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 <b>1</b> and of some of its amino derivatives (<b>4a, 4e, 4g,</b> and <b>4l</b>) and on DFT calculations concerning the nucleophilic reactivity of <b>1</b>. We have found...
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MDPI AG
2021-12-01
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| Series: | International Journal of Molecular Sciences |
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| Online Access: | https://www.mdpi.com/1422-0067/22/24/13460 |
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| author | Elena Chugunova Nurgali Akylbekov Alexey Dobrynin Alexander Burilov Carla Boga Gabriele Micheletti Vincenzo Frenna Edoardo Jun Mattioli Matteo Calvaresi Domenico Spinelli |
| author_facet | Elena Chugunova Nurgali Akylbekov Alexey Dobrynin Alexander Burilov Carla Boga Gabriele Micheletti Vincenzo Frenna Edoardo Jun Mattioli Matteo Calvaresi Domenico Spinelli |
| author_sort | Elena Chugunova |
| collection | DOAJ |
| description | This research focuses on the X-ray structure of 4,6-dichloro-5-nitrobenzofuroxan <b>1</b> and of some of its amino derivatives (<b>4a, 4e, 4g,</b> and <b>4l</b>) and on DFT calculations concerning the nucleophilic reactivity of <b>1</b>. We have found that by changing the solvent used for crystallization, it is possible to obtain 4,6-dichloro-5-nitrobenzofuroxan (<b>1</b>) in different polymorphic structures. Moreover, the different torsional angles observed for the nitro group in <b>1</b> and in its amino derivatives (<b>4a</b>, <b>4e</b>, <b>4g,</b> and <b>4l</b>) 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. |
| first_indexed | 2024-03-10T03:55:58Z |
| format | Article |
| id | doaj.art-d34415d4fe7449a08cdd276fa5ad6af3 |
| institution | Directory Open Access Journal |
| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-10T03:55:58Z |
| publishDate | 2021-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | International Journal of Molecular Sciences |
| spelling | doaj.art-d34415d4fe7449a08cdd276fa5ad6af32023-11-23T08:46:41ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672021-12-0122241346010.3390/ijms2224134604,6-Dichloro-5-Nitrobenzofuroxan: Different Polymorphisms and DFT Investigation of Its Reactivity with NucleophilesElena Chugunova0Nurgali Akylbekov1Alexey Dobrynin2Alexander Burilov3Carla Boga4Gabriele Micheletti5Vincenzo Frenna6Edoardo Jun Mattioli7Matteo Calvaresi8Domenico Spinelli9Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Akad. Arbuzov st. 8, 420088 Kazan, RussiaLaboratory of Engineering Profile “Physical and Chemical Methods of Analysis”, Korkyt Ata Kyzylorda University, Aitekebie str. 29A, Kyzylorda 120014, KazakhstanArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Akad. Arbuzov st. 8, 420088 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Akad. Arbuzov st. 8, 420088 Kazan, RussiaDepartment of Industrial Chemistry ‘Toso Montanari’ ALMA MATER STUDIORUM, Università di Bologna, Viale del Risorgimento 4, 40136 Bologna, ItalyDepartment of Industrial Chemistry ‘Toso Montanari’ ALMA MATER STUDIORUM, Università di Bologna, Viale del Risorgimento 4, 40136 Bologna, ItalyDepartment STEBICEF, University of Palermo, Ed.17, Viale delle Scienze, 90128 Palermo, ItalyDepartment of Chemistry ‘G. Ciamician’ ALMA MATER STUDIORUM, Università di Bologna, Via Selmi 2, 40126 Bologna, ItalyDepartment of Chemistry ‘G. Ciamician’ ALMA MATER STUDIORUM, Università di Bologna, Via Selmi 2, 40126 Bologna, ItalyDepartment of Chemistry ‘G. Ciamician’ ALMA MATER STUDIORUM, Università di Bologna, Via Selmi 2, 40126 Bologna, ItalyThis research focuses on the X-ray structure of 4,6-dichloro-5-nitrobenzofuroxan <b>1</b> and of some of its amino derivatives (<b>4a, 4e, 4g,</b> and <b>4l</b>) and on DFT calculations concerning the nucleophilic reactivity of <b>1</b>. We have found that by changing the solvent used for crystallization, it is possible to obtain 4,6-dichloro-5-nitrobenzofuroxan (<b>1</b>) in different polymorphic structures. Moreover, the different torsional angles observed for the nitro group in <b>1</b> and in its amino derivatives (<b>4a</b>, <b>4e</b>, <b>4g,</b> and <b>4l</b>) 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.https://www.mdpi.com/1422-0067/22/24/13460benzofuroxansX-ray structurespolymorphismnucleophilic substitutionsDFT calculations |
| spellingShingle | Elena Chugunova Nurgali Akylbekov Alexey Dobrynin Alexander Burilov Carla Boga Gabriele Micheletti Vincenzo Frenna Edoardo Jun Mattioli Matteo Calvaresi Domenico Spinelli 4,6-Dichloro-5-Nitrobenzofuroxan: Different Polymorphisms and DFT Investigation of Its Reactivity with Nucleophiles International Journal of Molecular Sciences benzofuroxans X-ray structures polymorphism nucleophilic substitutions DFT calculations |
| 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 | benzofuroxans X-ray structures polymorphism nucleophilic substitutions DFT calculations |
| url | https://www.mdpi.com/1422-0067/22/24/13460 |
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