylation: Theoretical study
spellingShingle Solvent effect on the aniline acetylation: Theoretical study
Caglieri, Silvana
Acetylation of amines
Organic synthesis
Nucleophilic substitution
title_short Solvent effect on the aniline acetylation: Theoretical study
title_full Solvent effect on the aniline acetylation: Theoretical study
title_fullStr Solvent effect on the aniline acetylation: Theoretical study
title_full_unstemmed Solvent effect on the aniline acetylation: Theoretical study
title_sort Solvent effect on the aniline acetylation: Theoretical study
dc.creator.none.fl_str_mv Caglieri, Silvana
author Caglieri, Silvana
author_facet Caglieri, Silvana
author_role author
dc.subject.none.fl_str_mv Acetylation of amines
Organic synthesis
Nucleophilic substitution
topic Acetylation of amines
Organic synthesis
Nucleophilic substitution
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 and 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 investigation and an experimental work, agreed that this reaction takes place with the formation of a tetrahedral intermediate. A theoretical study of aniline acetylation in several solvents 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 DFT - Density Functional Theory 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- 2 nd order Mo/ller–Plesset method. Following the same procedure it was identified the geometric parameters and energy of intermediate. The nature of solvent has an important effect on the reaction. In order to investigate the solvent effect on the aniline acetylation, both aprotic solvents such as: acetonitrile and acetone and protic solvents such as: methanol and ethanol were used. The effect of the solvent was performed with IEFPCM o PCM (Polarizable Continuum Model) method. Values of activation energy are reported in Table. Acetonitrile (aprotic solvent with the highest dielectric constant showed in the table) reveals to be the best solvent in term of activity for the reaction. This behavior could be associated with greater stability of the intermediate of the reaction.
Fil: Caglieri, Silvana. 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 and 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 investigation and an experimental work, agreed that this reaction takes place with the formation of a tetrahedral intermediate. A theoretical study of aniline acetylation in several solvents 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 DFT - Density Functional Theory 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- 2 nd order Mo/ller–Plesset method. Following the same procedure it was identified the geometric parameters and energy of intermediate. The nature of solvent has an important effect on the reaction. In order to investigate the solvent effect on the aniline acetylation, both aprotic solvents such as: acetonitrile and acetone and protic solvents such as: methanol and ethanol were used. The effect of the solvent was performed with IEFPCM o PCM (Polarizable Continuum Model) method. Values of activation energy are reported in Table. Acetonitrile (aprotic solvent with the highest dielectric constant showed in the table) reveals to be the best solvent in term of activity for the reaction. This behavior could be associated with greater stability of the intermediate of the reaction.
publishDate 2015
dc.date.none.fl_str_mv 2015
2024-07-25T21:06:57Z
2024-07-25T21:06:57Z
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 13a Conferencia Latinoamericana de Físico-Química Orgánica / 13th Latin American Conference on Physical Organic Chemistry
http://hdl.handle.net/20.500.12272/11173
-
identifier_str_mv 13a Conferencia Latinoamericana de Físico-Química Orgánica / 13th Latin American Conference on Physical Organic Chemistry
-
url http://hdl.handle.net/20.500.12272/11173
dc.language.none.fl_str_mv eng
language eng
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
2024-07-25T21:06:57Z
http://creativecommons.org/licenses/by-nc-nd/4.0/
Attribution-NonCommercial-NoDerivatives 4.0 Internacional
Caglieri , Silvana
https://creativecommons.org/licenses/by-nc-sa/4.0/
eu_rights_str_mv openAccess
rights_invalid_str_mv 2024-07-25T21:06:57Z
http://creativecommons.org/licenses/by-nc-nd/4.0/
Attribution-NonCommercial-NoDerivatives 4.0 Internacional
Caglieri , Silvana
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
_version_ 1877230889917743104
score 13.265058

Publicaciones similares