Highly efficient and selective partial reduction of nitroarenes to N-arylhydroxylamines catalysed by phosphine oxide-decorated polymer immobilized ionic liquid stabilized ruthenium nanoparticles

Paterson, Reece; Alharbi, Husam Y.; Wills, Corinne; Chamberlain, Thomas W.; Bourne, Richard A.; Griffiths, Ann; Collins, Sean M.; Wu, Ke‐Jun; Simmons, M. Y.; Menzel, Robert; Masey, Alexander F.; Knight, Julian G.; Doherty, Simon

doi:10.1016/j.jcat.2022.11.023

Cited by 7 publications

(3 citation statements)

References 132 publications

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“…Examination of the development of the hydrogenation reaction showed that the amount of aryl amine did not increase significantly after removing the catalyst. This eliminates the possibility of Au leaching and redeposition during the reaction and confirms the heterogeneous nature of the catalyst 53 …”

Section: Resultssupporting

confidence: 52%

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Designing magnetic catalysts based on gold nanoparticles supported by ethylenediamine tetraacetic acid functionalized amino‐modified poly(N‐isopropyl acrylamide) for reduction of nitro compounds in water

Kafshboran,

Ghasemi

2024

Polymer International

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A novel smart catalyst was developed with amino‐modified thermo‐responsive poly (N‐isopropyl acrylamide) (PNIPAM) grafts on silica‐coated MNPs using the conventional free radical polymerization process. By this methodology, the polymer was successfully grafted mainly onto the silica modified iron oxide nanoparticles (Fe3O4@Si). The PNIPAM‐grafted Fe3O4@Si was then subjected to ethylenediamine treatment to produce the amino‐functionalized support (Fe3O4@Si@PNIPAM‐NH2), which was subsequently modified with carboxyl functional groups by using EDTA (ethylenediaminetetraacetic acid) to create Fe3O4@Si@PNIPAM‐NH2‐EDTA. Au nanoparticles were then decorated on this support through its two amines and four carboxylates Different methods were used to study this novel catalyst, including ICP, FT‐IR, TGA, DLS, SEM, EDX, VSM, XRD, and CHN. The reduction of several aryl‐nitro derivatives demonstrated a significant catalytic activity for the as‐synthesized gold catalyst (Fe3O4@Si‐PNIPAM‐NH2‐EDTA‐Au). The Au catalyst can be successfully removed from the reaction components using magnetic fields and used again in 8 successive reduction reactions without significant gold leaching and loss of catalytic activity.This article is protected by copyright. All rights reserved.

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Section: Resultssupporting

confidence: 52%

“…This eliminates the possibility of Au leaching and redeposition during the reaction and confirms the heterogeneous nature of the catalyst. 53…”

Section: Catalyst Recycling and Leaching Investigationsmentioning

confidence: 99%

Designing magnetic catalysts based on gold nanoparticles supported by ethylenediamine tetraacetic acid functionalized amino‐modified poly(N‐isopropyl acrylamide) for reduction of nitro compounds in water

Kafshboran,

Ghasemi

2024

Polymer International

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“…Using 4-nitroacetophenone as the substrate gave a 100 % of conversion after 40 min at the same conditions, while the selectivity to the corresponding N-arylhydroxylamine decreased (74 %) due to the complete reduction to 4-aminoacetophenone, in good agreement with a previous report for this substrate. [13] Previous reports showed that halogen-substituted nitroarenes are not suitable substrates for the synthesis of the corresponding N-arylhydroxylamines due to the dehalogenation. [14] Surprisingly, in our catalytic reaction system the reduction of nitroarenes bearing chloroand bromo-groups at the 2-position achieved 100 % conversions to form the corresponding N-arylhydroxylamines in 97 % and 96 % yields, respectively (entries 2-3), with no observation of any dehalogenation products, which was attributed to the mild reaction conditions used in this work.…”

Section: Scope Of the Reactionmentioning

confidence: 99%

Pt/C‐catalyzed Selective Hydrogenation of Nitroarenes to N‐arylhydroxylamines under Mild Conditions

Chen,

Zhang,

Liu

et al. 2023

ChemistrySelect

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The synthesis of N‐arylhydroxylamines through the in‐situ hydrogenation of nitroarenes over commercial Pt/C catalyst was investigated. The effects of various reaction conditions including hydrogen donor, solvent, catalyst dosage, temperature and reaction time on the selective hydrogenation of nitrobenzene (NB) to N‐phenylhydroxylamine (PHA) were systematically investigated. The results showed that the yield of N‐phenylhydroxylamine reached 87.2 % using hydrazine hydrate as hydrogen donor in N,N‐dimethylformamide solvent at 30 °C for 60 min. And the catalyst showed no obvious activity loss after a 6‐times recycle. Meanwhile, the developed methodology can also transform a range of nitroarenes to the corresponding N‐arylhydroxylamines in excellent yields (74–99 %).

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Amino‐Modified Polymer Immobilized Ionic Liquid Stabilized Ruthenium Nanoparticles: Efficient and Selective Catalysts for the Partial and Complete Reduction of Quinolines

et al. 2023

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RuNPs stabilised by amino‐decorated imidazolium‐based polymer immobilized ionic liquids catalyse the dimethylamine borane mediated reduction of quinolines to 1,2‐dihydroquinoline (DHQ) and 1,2,3,4‐tetrahydroquinoline (THQ). Partial reduction of 3‐substituted quinolines to the corresponding 1,2‐dihydroquinoline was achieved with 100 % selectivity in toluene under mild conditions. This is the first report of the selective partial reduction of 3‐substituted quinolines to the corresponding 1,2‐dihydroquinolines with a heterogeneous nanoparticle‐based catalyst. A wide range of substituted quinolines have also been reduced to the corresponding 1,2,3,4‐tetrahydroquinoline with high selectivity and good yields by adjusting the reaction time. The 1,2‐dihydroquinolines readily release dihydrogen in toluene at 60 °C in the absence of catalyst with no evidence for disproportionation and as such are potential organo‐hydride reagents. The initial TOF of 610 mol quinoline converted mol Ru−1 h−1 for the reduction of quinoline is among the highest to be reported for a metal nanoparticle‐based catalyst and the conversion of 96 % obtained after 4 h at 65 °C is significantly higher than its platinum nanoparticle counterpart PtNP@NH2‐PEGPIILS as well as 5 wt/% Ru/C, which only reached 9 % and 11 % conversion, respectively, at the same time. Hot filtration experiments showed that the active species was heterogeneous.

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Highly efficient and selective partial reduction of nitroarenes to N-arylhydroxylamines catalysed by phosphine oxide-decorated polymer immobilized ionic liquid stabilized ruthenium nanoparticles

Cited by 7 publications

References 132 publications

Designing magnetic catalysts based on gold nanoparticles supported by ethylenediamine tetraacetic acid functionalized amino‐modified poly(N‐isopropyl acrylamide) for reduction of nitro compounds in water

Designing magnetic catalysts based on gold nanoparticles supported by ethylenediamine tetraacetic acid functionalized amino‐modified poly(N‐isopropyl acrylamide) for reduction of nitro compounds in water

Pt/C‐catalyzed Selective Hydrogenation of Nitroarenes to N‐arylhydroxylamines under Mild Conditions

Amino‐Modified Polymer Immobilized Ionic Liquid Stabilized Ruthenium Nanoparticles: Efficient and Selective Catalysts for the Partial and Complete Reduction of Quinolines

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