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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...

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Autores principales: Xu, Feng, Chen, Jian-Li, Jiang, Zhi-Jiang, Cheng, Peng-Fei, Yu, Zhi-Qun, Su, Wei-Ke
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2020
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.
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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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