Ammonium Dinitramide as a Prospective N–NO<sub>2</sub> Synthon: Electrochemical Synthesis of Nitro-<i>NNO</i>-Azoxy Compounds from Nitrosoarenes
In this study, the electrochemical coupling of nitrosoarenes with ammonium dinitramide is discovered, leading to the facile construction of the nitro-<i>NNO</i>-azoxy group, which represents an important motif in the design of energetic materials. Compared to known approaches to nitro-&l...
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2024-11-01
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| author | Alexander S. Budnikov Nikita E. Leonov Michael S. Klenov Mikhail I. Shevchenko Tatiana Y. Dvinyaninova Igor B. Krylov Aleksandr M. Churakov Ivan V. Fedyanin Vladimir A. Tartakovsky Alexander O. Terent’ev |
| author_facet | Alexander S. Budnikov Nikita E. Leonov Michael S. Klenov Mikhail I. Shevchenko Tatiana Y. Dvinyaninova Igor B. Krylov Aleksandr M. Churakov Ivan V. Fedyanin Vladimir A. Tartakovsky Alexander O. Terent’ev |
| author_sort | Alexander S. Budnikov |
| collection | DOAJ |
| description | In this study, the electrochemical coupling of nitrosoarenes with ammonium dinitramide is discovered, leading to the facile construction of the nitro-<i>NNO</i>-azoxy group, which represents an important motif in the design of energetic materials. Compared to known approaches to nitro-<i>NNO</i>-azoxy compounds involving two chemical steps (formation of azoxy group containing a leaving group and its nitration) and demanding expensive, corrosive, and hygroscopic nitronium salts, the presented electrochemical method consists of a single step and is based solely on nitrosoarenes and ammonium dinitramide. The dinitramide salt plays the roles of both the electrolyte and reactant for the coupling. Despite the fact that many side reactions can be expected due to the redox-activity of both the reagents and target products, under optimized conditions the synthesis is performed in an undivided cell under constant current conditions with high current density and can be easily scaled up without a reduction in the product yield. Moreover, the synthesized nitro-<i>NNO</i>-azoxy compounds are discovered to be potent fungicides active against a broad range of phytopathogenic fungi. |
| format | Article |
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| institution | OA Journals |
| issn | 1420-3049 |
| language | English |
| publishDate | 2024-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj-art-fb17c9ef728643a2aa63d7cd3834e4f72025-08-20T01:55:38ZengMDPI AGMolecules1420-30492024-11-012923556310.3390/molecules29235563Ammonium Dinitramide as a Prospective N–NO<sub>2</sub> Synthon: Electrochemical Synthesis of Nitro-<i>NNO</i>-Azoxy Compounds from NitrosoarenesAlexander S. Budnikov0Nikita E. Leonov1Michael S. Klenov2Mikhail I. Shevchenko3Tatiana Y. Dvinyaninova4Igor B. Krylov5Aleksandr M. Churakov6Ivan V. Fedyanin7Vladimir A. Tartakovsky8Alexander O. Terent’ev9N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prosp., 119991 Moscow, RussiaN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prosp., 119991 Moscow, RussiaN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prosp., 119991 Moscow, RussiaN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prosp., 119991 Moscow, RussiaN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prosp., 119991 Moscow, RussiaN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prosp., 119991 Moscow, RussiaN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prosp., 119991 Moscow, RussiaA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova Str., 119991 Moscow, RussiaN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prosp., 119991 Moscow, RussiaN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prosp., 119991 Moscow, RussiaIn this study, the electrochemical coupling of nitrosoarenes with ammonium dinitramide is discovered, leading to the facile construction of the nitro-<i>NNO</i>-azoxy group, which represents an important motif in the design of energetic materials. Compared to known approaches to nitro-<i>NNO</i>-azoxy compounds involving two chemical steps (formation of azoxy group containing a leaving group and its nitration) and demanding expensive, corrosive, and hygroscopic nitronium salts, the presented electrochemical method consists of a single step and is based solely on nitrosoarenes and ammonium dinitramide. The dinitramide salt plays the roles of both the electrolyte and reactant for the coupling. Despite the fact that many side reactions can be expected due to the redox-activity of both the reagents and target products, under optimized conditions the synthesis is performed in an undivided cell under constant current conditions with high current density and can be easily scaled up without a reduction in the product yield. Moreover, the synthesized nitro-<i>NNO</i>-azoxy compounds are discovered to be potent fungicides active against a broad range of phytopathogenic fungi.https://www.mdpi.com/1420-3049/29/23/5563electrochemistryN–N couplingazoxy compoundsammonium dinitramidenitroso compoundsantifungal agents |
| spellingShingle | Alexander S. Budnikov Nikita E. Leonov Michael S. Klenov Mikhail I. Shevchenko Tatiana Y. Dvinyaninova Igor B. Krylov Aleksandr M. Churakov Ivan V. Fedyanin Vladimir A. Tartakovsky Alexander O. Terent’ev Ammonium Dinitramide as a Prospective N–NO<sub>2</sub> Synthon: Electrochemical Synthesis of Nitro-<i>NNO</i>-Azoxy Compounds from Nitrosoarenes Molecules electrochemistry N–N coupling azoxy compounds ammonium dinitramide nitroso compounds antifungal agents |
| title | Ammonium Dinitramide as a Prospective N–NO<sub>2</sub> Synthon: Electrochemical Synthesis of Nitro-<i>NNO</i>-Azoxy Compounds from Nitrosoarenes |
| title_full | Ammonium Dinitramide as a Prospective N–NO<sub>2</sub> Synthon: Electrochemical Synthesis of Nitro-<i>NNO</i>-Azoxy Compounds from Nitrosoarenes |
| title_fullStr | Ammonium Dinitramide as a Prospective N–NO<sub>2</sub> Synthon: Electrochemical Synthesis of Nitro-<i>NNO</i>-Azoxy Compounds from Nitrosoarenes |
| title_full_unstemmed | Ammonium Dinitramide as a Prospective N–NO<sub>2</sub> Synthon: Electrochemical Synthesis of Nitro-<i>NNO</i>-Azoxy Compounds from Nitrosoarenes |
| title_short | Ammonium Dinitramide as a Prospective N–NO<sub>2</sub> Synthon: Electrochemical Synthesis of Nitro-<i>NNO</i>-Azoxy Compounds from Nitrosoarenes |
| title_sort | ammonium dinitramide as a prospective n no sub 2 sub synthon electrochemical synthesis of nitro i nno i azoxy compounds from nitrosoarenes |
| topic | electrochemistry N–N coupling azoxy compounds ammonium dinitramide nitroso compounds antifungal agents |
| url | https://www.mdpi.com/1420-3049/29/23/5563 |
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