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Selective hydrogenation of nitroaromatics to N-arylhydroxylamines in a micropacked bed reactor with passivated catalyst
In this contribution, a protocol was established for the selective catalytic hydrogenation of nitroarenes to the corresponding N-arylhydroxylamines. The reduction of 1-(4-chlorophenyl)-3-((2-nitrobenzyl)oxy)-1H-pyrazole, an intermediate in the synthesis of the antifungal reagent pyraclostrobin that...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9055875/ https://www.ncbi.nlm.nih.gov/pubmed/35520060 http://dx.doi.org/10.1039/d0ra05715k |
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author | Xu, Feng Chen, Jian-Li Jiang, Zhi-Jiang Cheng, Peng-Fei Yu, Zhi-Qun Su, Wei-Ke |
author_facet | Xu, Feng Chen, Jian-Li Jiang, Zhi-Jiang Cheng, Peng-Fei Yu, Zhi-Qun Su, Wei-Ke |
author_sort | Xu, Feng |
collection | PubMed |
description | In this contribution, a protocol was established for the selective catalytic hydrogenation of nitroarenes to the corresponding N-arylhydroxylamines. The reduction of 1-(4-chlorophenyl)-3-((2-nitrobenzyl)oxy)-1H-pyrazole, an intermediate in the synthesis of the antifungal reagent pyraclostrobin that includes carbon–chlorine bonds, benzyl groups, carbon–carbon double bonds and other structures that are easily reduced, was chosen as the model reaction for catalyst evaluation and condition optimization. Extensive passivant evaluation showed that RANEY®-nickel treated with ammonia/DMSO (1 : 10, v/v) afforded the optimal result, especially with a particle size of 400–500 mesh. To combine the modified catalyst with continuous-flow reaction technology, the reaction was conducted at room temperature, rendering the desired product with a conversion rate of 99.4% and a selectivity of 99.8%. The regeneration of catalytic activity was also studied, and an in-column strategy was developed by pumping the passivate liquid overnight. Finally, the generality of the method was explored, and 7 substrates were developed, most of which showed a good conversion rate and selectivity, indicating that the method has a certain degree of generality. |
format | Online Article Text |
id | pubmed-9055875 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-90558752022-05-04 Selective hydrogenation of nitroaromatics to N-arylhydroxylamines in a micropacked bed reactor with passivated catalyst Xu, Feng Chen, Jian-Li Jiang, Zhi-Jiang Cheng, Peng-Fei Yu, Zhi-Qun Su, Wei-Ke RSC Adv Chemistry In this contribution, a protocol was established for the selective catalytic hydrogenation of nitroarenes to the corresponding N-arylhydroxylamines. The reduction of 1-(4-chlorophenyl)-3-((2-nitrobenzyl)oxy)-1H-pyrazole, an intermediate in the synthesis of the antifungal reagent pyraclostrobin that includes carbon–chlorine bonds, benzyl groups, carbon–carbon double bonds and other structures that are easily reduced, was chosen as the model reaction for catalyst evaluation and condition optimization. Extensive passivant evaluation showed that RANEY®-nickel treated with ammonia/DMSO (1 : 10, v/v) afforded the optimal result, especially with a particle size of 400–500 mesh. To combine the modified catalyst with continuous-flow reaction technology, the reaction was conducted at room temperature, rendering the desired product with a conversion rate of 99.4% and a selectivity of 99.8%. The regeneration of catalytic activity was also studied, and an in-column strategy was developed by pumping the passivate liquid overnight. Finally, the generality of the method was explored, and 7 substrates were developed, most of which showed a good conversion rate and selectivity, indicating that the method has a certain degree of generality. The Royal Society of Chemistry 2020-08-03 /pmc/articles/PMC9055875/ /pubmed/35520060 http://dx.doi.org/10.1039/d0ra05715k Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Xu, Feng Chen, Jian-Li Jiang, Zhi-Jiang Cheng, Peng-Fei Yu, Zhi-Qun Su, Wei-Ke Selective hydrogenation of nitroaromatics to N-arylhydroxylamines in a micropacked bed reactor with passivated catalyst |
title | Selective hydrogenation of nitroaromatics to N-arylhydroxylamines in a micropacked bed reactor with passivated catalyst |
title_full | Selective hydrogenation of nitroaromatics to N-arylhydroxylamines in a micropacked bed reactor with passivated catalyst |
title_fullStr | Selective hydrogenation of nitroaromatics to N-arylhydroxylamines in a micropacked bed reactor with passivated catalyst |
title_full_unstemmed | Selective hydrogenation of nitroaromatics to N-arylhydroxylamines in a micropacked bed reactor with passivated catalyst |
title_short | Selective hydrogenation of nitroaromatics to N-arylhydroxylamines in a micropacked bed reactor with passivated catalyst |
title_sort | selective hydrogenation of nitroaromatics to n-arylhydroxylamines in a micropacked bed reactor with passivated catalyst |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9055875/ https://www.ncbi.nlm.nih.gov/pubmed/35520060 http://dx.doi.org/10.1039/d0ra05715k |
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