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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...

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Autores principales: Chugunova, Elena, Akylbekov, Nurgali, Dobrynin, Alexey, Burilov, Alexander, Boga, Carla, Micheletti, Gabriele, Frenna, Vincenzo, Mattioli, Edoardo Jun, Calvaresi, Matteo, Spinelli, Domenico
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2021
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.
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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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