New biobased tetrabutylphosphonium ionic liquids: synthesis, characterization and use as a solvent or co-solvent for mild and greener Pd-catalyzed hydrogenation processes

Hayouni, Safa; Robert, Anthony; Ferlin, Nadège; Amri, Hassen; Bouquillon, Sandrine

doi:10.1039/c6ra23056c

Cited by 22 publications

(25 citation statements)

References 83 publications

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“…1 H NMR (400 MHz, [D 6 ]DMSO, 23 °C, TMS): δ = 2.26–2.15 (m, 16H), 1.81 (s, 4H), 1.53–1.35 (m, 32H), 0.92 (t, 3 J HH = 7.0 Hz, 24H); 13 C NMR (101 MHz, [D 6 ]DMSO, 23 °C, TMS): δ = 176.64 (s), 38.41 (s), 23.84 (d, 3 J CP = 15.6 Hz), 23.14 (d, 2 J CP = 4.4 Hz), 17.81 (d, 1 J CP = 47.6 Hz), 13.75 (s); CHN analysis (%) for C 36 H 75 O 4 P 2 : C (68.21), H (11.93); found C (68.25), H (12.01). This compound has been previously reported …”

Section: Methodsmentioning

confidence: 76%

“…As far as we are aware, with the exception of TBPM, TBAA and TBPA ( B5 , B7 and B9 respectively, Table ), all organic bases reported in Table have not previously been employed in Ullmann C–N cross coupling reactions. However some have been used as ionic liquids or as catalysts for aminoxylation of aldehydes . All organic bases were prepared by reacting either tetraalkylammonium hydroxide or tetraalkylphosphonium hydroxide with the corresponding acid.…”

Section: Resultsmentioning

confidence: 99%

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New Insights into the Reaction Capabilities of Ionic Organic Bases in Cu‐Catalyzed Amination

Sale

Braddock

et al. 2019

Eur J Org Chem

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The application of ionic organic bases in the copper‐catalyzed amination reaction (Ullmann reaction) has been studied at room temperature, with sub‐mol‐% catalyst loadings, and with more challenging amines at elevated temperatures. The cation present in the base has been shown to have little effect on the reaction at standard catalyst and ancillary ligand loadings, whereas the choice of anion is crucial for good reactivity. A substrate scope carried out at room temperature with the best performing bases, TBAM and TBPM, showed both bases to be highly effective under these mild reaction conditions. Moreover, under sub‐mol % catalyst loadings and room temperature conditions, TBPM gave good to excellent yields for a number of different amines and functionalized aryl iodides (14 examples). However, reactions involving more challenging amines gave little or no yield. By using more forceful conditions (120 °C) moderate to excellent yields of cross‐coupled products containing more challenging amines was achievable using TBPM and to a lesser extent with TBAM. As part of this work a study on the stability of the organic bases at 120 °C was undertaken. TBAM is shown to decompose to give nBu3N and mono‐butylmalonate at higher temperatures, and this can be correlated to a decrease in performance in the coupling reaction. The phosphonium cations in TBPM did not undergo analogous reactivity but were shown instead to experience some degree of deprotonation at the α‐CH2 to generate phosphonium ylides. This however did not lead to a significantly degradation in the activity of the TBPM in the cross‐coupling reaction.

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Section: Methodsmentioning

confidence: 76%

Section: Resultsmentioning

confidence: 99%

New Insights into the Reaction Capabilities of Ionic Organic Bases in Cu‐Catalyzed Amination

Sale

Braddock

et al. 2019

Eur J Org Chem

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“…All the phosphonium salts were liquid at room temperature, while various ammonium ILs were solids at ambient conditions. The lowering of the melting point (by replacing a nitrogen atom with a phosphorus one) was observed in works by other groups [ 56 , 118 , 119 ]. An explanation for this phenomenon can be found in the increase of the atomic radius moving from nitrogen to phosphorus, which causes a lowering in the lattice energy and gives more flexibility to the structure.…”

Section: Thermal Analysismentioning

confidence: 77%

“…d -glucuronic acid and d -galacturonic acid have been used in synthesizing new ILs ( Scheme 11 A) mainly through a neutralization pathway [ 54 , 55 , 56 , 57 ]: The uronic acid is typically combined with an alkaline ionic compound (hydroxide or bicarbonate anion). The strategy is the same as for the neutralization of d -gluconic acid (see Section 2.3 ).…”

Section: Synthesismentioning

confidence: 99%

Sugar-Based Ionic Liquids: Multifaceted Challenges and Intriguing Potential

2021

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Carbohydrates represent a promising option in transitioning from oil-based chemical resources to renewable ones, with the goal of developing chemistries for a sustainable future. Cellulose, hemicellulose, and largely available monosaccharides already provide useful chemical building blocks, so-called platform chemicals, such as levulinic acid and hydroxymethyl furfural, as well as solvents like cyrene or gamma-valerolactone. Therefore, there is great anticipation for novel applications involving materials and chemicals derived from sugars. In the field of ionic liquids (ILs), sugar-based ILs have been overlooked for a long time, mainly on account of their multistep demanding preparation. However, exploring new strategies for accessing sugar-based ILs, their study, and their exploitation, are attracting increasing interest. This is due to the growing concerns about the negative (eco)toxicity profile of most ILs in conjunction with their non-sustainable nature. In the present review, a literature survey concerning the development of sugar-based ILs since 2011 is presented. Their preparation strategies and thermal behavior analyses, sorted by sugar type, make up the first two sections with the intention to provide the reader with a useful guide. A final overview of the potential applications of sugar-based ILs and their future perspectives complement the present analysis.

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“…Furthermore, IL is also known as 'green solvent' due to negligible vapour pressure [2]. A growing trend has been seen in the development of IL in various applications such as organic synthesis, biocatalysis [3], electrochemistry [4], extraction [5] and in pharmaceutical [6]. IL can be classified into two classes; aprotic and protic ionic liquids.…”

Section: Introductionmentioning

confidence: 99%

Salicylate-Based Protic Ionic Liquids as a Potential Antioxidant

2019

MJAS

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Salicylate-based protic ionic liquids (PILs) were synthesised, characterised and assessed in this study for potential antioxidant in drug design. The synthesised PILs were known as 3-dimethylamino-1-propanol salicylate (3DMAPS) and 3-diethylamino-1propanol salicylate (3DEAPS). Proton nuclear magnetic resonance ( 1 HNMR), Fourier transformation infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) were used to characterise the synthesised PILs. Furthermore, the antioxidant activity of the synthesised PILs was determined using the 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical assay. Both 3DMAPS and 3DEAPS showed a good antioxidant activity compared to parent acid (salicylic acid) as these two compounds could scavenge 20% of DPPH free radical at a concentration of 66.76 ± 0.09 µM and 27.27 ± 0.10 µM, respectively. AbstrakCecair ionik protik (PILs) berasaskan salisilat disintesis, dicirikan dan dinilai untuk potensi antioksidan dalam reka bentuk dadah. Dua PILs iaitu 3-dimetilamino-1-propanol salisilat (3DMAPS) dan 3-diethilamino-1-propanol salisilat (3DEAPS) telah berjaya disintesis. Proton resonans magnetik nuklear ( 1 HNMR), spektroskopi transformasi inframerah (FTIR) dan analisis termogravimetrik (TGA) digunakan untuk pencirian PIL yang di sintesis. Tambahan pula, aktiviti antioksidan PIL ditentukan dengan menggunakan ujian radikal bebas 2,2-difenil-1-pikrilhidrazil (DPPH). Kedua-dua 3DMAPS dan 3DEAPS menunjukkan aktiviti antioksidan yang baik berbanding dengan asid induk (asid salisilat) kerana kedua-dua sebatian ini boleh membakar 20% radikal bebas DPPH masing-masing pada kepekatan 66.76 ± 0.09 μM dan 27.27 ± 0.10 μM.Kata kunci: cecair ionic protik, asid salisilik, perangkap radikal, radikal bebas, ujian DPPH

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New biobased tetrabutylphosphonium ionic liquids: synthesis, characterization and use as a solvent or co-solvent for mild and greener Pd-catalyzed hydrogenation processes

Abstract: Phosphonium-based ionic liquids with natural organic derived anions were easily prepared and showed good performance and recyclability in Pd-catalyzed hydrogenation processes at room temperature under atmospheric H2 pressure.

Cited by 22 publications

References 83 publications

New Insights into the Reaction Capabilities of Ionic Organic Bases in Cu‐Catalyzed Amination

New Insights into the Reaction Capabilities of Ionic Organic Bases in Cu‐Catalyzed Amination

Sugar-Based Ionic Liquids: Multifaceted Challenges and Intriguing Potential

Salicylate-Based Protic Ionic Liquids as a Potential Antioxidant

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