Theoretical study of alkaline acetylation of p-methylaniline

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...

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Autores principales: Caglieri, Silvana, Servetti, Gustavo
Formato: Artículo publisherVersion
Lenguaje:Inglés
Publicado: 2024
Materias:
Alkaline acetylation
Organic synthesis
Acetic anhydride
Acceso en línea:http://hdl.handle.net/20.500.12272/11171
Aporte de:
RIA - Repositorio Institucional Abierto (UTN) de Universidad Tecnológica Nacional
id I68-R174-20.500.12272-11171
record_format dspace
spelling I68-R174-20.500.12272-111712024-07-25T20:50:38Z Theoretical study of alkaline acetylation of p-methylaniline Caglieri, Silvana Servetti, Gustavo Alkaline acetylation Organic synthesis Acetic anhydride 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 2024-07-25T20:50:38Z 2024-07-25T20:50:38Z 2015 info:eu-repo/semantics/article publisherVersion Torino Incontra Congress Center.2015 http://hdl.handle.net/20.500.12272/11171 - eng openAccess 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/ pdf
institution Universidad Tecnológica Nacional
institution_str I-68
repository_str R-174
collection RIA - Repositorio Institucional Abierto (UTN)
language Inglés
topic Alkaline acetylation
Organic synthesis
Acetic anhydride
spellingShingle Alkaline acetylation
Organic synthesis
Acetic anhydride
Caglieri, Silvana
Servetti, Gustavo
Theoretical study of alkaline acetylation of p-methylaniline
topic_facet Alkaline acetylation
Organic synthesis
Acetic anhydride
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.
format Artículo
publisherVersion
author Caglieri, Silvana
Servetti, Gustavo
author_facet Caglieri, Silvana
Servetti, Gustavo
author_sort Caglieri, Silvana
title Theoretical study of alkaline acetylation of p-methylaniline
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
publishDate 2024
url http://hdl.handle.net/20.500.12272/11171
work_keys_str_mv AT caglierisilvana theoreticalstudyofalkalineacetylationofpmethylaniline
AT servettigustavo theoreticalstudyofalkalineacetylationofpmethylaniline
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