Highly Selective Reduction of <i>α, β</i>‐Unsaturated Aldehydes and Ketones under Ambient Conditions using Tetraalkylphosphonium‐based Ionic Liquids

Ralphs, Kathryn; McCourt, Éadaoin; Ormandy, Christopher; Souza, Thiago Alves de; Nockemann, Peter; Jacquemin, Johan; Manyar, Haresh

doi:10.1002/slct.201801092

Cited by 9 publications

(4 citation statements)

References 36 publications

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“…However, to address global environmental sustainability issues, green chemical processes must be developed, and the most straightforward way is to conduct it without using any solvent. Even though green solvents like water, , ionic liquids, , and supercritical CO 2 , have been reported, a solvent-free reaction system for CAL hydrogenation has not been reported to date. This challenge prompted us to design a catalyst using a method that immobilizes the solvent on a support, where the solvent can be easily recovered and reused.…”

Section: Introductionmentioning

confidence: 99%

Highly Active Pt–Co Bimetallic Nanoparticles on Ionic Liquid-Modified SBA-15 for Solvent-Free Selective Hydrogenation of Cinnamaldehyde

Kusumawati,

Sasaki,

Shirai

2023

ACS Appl. Nano Mater.

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Small Pt–Co bimetallic nanoparticles were prepared on ionic liquid-functionalized SBA-15. The prepared 2Pt–2Co/IL@SBA-15 showed high activity and selectivity in cinnamaldehyde hydrogenation to form cinnamyl alcohol under solvent-free conditions. The reaction proceeded efficiently without any addition of solvent with simple product recovery. 2Pt–2Co/IL@SBA-15 exhibited superior activity compared to the monometallic catalysts and Pt–Co on unmodified SBA-15, with 97.1% conversion and 96.2% selectivity to cinnamyl alcohol. The formation of small Pt–Co bimetallic nanoparticles and the presence of an ionic liquid are the keys to its high activity. XAFS analysis and STEM EDS mapping revealed that Pt–Co bimetallic nanoparticles were formed with both Pt and Co exposed on the surface of the nanoparticles. The charge transfer from Co to Pt on the surface of bimetallic nanoparticles results in a high selectivity for cinnamyl alcohol formation. The ionic liquid assisted the formation of small Pt–Co nanoparticles inside the pores of SBA-15 and acted as an “immobilized solvent” allowing the hydrogenation reaction to proceed efficiently without the need for an additional solvent. Moreover, the ionic liquid is strongly bonded to SBA-15, preventing aggregation of bimetallic nanoparticles, resulting in high durability and stability that allows the catalyst to be used six times without significant activity loss.

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Section: Introductionmentioning

confidence: 99%

Highly Active Pt–Co Bimetallic Nanoparticles on Ionic Liquid-Modified SBA-15 for Solvent-Free Selective Hydrogenation of Cinnamaldehyde

Kusumawati,

Sasaki,

Shirai

2023

ACS Appl. Nano Mater.

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“…Ionic liquids have shown promising catalytic activities, , and provide an attractive alternative to solid acids with benefits such as good thermal stability, ease of handling, and good recyclability . SO 3 H functionalized ionic liquids have been investigated by Li et al and Liu et al Liu et al found [(HSO 3 -p) 2 im][HSO 4 ] to be the most active catalyst, exhibiting 95% conversion of glycerol and selectivity to di and triacetin of 51.4 and 5.5%, respectively, after 30 min at 100 °C.…”

Section: Introductionmentioning

confidence: 99%

Esterification of Glycerol with Acetic Acid Using Nitrogen-Based Brønsted-Acidic Ionic Liquids

Keogh

Tiwari

Manyar

2019

Ind. Eng. Chem. Res.

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Glycerol esterification with acetic acid produces a mixture of mono, di, and triacetins, which are commercially important value-added products with a wide range of industrial uses including their application as fuel-additives, thus contributing to environmental sustainability and economic viability of the biorefinery concept. Glycerol esterification with acetic acid was studied using a range of nitrogen-based Brønsted-acidic ionic liquids. Cost-effective and easily synthesized Brønsted-acidic ionic liquids based on alkyl-pyrrolidone and alkyl-amine cations were synthesized and characterized using 1H NMR spectroscopy. The catalytic activity of the Brønsted-acidic ionic liquids produced were investigated for the production of di and triacetin from glycerol and acetic acid. Amongst all ionic liquids evaluated in this study, N-methyl-2-pyrrolidinium hydrogen sulfate [H-NMP][HSO4] was found to be the most active and cost-effective catalyst. The effect of significant reaction parameters on selectivity to the trisubstituted product, triacetin, was modeled using a design of experiment (DoE) approach with a response surface methodology involving a central composite design. The esterification process was optimized to maximize the production of triacetin. Optimizing the process this way naturally leads to lower levels of mono and diacetin. Amongst the reaction parameters evaluated, temperature had the greatest influence on product selectivity, followed by the glycerol to acetic acid molar ratio, and the model also showed dependence on the synergistic interaction between the temperature and mole ratio. It is worth noting that agitation speed had minimal influence on product selectivity. Under optimized reaction conditions, >99% glycerol conversion was achieved with 42.3% selectivity to triacetin, and a combined di and triacetin selectivity of >95% within 1 h.

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“…The selective hydrogenation of α, β ‐unsaturated aldehydes and ketones is a useful functional group transformation in organic synthesis and is of high importance in the fine chemical industry especially in the production of pharmaceuticals, fragrances and flavours [39] . As we have mentioned previously especially in the case of nucleophilic hydride reagents and because of the steric and electronic reasons, generally aldehydes are more susceptible to reduction than ketones.…”

Section: Catalytic Activitymentioning

confidence: 99%

Highly Selective Reduction of Carbonyl Compounds and O‐Acetylation of Arylalcohols in the Presence of a Nickel Ion‐Containing 1,4‐Diazabicyclo[2.2.2]octane (DABCO)‐Based Ionic Liquid

et al. 2023

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During this study, an easy procedure is presented for the preparation of a new nickel ion-containing DABCO based ionic liquid. The prepared reagent was characterized using FT-IR, FESEM, EDX, XRD, ICP-OES, TGA and DRS analyses. In continue the catalytic activity of this reagent which is formulated as [C 4 (DABCO) 2 ].NiCl 4 was investigated in the reduction of a variety of carbonyl compounds to their corresponding alcohols with NaBH 4 . The promoting ability of this catalyst was also confirmed in the acetylation of alcohols with CH 3 COCl. All reactions were carried out in short times with high to excellent yields. The catalyst was also recoverable and reusable in the studied reactions.

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Highly Selective Reduction of α, β‐Unsaturated Aldehydes and Ketones under Ambient Conditions using Tetraalkylphosphonium‐based Ionic Liquids

Cited by 9 publications

References 36 publications

Highly Active Pt–Co Bimetallic Nanoparticles on Ionic Liquid-Modified SBA-15 for Solvent-Free Selective Hydrogenation of Cinnamaldehyde

Highly Active Pt–Co Bimetallic Nanoparticles on Ionic Liquid-Modified SBA-15 for Solvent-Free Selective Hydrogenation of Cinnamaldehyde

Esterification of Glycerol with Acetic Acid Using Nitrogen-Based Brønsted-Acidic Ionic Liquids

Highly Selective Reduction of Carbonyl Compounds and O‐Acetylation of Arylalcohols in the Presence of a Nickel Ion‐Containing 1,4‐Diazabicyclo[2.2.2]octane (DABCO)‐Based Ionic Liquid

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