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4,6-Dichloro-5-Nitrobenzofuroxan: Different Polymorphisms and DFT Investigation of Its Reactivity with Nucleophiles
This research focuses on the X-ray structure of 4,6-dichloro-5-nitrobenzofuroxan 1 and of some of its amino derivatives (4a, 4e, 4g, and 4l) and on DFT calculations concerning the nucleophilic reactivity of 1. We have found that by changing the solvent used for crystallization, it is possible to obt...
Autores principales: | , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8709177/ https://www.ncbi.nlm.nih.gov/pubmed/34948257 http://dx.doi.org/10.3390/ijms222413460 |
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author | Chugunova, Elena Akylbekov, Nurgali Dobrynin, Alexey Burilov, Alexander Boga, Carla Micheletti, Gabriele Frenna, Vincenzo Mattioli, Edoardo Jun Calvaresi, Matteo Spinelli, Domenico |
author_facet | Chugunova, Elena Akylbekov, Nurgali Dobrynin, Alexey Burilov, Alexander Boga, Carla Micheletti, Gabriele Frenna, Vincenzo Mattioli, Edoardo Jun Calvaresi, Matteo Spinelli, Domenico |
author_sort | Chugunova, Elena |
collection | PubMed |
description | This research focuses on the X-ray structure of 4,6-dichloro-5-nitrobenzofuroxan 1 and of some of its amino derivatives (4a, 4e, 4g, and 4l) and on DFT calculations concerning the nucleophilic reactivity of 1. We have found that by changing the solvent used for crystallization, it is possible to obtain 4,6-dichloro-5-nitrobenzofuroxan (1) in different polymorphic structures. Moreover, the different torsional angles observed for the nitro group in 1 and in its amino derivatives (4a, 4e, 4g, and 4l) are strictly dependent on the steric hindrance of the substituent at C-4. DFT calculations on the course of the nucleophilic substitution confirm the role of the condensed furoxan ring in altering the aromaticity of the carbocyclic frame, while chlorine atoms strongly influence the dihedral angle and the rotational barrier of the nitro group. These results corroborate previous observations based on experimental kinetic data and give a deep picture of the reaction with amines, which proceeds via a “non-aromatic” nucleophilic substitution. |
format | Online Article Text |
id | pubmed-8709177 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-87091772021-12-25 4,6-Dichloro-5-Nitrobenzofuroxan: Different Polymorphisms and DFT Investigation of Its Reactivity with Nucleophiles Chugunova, Elena Akylbekov, Nurgali Dobrynin, Alexey Burilov, Alexander Boga, Carla Micheletti, Gabriele Frenna, Vincenzo Mattioli, Edoardo Jun Calvaresi, Matteo Spinelli, Domenico Int J Mol Sci Article This research focuses on the X-ray structure of 4,6-dichloro-5-nitrobenzofuroxan 1 and of some of its amino derivatives (4a, 4e, 4g, and 4l) and on DFT calculations concerning the nucleophilic reactivity of 1. We have found that by changing the solvent used for crystallization, it is possible to obtain 4,6-dichloro-5-nitrobenzofuroxan (1) in different polymorphic structures. Moreover, the different torsional angles observed for the nitro group in 1 and in its amino derivatives (4a, 4e, 4g, and 4l) are strictly dependent on the steric hindrance of the substituent at C-4. DFT calculations on the course of the nucleophilic substitution confirm the role of the condensed furoxan ring in altering the aromaticity of the carbocyclic frame, while chlorine atoms strongly influence the dihedral angle and the rotational barrier of the nitro group. These results corroborate previous observations based on experimental kinetic data and give a deep picture of the reaction with amines, which proceeds via a “non-aromatic” nucleophilic substitution. MDPI 2021-12-15 /pmc/articles/PMC8709177/ /pubmed/34948257 http://dx.doi.org/10.3390/ijms222413460 Text en © 2021 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Chugunova, Elena Akylbekov, Nurgali Dobrynin, Alexey Burilov, Alexander Boga, Carla Micheletti, Gabriele Frenna, Vincenzo Mattioli, Edoardo Jun Calvaresi, Matteo Spinelli, Domenico 4,6-Dichloro-5-Nitrobenzofuroxan: Different Polymorphisms and DFT Investigation of Its Reactivity with Nucleophiles |
title | 4,6-Dichloro-5-Nitrobenzofuroxan: Different Polymorphisms and DFT Investigation of Its Reactivity with Nucleophiles |
title_full | 4,6-Dichloro-5-Nitrobenzofuroxan: Different Polymorphisms and DFT Investigation of Its Reactivity with Nucleophiles |
title_fullStr | 4,6-Dichloro-5-Nitrobenzofuroxan: Different Polymorphisms and DFT Investigation of Its Reactivity with Nucleophiles |
title_full_unstemmed | 4,6-Dichloro-5-Nitrobenzofuroxan: Different Polymorphisms and DFT Investigation of Its Reactivity with Nucleophiles |
title_short | 4,6-Dichloro-5-Nitrobenzofuroxan: Different Polymorphisms and DFT Investigation of Its Reactivity with Nucleophiles |
title_sort | 4,6-dichloro-5-nitrobenzofuroxan: different polymorphisms and dft investigation of its reactivity with nucleophiles |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8709177/ https://www.ncbi.nlm.nih.gov/pubmed/34948257 http://dx.doi.org/10.3390/ijms222413460 |
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