Theoretical study of acid acetylation of aniline

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. Acetylation of amine is a nucleophilic substitution reaction. This reaction can be c...

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Autores principales: Caglieri, Silvana, Servetti, Gustavo Iván, Picco, Eduardo
Formato: Artículo publisherVersion
Lenguaje:Inglés
Publicado: 2024
Materias:
Acetylation
Organic synthesis
Nucleophilic
Acceso en línea:http://hdl.handle.net/20.500.12272/11141
Aporte de:
RIA - Repositorio Institucional Abierto (UTN) de Universidad Tecnológica Nacional
id I68-R174-20.500.12272-11141
record_format dspace
spelling I68-R174-20.500.12272-111412024-07-22T22:37:18Z Theoretical study of acid acetylation of aniline Caglieri, Silvana Servetti, Gustavo Iván Picco, Eduardo Acetylation Organic synthesis Nucleophilic 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. Acetylation of amine is a nucleophilic substitution reaction. This reaction can be catalyzed by Brönsted acid. In the mechanism, the acetic anhydride first accepts a proton at the carbonyl oxygen and this change enhances the positive charge on the carbonyl carbon. This protonation facilitates the successive addition of amine at the position to form a tetrahedral intermediate, determining step of the rate of the reaction. Computational method to study the reaction using acid catalysis [1] and an experimental work [2], agreed that this reaction takes place with the formation of a tetrahedral intermediate. A theoretical study of acid acetylation of aniline 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 [3] 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. Figure 1 show the optimized structure of the intermediate and the Table 1 lists the geometric parameters, lengths and binding angles values, obtained. The calculations show 18.37 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 Iván. Universidad Tecnológica Nacional . Facultad Regional Córdoba. Centro de Investigación y Transferencia en Ingeniería Química Ambiental; Argentina. Fil: Picco, Eduardo. Universidad Tecnológica Nacional . Facultad Regional Córdoba. Centro de Investigación y Transferencia en Ingeniería Química Ambiental; Argentina. Peer Reviewed 2024-07-22T22:37:18Z 2024-07-22T22:37:18Z 2014 info:eu-repo/semantics/article publisherVersion International Conference on Pure and Applied Chemistry .2014 http://hdl.handle.net/20.500.12272/11141 - eng openAccess http://creativecommons.org/licenses/by-nc-nd/4.0/ Attribution-NonCommercial-NoDerivatives 4.0 Internacional Caglieri , Silvana; Servetti, Gustavo Ivàn; Picco, Eduardo 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
Organic synthesis
Nucleophilic
spellingShingle Acetylation
Organic synthesis
Nucleophilic
Caglieri, Silvana
Servetti, Gustavo Iván
Picco, Eduardo
Theoretical study of acid acetylation of aniline
topic_facet Acetylation
Organic synthesis
Nucleophilic
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. Acetylation of amine is a nucleophilic substitution reaction. This reaction can be catalyzed by Brönsted acid. In the mechanism, the acetic anhydride first accepts a proton at the carbonyl oxygen and this change enhances the positive charge on the carbonyl carbon. This protonation facilitates the successive addition of amine at the position to form a tetrahedral intermediate, determining step of the rate of the reaction. Computational method to study the reaction using acid catalysis [1] and an experimental work [2], agreed that this reaction takes place with the formation of a tetrahedral intermediate. A theoretical study of acid acetylation of aniline 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 [3] 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. Figure 1 show the optimized structure of the intermediate and the Table 1 lists the geometric parameters, lengths and binding angles values, obtained. The calculations show 18.37 kcal/mol of activation energy.
format Artículo
publisherVersion
author Caglieri, Silvana
Servetti, Gustavo Iván
Picco, Eduardo
author_facet Caglieri, Silvana
Servetti, Gustavo Iván
Picco, Eduardo
author_sort Caglieri, Silvana
title Theoretical study of acid acetylation of aniline
title_short Theoretical study of acid acetylation of aniline
title_full Theoretical study of acid acetylation of aniline
title_fullStr Theoretical study of acid acetylation of aniline
title_full_unstemmed Theoretical study of acid acetylation of aniline
title_sort theoretical study of acid acetylation of aniline
publishDate 2024
url http://hdl.handle.net/20.500.12272/11141
work_keys_str_mv AT caglierisilvana theoreticalstudyofacidacetylationofaniline
AT servettigustavoivan theoreticalstudyofacidacetylationofaniline
AT piccoeduardo theoreticalstudyofacidacetylationofaniline
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