Synthesis and Catalytic Activity of Novel Heternuclear Dication Brønsted Acidic Ionic Liquids

Wen-hui, Cui; Zhang, Youming; Jia, Ruyan; Yu, Wei; Wei, Tai‐Bao

doi:10.6023/cjoc201409040

Cited by 3 publications

(2 citation statements)

References 16 publications

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“…[7][8][9][10] The functionalized ionic liquids have been used to catalyze aldol condensation reactions. For example, acid ionic liquids were used for butanal self-condensation and for aldol condensation of aromatic aldehydes with ketones, [10][11][12][13] basic ionic liquids were employed for aldol condensation of aldehydes with ketones, [14][15][16] and several acid-base bifunctional ionic liquids were synthesized for catalyzing pentanal self-condensation. 17 We separately evaluated the catalytic performance of an acid ionic liquid [HSO 3 -b-N(Et) 3 ]p-TSA in butanal self-condensation and the catalytic performance of an acid-base bifunctional ionic liquid [PEmim]Cl-0.5Zn(CH 3 COO) 2 in petanal self-condensation.…”

Section: Introductionmentioning

confidence: 99%

Silica‐immobilized acid ionic liquid: An efficient catalyst for pentanal self‐condensation

Wang

Yang

et al. 2020

J of Chemical Tech & Biotech

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BACKGROUND: Pentanal self-condensation to 2-propyl-2-heptenal is an important process of carbon chain extension for the industrial manufacture of 2-propylheptanol, which is an important plasticizer alcohol. The existing industrial processes all use liquid alkali catalysts, so they suffer from problems such as difficult recovery and high costs for treatment of alkalicontaining wastewater. In the present work, three immobilized acid ionic liquids were prepared separately with SiO 2 , MCM-41, and SBA-15 as support for pentanal self-condensation. RESULTS: The structures of the as-prepared immobilized acid ionic liquids were confirmed with the help of FT-IR, TG, SEM-EDS, and N 2 adsorption-desorption techniques. The characterization and activity evaluation results indicate that there are positive correlations among the number of hydroxyl groups on the support surface, ionic liquid loading, and the catalytic activity. Among the three immobilized acid ionic liquids, silica-immobilized acid ionic liquids (SiO 2-IL-SO 3 H) showed an extraordinary catalytic performance for pentanal self-condensation because of its higher ionic liquid loading. The yield and selectivity of 2-propyl-2-heptenal could respectively reach 73.9% and 91.5% under suitable reaction conditions and a high turnover number (TON) of 179.1 was obtained. CONCLUSION: Pyridine adsorption infrared spectroscopy and density functional theory (DFT) simulation were employed to investigate the structure and acidity of SiO 2-IL-SO 3 H. The optimized structures were obtained, and the calculation results indicate that the acidity of SiO 2-IL-SO 3 H is higher than the corresponding homogeneous ionic liquid system, which may be the main reason for its excellent catalytic performance and catalytic efficiency.

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Section: Introductionmentioning

confidence: 99%

Silica‐immobilized acid ionic liquid: An efficient catalyst for pentanal self‐condensation

Wang

Yang

et al. 2020

J of Chemical Tech & Biotech

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“…Functionalized ionic liquids possess the advantages of both liquid and solid catalysts such as good mobility, high active site density, uniformly distributed active site strength, easy separation, good activity and reusability, and mild reaction conditions. Acid functionalized ionic liquids or base functionalized ionic liquids have been reported to catalyze aldol condensation separately in the literature . Our group prepared a series of sulfonic acid functionalized ionic liquids with a triethylammonium cation for butanal self‐condensation and found that [HSO 3 ‐b‐N(Et) 3 ] p ‐TSA exhibited excellent catalytic activity and reusability; the yield and selectivity of 2‐ethyl‐2‐hexenal were 78.4% and 87.8%, respectively at the suitable reaction conditions.…”

Section: Introductionmentioning

confidence: 99%

Synergistic catalysis of acid–base bifunctional ionic liquids for pentanal self‐condensation reaction

Kong

Yang

et al. 2019

J of Chemical Tech & Biotech

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BACKGROUND: Pentanal self-condensation to 2-propyl-2-heptenal is an important process of carbon chain extension for industrial manufacture of 2-propylheptanol. This reaction in industry employs an aqueous caustic alkali catalyst, causing several problems of equipment corrosion, treatment of alkali wastewater, etc. Herein, several acid-base bifunctional ionic liquids were synthesized for catalyzing pentanal self-condensation. RESULTS: [PEmim]Cl-0.5Zn(CH 3 COO) 2 exhibited a better catalytic performance, and the yield and selectively of 2-propyl-2-heptenal could reach 82.0% and 86.6%, respectively. The recovered [PEmim]Cl-0.5Zn(CH 3 COO) 2 could be reused three times after being regenerated without a significant loss in its catalytic performance. The structures and charge properties of [PEmim]Cl-Zn(CH 3 COO) 2 and a complex of [PEmim]Cl-Zn(CH 3 COO) 2 and pentanal were simulated by density functional theory calculation. The results show that the action of acid and base sites of [PEmim]Cl-Zn(CH 3 COO) 2 can effectively activate pentanal by enhancing the electrophilicity or nucleophilicity of different pentanal molecules. CONCLUSION: The acid-base synergetic effect of [PEmim]Cl-Zn(CH 3 COO) 2 could account for its high catalytic performance. An acid-base synergetic catalysis mechanism of [PEmim]Cl-Zn(CH 3 COO) 2 in pentanal self-condensation was established. Characterization of ABBILsThe 1 H-NMR spectra were recorded in deuterium oxide (D 2 O) or deuterated chloroform (CDCl 3 ) on a Bruker Avance 400 spectrometer (Bruker, Karlsruhe, Germany) operating at 400 MHz with tetramethyl silane (TMS) as an internal standard.Pyridine was used as an infrared (IR) spectroscopic probe molecule to determine the acidity of ionic liquids. 24 The Fourier-transform infrared (FT-IR) spectra of pyridine and ionic J Chem Technol Biotechnol 2020; 95: 710-718 DFT calculation for insight into synergetic effect of [PEmim]Cl-Zn(CH 3 COO) 2Computational methods are useful ways to gain insight about the behaviors of the catalytic systems. 30 To provide evidence for the high catalytic activity of [PEmim]Cl-Zn(CH 3 COO) 2 , DFT calculation was performed for simulating the structure of [PEmim]Cl-Zn(CH 3 COO) 2 and the interaction between pentanal and [PEmim]Cl-Zn(CH 3 COO) 2 .Geometry optimization of Zn(CH 3 COO) 2 , [PEmim]Cl and [PEmim]Cl-Zn(CH 3 COO) 2 was carried out first. The optimized structures of the earlier substances were confirmed as energy minima by frequency calculation. The ESP surfaces for those structures were constructed and shown in Fig. 2, where the regions of more negative and positive charges were represented by red and blue colors, respectively.The ESP surfaces of [PEmim]Cl and Zn(CH 3 COO) 2 are shown in Fig. 2(a, b). There are two four-coordination structures in J Chem Technol Biotechnol 2020; 95: 710-718

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Acidic Ionic Liquids

2016

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Ionic liquid with acidic properties is an important branch in the wide ionic liquid field and the aim of this article is to cover all aspects of these acidic ionic liquids, especially focusing on the developments in the last four years. The structural diversity and synthesis of acidic ionic liquids are discussed in the introduction sections of this review. In addition, an unambiguous classification system for various types of acidic ionic liquids is presented in the introduction. The physical properties including acidity, thermo-physical properties, ionic conductivity, spectroscopy, and computational studies on acidic ionic liquids are covered in the next sections. The final section provides a comprehensive review on applications of acidic ionic liquids in a wide array of fields including catalysis, CO2 fixation, ionogel, electrolyte, fuel-cell, membrane, biomass processing, biodiesel synthesis, desulfurization of gasoline/diesel, metal processing, and metal electrodeposition.

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Synthesis and Catalytic Activity of Novel Heternuclear Dication Brønsted Acidic Ionic Liquids

Cited by 3 publications

References 16 publications

Silica‐immobilized acid ionic liquid: An efficient catalyst for pentanal self‐condensation

Silica‐immobilized acid ionic liquid: An efficient catalyst for pentanal self‐condensation

Synergistic catalysis of acid–base bifunctional ionic liquids for pentanal self‐condensation reaction

Acidic Ionic Liquids

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