Ionic Liquid Catalyzed Reactions E-Book

Zhimin Liu

• Herausgeber: Wiley-VCH
• Kategorie: Fachliteratur
• Sprache: Englisch

Seitenzahl: 660

Veröffentlichungsjahr: 2025

Beschreibung

Understand the applications of ionic liquid catalysis with this cutting-edge overview

Ionic liquids have distinctive properties that have made them the subject of vigorous research in recent decades. They have primarily been seen as potential green alternatives to volatile organic solvents, and therefore as a vital tool in the development of sustainable industry. In fact, however, ionic liquids can also serve as catalysts, catalyst immobilizers, and initiators, with the result that they have been applied in over 100 known types of chemical reactions.

Ionic Liquid Catalyzed Reactions: Green Concepts and Sustainable Applications offers a detailed overview of these reactions and the catalytic mechanism of ionic liquids. It surveys cutting-edge research into ionic liquid catalysis and the concepts, perspectives, and skills needed for scientists to incorporate it into a range of experimental fields. It is a must-own for anyone looking to understand the range and variety of uses for ionic liquid catalysis.

Ionic Liquid Catalyzed Reactions readers will also find:

• Case studies throughout showing ionic liquid catalysis applications
• Information for scientists working in organic chemistry, electrochemistry, biotechnology, and many more
• Detailed coverage of reactions including CO₂ conversion, biomass transformation, organic synthesis, and many others

Ionic Liquid Catalyzed Reactions is ideal for catalytic chemists, organic chemists, environmental chemists, electrochemists, and anyone else working with chemical catalysis in need of new experimental methods.

Leseprobe

Table of Contents

Cover

Table of Contents

Title Page

Copyright

Preface

Acknowledgments

Chapter 1: Background and Overview

1.1 Introduction

1.2 Ionic Liquids

1.3 Structure of This Book

References

Chapter 2: Ionic Liquid–Catalyzed Transformation of Carbon Dioxide to Chemicals Under Metal-free Conditions

2.1 Synthesis of Organic Carbonates

2.2 Synthesis of N-containing Heterocycles

2.3 Reductive Transformation of CO2

2.4 Synthesis of Other Compounds

2.5 Remarks and Perspectives

References

Chapter 3: Ionic Liquid–Mediated Reductive Transformation of Carbon Dioxide with Hydrogen

3.1 Direct Hydrogenation of CO2

3.2 N-formylation or N-methylation Reaction of Amines with CO2/H2

3.3 Hydroformylation of Olefin with CO2/H2

3.4 Hydromethylamination of Olefin with CO2/H2 and Amines

3.5 Carbonylation of Alcohol/Ethers with CO2/H2

3.6 Remarks and Perspectives

References

Chapter 4: Electroreduction of Carbon Dioxide in Ionic Liquid–Based Electrolytes

4.1 Fundamentals of CO2 Electroreduction

4.2 IL-based Electrolytes for CO2 Electroreduction

4.3 Electroreduction of CO2 to Various Chemicals in IL-based Electrolytes

4.4 Electrotransformation of CO2 into Value-added Chemicals

4.5 Remarks and Perspectives

References

Chapter 5: Ionic Liquid–Catalyzed Chemical Transformation of Lignocellulose

5.1 Ionic Liquid–Catalyzed Transformation of Cellulose and Its Derivatives

5. 2 Ionic Liquid–catalyzed Transformation of Hemicellulose and Xylose to Furfural

5.3 Ionic Liquid–Catalyzed Transformation of Lignin and Its Platforms

5.4 Remarks and Perspectives

References

Chapter 6: Ionic Liquid–Catalyzed Oxidation Reactions

6.1 Oxidation of Alcohols/Aldehydes

6.2 Oxidation of Organic Sulfides and Oxidative Desulfurization

6.3 Oxidative Cyclization of Olefins and Allylic Alcohols

6.4 Oxidation of Amines

6.5 Baeyer–Villiger Oxidation

6.6 Oxidation of Other Compounds

6.7 Remarks and Perspectives

References

Chapter 7: Ionic Liquid–Catalyzed Water−Involved Reactions

7.1 Dehydrative Esterification

7.2 Dehydrative Etherification of Alcohols

7.3 Dehydration Alkenylation

7.4 Dehydrative Amidation

7.5 Ionic Liquid–catalyzed Hydration Reaction

7.6 Hydrolysis of Esters/ Ethers

7.7 Remarks and Perspectives

References

Chapter 8: Ionic Liquid–Catalyzed Other Organic Reactions

8.1 Alkylation Reaction

8.2 Michael Addition Reaction

8.3 Diels–Alder Reactions

8.4 Markovnikov Addition

8.5 Knoevenagel Condensation

8.6 Aldol Condensation Reaction

8.7 Ring-Closing and Bond Metathesis

8.8 Remarks and Perspectives

References

Chapter 9: Ionic Liquid–Catalyzed Recycling of Spent Polymers

9.1 Degradation of Polyesters

9.2 Degradation of Polyamides

9.3 Upcycling of Polyolefins

9.4 Co-upcycling of Polyvinyl Chloride and Polyester

9.5 Remarks and Perspectives

References

Index

End User License Agreement

List of Illustrations

Chapter 1

Scheme 1.1 Chemical structures of typical Brønsted acidic ILs.

Scheme 1.2 Chemical structures of typical Brønsted–Lewis acidic ILs.

Scheme 1.3 Chemical structures of cations in typical heteropolyacid-based ILs.

Scheme 1.4 Chemical structures of AA anions.

Scheme 1.5 Proposed absorption mechanism of CO2 by AAILs. (a) , (b) [P66614][Met], (c) [P...

Scheme 1.6 Possible reaction between [Apbim][BF4] and CO2. Adapted from [53].

Scheme 1.7 Chemical structures of [P66614][p-AA] and [P66614][p-ANA]. Adapted from [58].

Scheme 1.8 Chemical structures of azolate ILs and complexes of azolate. Adapted fr...

Scheme 1.9 Chemical structures of alcoholate and phenolate ILs (top) and CO2 absorption b...

Scheme 1.10 Chemical structures of some typical CO2-reactive ILs with multiple sites. (a) ...

Scheme 1.11 Chiral ILs with imidazolium-bearing chiral functional moieties.

Chapter 2

Figure 2.1 Electronic formula of CO2.

Scheme 2.1 Catalytic and dehydrating mechanism for the synthesis of DMC from CO2 a...

Scheme 2.2 Energy profile of DMC synthesis from CO2 and CH3OH [kcal mol−1]. Values...

Scheme 2.3 Chemical structures of bifunctional ILs. From Ref. [6], with permission from S...

Scheme 2.4 The reaction of atmospheric CO2 with propargylic and primary alcohols over AgC...

Scheme 2.5 Chemical structures of Hünig’s base–appended basic ILs. F...

Scheme 2.6 Three-component reaction of CO2, olefin and alcohol catalyzed by [BMIm]Cl/Ru3(...

Scheme 2.7 Chemical structures of functionalized imidazolium ILs with halide anions. Adap...

Scheme 2.8 Proposed mechanism for the thiourea-functionalized imidazolium IL-catalyzed cy...

Scheme 2.9 Cycloaddition of CO2 to epoxides catalyzed by . From Ref. [18], with permissio...

Scheme 2.10 I catalyzed cycloaddition of epoxides with CO2 under optimal reaction conditio...

Scheme 2.11 Synthesis of cyclic carbonates from epibromohydrin, CO2, and acids. From Ref. ...

Scheme 2.12 Possible reaction mechanism of -catalyzed reaction of epibromohydrin with CO2 ...

Scheme 2.13 [BMIm]Br-catalyzed synthesis of styrene carbonate from styrene, TBHP, and CO2....

Scheme 2.14 One-pot synthesis of cyclic carbonates from olefins and CO2 catalyzed by [BMIm...

Scheme 2.15 Some typical AQ-based ILs. Adapted from [26–28].

Scheme 2.16 Possible catalytic cycle of catalyzing cycloaddition of epoxides with CO2. Fr...

Scheme 2.17 Synthesis of cyclic carbonates from CO2 and epoxides catalyzed by . From Ref. ...

Scheme 2.18 Synthesis of cyclic carbonates from CO2 and epoxides over scorpionate IL. From...

Scheme 2.19 Chemical structures of typical other N-containing cation ILs. Adapted from [29...

Scheme 2.20 Chemical structures of quaternary phosphonium IL salts bearing hydrogen bond d...

Scheme 2.21 The coupling reaction of atmospheric CO2 and epoxides catalyzed by bifunctiona...

Scheme 2.22 Carboxylation of epoxidized fatty acid esters with CO2 over bifunctional phosp...

Scheme 2.23 Plausible mechanism for cyclic carbonate formation catalyzed by [Bu4P][BenIm]....

Scheme 2.24 [Bu4P][2-OP]-catalyzed cycloaddition of CO2 to epoxides. From Ref. [51], with ...

Scheme 2.25 Chemical structures of dual amino-functionalized imidazolium ILs From Ref. [15...

Scheme 2.26 Chemical structures of the halide-free ILs. (a) Histidine-derived carboxylate ...

Scheme 2.27 Proposed mechanism for [HDBU][BO2]-catalyzed cycloaddition of CO2 and epoxides...

Scheme 2.28 Cyclization of propargylic alcohols with CO2 catalyzed by (a) [HDBU][MIm] and ...

Scheme 2.29 (a) Chemical structures of [Bu4P]+-based ILs with multiple interaction sites i...

Scheme 2.30 Synthesis of -alkylidene cyclic carbonates from CO2 and propargylic alcohols c...

Scheme 2.31 Possible reaction pathway. [60], with permission from American Chemical Societ...

Scheme 2.32 Chemical structures of basic IL catalysts.

Scheme 2.33 Cyclization of 2-aminobenzonitriles with CO2 over [HDBU][TFE]. From Ref. [67],...

Scheme 2.34 Proposed mechanism of the [HDBU][TFE]-catalyzed reaction. From Ref. [68], with...

Scheme 2.35 Chemical structures of Lewis basic ILs. From Ref. [70], with permission from R...

Scheme 2.36 IL-catalyzed cycloaddition of CO2 to aziridines. From Ref. [70], with permissi...

Scheme 2.37 Chemical structures of protic onium salts with halide anions. From Ref. [71], ...

Scheme 2.38 Chemical structure of Br[DBNPEG150DBN]Br.

Scheme 2.39 One-pot reaction of CO2 and olefin with TsNClNa catalyzed by [Bu4N][Br3]/[Bu4N...

Scheme 2.40 Cyclization of propargylic amines with CO2 catalyzed by [HDBU][2-MIm]. From Re...

Scheme 2.41 IL-catalyzed cyclization propargylic amines with CO2. From Ref. [76], with per...

Scheme 2.42 The coupling reactions of ,-disubstituted propargylic alcohols with CO2 and al...

Scheme 2.43 The complex reaction for the one-pot conversion of CO2, epoxies, and amines to...

Scheme 2.44 Synthesis of 2-oxazolidinones through three-component reactions, and possible ...

Scheme 2.45 [Bu4P][2-MIm]-catalyzed carbonylation of o-phenylenediamines/2-aminothiophenol...

Scheme 2.46 Formation of formyamides from amines with CO2 and PhSiH3. From Ref. [86], with...

Figure 2.2 (a) 1H NMR spectra of the [BMIm]Cl, phenylsilane, and their mixture ([D6]DMSO,...

Scheme 2.47 Synthesis of N,N-disubstituted formamides from amines, aldehydes, CO2, and hyd...

Scheme 2.48 Proposed reaction mechanism for [C12DBU]Br-catalyzed formylation of secondary ...

Scheme 2.49 Hierarchical reductions of CO2 with amines and PhSiH3.

Scheme 2.50 Proposed mechanism for N-formylation of amines with CO2 and hydrosilanes. From...

Scheme 2.51 Reductive functionalization of CO2 with amine to afford formamide, aminal, and...

Scheme 2.52 Proposed reaction pathway on reductive functionalization of CO2 with amine to ...

Scheme 2.53 Four-electron reduction of CO2 with amines and PMHS to form aminals. From Ref....

Scheme 2.54 Synthesis of various benzothiazoles and benzimidazoles. From Ref. [95], with p...

Scheme 2.55 Synthesis of carbamates from amines, CO2, and silicate esters over [HDBU][OAc]...

Chapter 3

Scheme 3.1 Reaction pathways for direct CO2 hydrogenation. From Ref. [1], with permission...

Scheme 3.2 Low-temperature RWGS over Ru3(CO)12 in [HMIm][BF4]. From Ref. [4], with permis...

Scheme 3.3 Possible reaction mechanism for Ru3 (CO)12-catalyzed RWGS in [HMIm][BF4].From ...

Scheme 3.4 The chemical structure of [MaMMIm][OTf], [DAMI][OTf] and [DAMI][CF3CF2CF2CF2SO...

Scheme 3.5 Ru3(CO)12/[BMMIm][OAc]/DMSO/H2O catalyzed CO2 hydrogenation to formic acid. Ad...

Scheme 3.6 Possible reaction pathway for CO2 hydrogenation to free formic acid over . Fro...

Scheme 3.7 (a) The chemical structure of task-specific fluorinated imidazolium IL. (b) Re...

Scheme 3.8 (a) CO2 hydrogenationof hydrocarbons over in [BMIm][PF6]. Reaction conditio...

Scheme 3.9 Chemoselective hydrogenation of CO2 over RuFe NPs in different IL. From Ref. [...

Scheme 3.10 (a) N-formylation of primary and secondary amines with CO2/H2 catalyzed by [P...

Scheme 3.11 (a) The chemical structure of, (b) N-formylation of various amines with CO2/...

Scheme 3.12 (a) Chemical structure of tetrabutylphosphonium-based CO2-reactive ILs, (b) t...

Scheme 3.13 [BMIm][OAc] promoted N-formylation of amines with CO2/H2 over Ru/C. From Ref. ...

Scheme 3.14 Selective reduction of CO2 with cyclic amines and H2 over Pd/C in [BMIm][BF4]....

Scheme 3.15 Plausible pathways for formation of formylpiperidine, 1,2-bis(piperidine)ethan...

Scheme 3.16 -catalyzed mediated hydroformylation of alken...

Scheme 3.17 [BMIm]Cl-promoted hydroformylation of alkenes with CO2 over [Ru(CO)3]Cl2]2/Co2...

Scheme 3.18 Hydromethylamination of olefin with amines and CO2/H2 catalyzed by Ru3(CO)12/B...

Scheme 3.19 Hydromethylamination of olefin with amines and CO2/H2 over Ru3(CO)12/[BMMIm]Cl...

Scheme 3.20 (a) Magnification of the selected region of the spectrum of the reaction solu...

Chapter 4

Scheme 4.1 General homogeneous reaction pathways for electrocatalysis with electron sourc...

Figure 4.1 The CO2 electroreduction pathways of generating (a) HCOOH/HCOO− and (b)...

Figure 4.2 Typical cation and anion structures of ILs for CO2 electroreduction.

Figure 4.3 Chemical structures of the imidazolium-based ILs. From Ref. [13], with permiss...

Figure 4.4 (a) Effect of different cations (1a, 2a, 3a) on the electrochemical CO2RR. Cyc...

Scheme 4.2 Proposed reduction pathways on the polarized Ag electrode in IL-based electrol...

Figure 4.5 (a) Molecular structures of [Et4N], [Et4N][BF4], [Et4N][PF6], and [BMIm][BF4];...

Figure 4.6 Mechanism of CO2RR to oxalic acid on Pb electrode in the [Et4N] (0.9M)─...

Figure 4.7 CVs of 1mM catalyst and 0.5M of different supporting electrolytes in MeCN solu...

Figure 4.8 (a) The current density of CO2RR (measured by Chrono-Amperometry) at 0.764V ve...

Figure 4.9 (a) Dependence of onset potential of HCOOH formation on the H2O content...

Figure 4.10 FE of CO and H2 and current density using electrolytes with different (a) [BM...

Figure 4.11 (a) Schematic figure of the synthesis of dendritic Cu nanomaterials. (b) HCOOH...

Figure 4.12 Molecular structures of fac-ReCl(2,2′-bpy)(CO)3, Ni(cyclam)2+, and Ada...

Scheme 4.3 Reaction pathways of the CO2-to-CO process on [FeTPPCl] molecular catalyst. Fr...

Figure 4.13 (a) Potential-dependent in-situ Raman spectra on Ag electrode in electrolytes...

Figure 4.14 (a) Schematic figure of the ternary IL-based electrolyte for CO2RR on Cu elect...

Figure 4.15 (a) Gibbs free-energy diagrams for CO2 to CH3OH over different simulated mode...

Figure 4.16 Proposed CO2 reduction mechanism schematic diagram at NGM/CP electrode. From R...

Figure 4.17 Proposed reaction pathways of CO2RR to CH3COOH over in electrolyte. From Ref...

Figure 4.18 (a) Potentially dependent product distribution of IL@Cu catalyst and (b) the c...

Figure 4.19 Proposed reaction mechanism for electrochemical reduction and polymerization o...

Scheme 4.4 Electrocarboxylation of ethyl cinnamate in [BMIm][BF4] From Ref. [98], with pe...

Scheme 4.5 The electrochemical carboxylation of 1,3-butadiene with CO2.From Ref. [99], wi...

Figure 4.20 (a) Synthesis of the -hydroxy acids from epoxides and CO2 and (b) the proposed...

Scheme 4.6 The electrochemical synthesis of cyclic carbonates from CO2 and epoxides. From...

Scheme 4.7 Electrosynthesis of organic carbonates from CO2 and alcohols [104].

Scheme 4.8 Electrosynthesis of organic carbamatesfrom CO2 and amines. From Ref. [106], wi...

Figure 4.21 (a) Electrochemical reaction of nitrobenzene with CO2; (b) possible pathway. F...

Chapter 5

Figure 5.1 Chemical structures of lignocellulose and its derivatives. From Ref. [1], with...

Scheme 5.1 Chemical structures of 2-phenyl-2-imidazoline-based SO3H-functionalized acidic...

Scheme 5.2 Chemical structure of different ILs for cellulose hydrolysis. From Ref. [10], ...

Scheme 5.3 Pathway for direct transformation of cellulose into HMF. From Ref. [11], with ...

Scheme 5.4 Chemical structures of [EMIm][OAc] and various acidic ILs. From Ref. [1...

Scheme 5.5 (a) Putative mechanism of CuCl2 and [C4SO3HMIm][CH3SO3] for converting of cell...

Scheme 5.6 Chemical structures of dual-core sulfonic acid ILs. From Ref. [13], with permi...

Scheme 5.7 Proposed metal halide interaction with glucose in [EMIm]Cl. CuCl2 and CrCl2 ca...

Scheme 5.8 Scheme for the transformation of cellulose to LA. From Ref. [2], with permissi...

Scheme 5.9 Chemical structures of Brønsted–Lewis acidic ILs. From Ref. [15]...

Scheme 5.10 The mechanism of catalytic conversion of cellulose to LA over . From Ref. [15]...

Figure 5.2 (a) Pyridine-FTIR spectra of the functionalized ILs (FILs) and (b) reusabilit...

Scheme 5.11 Chemical structures of Brønsted acid−functionalized 2-phenyl-2-i...

Scheme 5.12 Chemical structures of [H4-nPMo11VO40]n--based ILs with -functionalized cation...

Scheme 5.13 Possible pathway for cellulose oxidation to formic acid. From Ref. [18], with ...

Scheme 5.14 Schematic illustration of the transesterification of cellulose using vinyl est...

Scheme 5.15 Evolution mechanism of 5-methylfufural. From Ref. [21], with permission from S...

Figure 5.3 Effect of [Hpy][HSO4] on dehydration of hemicellulose to furfural. Conditions:...

Figure 5.4 The conversion of different herbaceous lignin types for MPC production. Reacti...

Scheme 5.16 The THF-soluble aromatics derived from lignin transformation over Brøns...

Scheme 5.17 Plausible reaction mechanism based on gas chromatography-mass spectrometry (G...

Scheme 5.18 Illustration of vanillin extraction from lignin over [BMIm][FeCl4] at room tem...

Scheme 5.19 Possible reaction mechanisms for oxidation depolymerization of lignin over [BM...

Figure 5.5 (a) UV–vis absorption spectra of 2-phenoxyacetophenone in N2 (b) and O2...

Scheme 5.20 Proposed reaction mechanism for 2-phenoxyacetophenone oxidation over [BnMIm][N...

Figure 5.6 Effects of reaction parameters on the conversion and yields in IL [OMIm][OAc] ...

Scheme 5.21 Possible reaction pathway for the oxidation of 2-phenoxyacetophenone catalyzed...

Scheme 5.22 The basic phenylpropane units (C9 units) of lignin marked in colors. Fr...

Scheme 5.23 Catalytic oxidation of lignin model compounds into DEM. From Ref. [30],...

Chapter 6

Scheme 6.1 Self-esterification of aryl- or alkyl-alcohols and cross-esterification of ben...

Scheme 6.2 NHC formation in [EMIm][OAc]. From Ref. [2], with permission from Royal Societ...

Scheme 6.3 Possible reaction pathway for oxidative esterification of alcohols over [EMIm]...

Scheme 6.4 [EMIm][OAc] catalyzes benzaldehyde coupling, oxidation of benzoin by air and t...

Scheme 6.5 Oxidation of alcohols by H2O2 over . Reaction conditions: 2 mmol benzyl alcoho...

Scheme 6.6 Preparation of and . From Ref. [4], with permission from ELSEVIER.

Scheme 6.7 Proposed mechanism for alcohol oxidation catalyzed by HPA-ILs. From Ref. [4], ...

Scheme 6.8 Selective oxidation of alcohols over [P and , respectively. Reaction condition...

Scheme 6.9 Chemical structures of (a) IL-PW and PIPA-13 and (b) IL with the oxidizing fun...

Scheme 6.10 Regeneration and reuse of [IBX-MIM][PF6]. From Ref....

Scheme 6.11 [BMIm][BF4] catalyzed alcohol oxidation with NaClO. Reaction conditions: 2 mmo...

Scheme 6.12 (a) Oxidation of thioethers with H2O2 over [BMIm][BF4] to sulfoxides. Reaction...

Scheme 6.13 Sulfoxidation of the different sulfides using H2O2 catalyzed by in [Bpy]BF4. ...

Scheme 6.14 Possible reaction mechanism for sulfoxidation using H2O2 over . From Ref. [11]...

Scheme 6.15 Enantioselective oxidation of methylphenyl sulfide over [P66614]2[WO2...

Scheme 6.16 (a) Oxidation of thioethers over [bMImB][Br3]2 to sulfoxides. Reaction conditi...

Scheme 6.17 Proposed mechanism for oxidation of sulfide to sulfoxide over . From Ref. [14]...

Figure 6.1 Pseudo-first-order kinetics for oxidation of dibenzothiophene (DBT), 4,6-dimet...

Figure 6.2 Possible mechanism of catalytic oxidation desulfurization using [(CH3)N(n...

Figure 6.3 (a) Time-dependent sulfur removal efficiency of DBT oxidation over different I...

Scheme 6.18 Possible reaction mechanisms with two different pathway. From Ref....

Scheme 6.19 Chemical structures of amide-based ILs. From Ref....

Figure 6.4 (a) Absorption spectra of 4-dinitroaniline in various ILs; (b) content of pero...

Figure 6.5 Influence of the amount of [Et3NH][FeCl4] on sulfur removal (left) and sulfur ...

Scheme 6.20 Chemical structures of heteropolyacid anion-based ILs. From Ref. [26], with pe...

Scheme 6.21 Synthetic routes of -hydroxy acids coordinated mononuclear peroxoniobate-based...

Scheme 6.22 Proposed reaction mechanism for cyclooctene oxidation over [NbO(OH)2R]-based I...

Scheme 6.23 Proposed mechanism for epoxidation of allylic alcohols with H2O2 catalyzed by ...

Scheme 6.24 Proposed mechanism for epoxidation of cyclooctene with H2O2 catalyzed by perox...

Scheme 6.25 The structure of the PICP–n catalyst and the synthesis of epoxy compoun...

Scheme 6.26 Structure of and its performance for catalyzing amine oxidation. From Ref. [3...

Scheme 6.27 Catalytic oxidation of benzylamine compounds using [Bu4N][OH]. From Ref. [34],...

Scheme 6.28 Plausible reaction mechanism for benzylamine oxidation over [Bu4N][OH]. From R...

Scheme 6.29 The proposed mechanism for BV oxidation with Me3SiOOSiMe3 over [BMIm][OTf]. Fr...

Scheme 6.30 BV mechanism of cyclic ketone oxidation over [HMIm][Al2Cl7] using double silic...

Figure 6.6 Chemical structures of multi-SO3H-functionalized heteropolyanion-based ionic c...

Scheme 6.31 Chemical structures of amino acid–based protic ILs. From Ref. [40], wit...

Chapter 7

Scheme 7.1 Chemical structures of typical BAILs.

Scheme 7.2 Dehydration esterification of propanoic acid and neo-pentanol catalyzed by [HS...

Scheme 7.3 Esterification of benzoic acid and its derivatives with n-butanol. Reaction co...

Figure 7.1 Illustration of auto-isolation of water generated during esterification cataly...

Scheme 7.4 The esterification of glycerol with acetic acid. From Ref. [11], with permissi...

Scheme 7.5 Esterification mechanism of acetic acid and alcohol catalyzed by [C2H6ONH2][HS...

Scheme 7.6 Chemical structures of phosphotungstic acid-based IL. From Ref. [14], with per...

Scheme 7.7 Reaction of EG and benzoic acid catalyzed by bisimidazolium tungstate ILs. Fro...

Scheme 7.8 Proposed reaction mechanism for the esterification reaction of EG and benzoic ...

Scheme 7.9 Dehydrative etherification of diols and monohydric alcohols to ether over [. R...

Scheme 7.10 Possible mechanism the dehydrative cyclization of 1,5-pentanediol catalyzed by...

Scheme 7.11 (a) Dehydrative cyclization of various vicinal diols over . Reaction condition...

Scheme 7.12 Proposed mechanism of cyclohexanol dehydration to cyclohexene catalyzed by [BM...

Scheme 7.13 Chemical structures of [HBMIm][TFA], [HTBD][TFA], and [HBIm][TFA].

Scheme 7.14 Possible catalytic pathways for the dehydrative formylation of amines with for...

Scheme 7.15 Synthesis of various amides from aromatic amines with carboxylic acids over [H...

Scheme 7.16 Proposed mechanism of the activation of carboxylic carbonyl by protic IL. From...

Scheme 7.17 Chemical structures of heteropolyanion-based ILs. From Ref. [28], with permiss...

Scheme 7.18 Direct amidation of carboxylic acids and amines over BAIL. From Ref. [29,30], ...

Scheme 7.19 A plausible mechanism for direct amination of carboxylic acids with amines ove...

Scheme 7.20 Mechanism for the acid (BAILs)-catalyzed (a) and SO3H-containing BAIL-catalyze...

Scheme 7.21 Chemical structures of azole anion–based ILs.

Scheme 7.22 Possible reaction mechanism for the [Bu4P][Im]/CO2-cocatalyzed hydration of pr...

Scheme 7.23 Mechanism of hydration and cyclization of 2-methyl-6-phenyl-3,5-hexadiyn-2-ol ...

Scheme 7.24 Scope in the hydration. Reaction conditions: substrate (1mmol), H2O (1mmol), [...

Scheme 7.26 Cation–anion synergistic mechanism for DMIC-catalyzed hydration of EO. ...

Scheme 7.27 Chemical structures of ILs with multiple HBs. From Ref. [38], with permission ...

Figure 7.2 Computational studies of the reaction mechanism. Reprinted with permission fro...

Scheme 7.28 Schematic diagram of the possible mechanism of [BMIm][OAc]-catalyzed the hydro...

Figure 7.3 Optimized geometries of reactant complex (Rcs) and its electrostatic potential...

Scheme 7.29 Synthesis of vicinal diols from various terminal cyclic carbonates catalyzed b...

Scheme 7.30 Hydrolysis cycle of propylene carbonate catalyzed by DMImC. From Ref. [41], wi...

Chapter 8

Scheme 8.1 The chemical structures of (a) [AlCuCl5]− and (b) [Ga3Cl10]−.

Scheme 8.2 Reaction mechanism of FC alkylation over Lewis acid and Brønsted acids....

Scheme 8.4 Mechanism details for the Michael Addition of acetylacetone to methyl vinyl ke...

Scheme 8.5 Chiral ILs with imidazolium-bearing chiral functional moieties. [14–30]...

Scheme 8.6 Michael additions of nitroolefins and various ketones/aldehydes catalyzed by d...

Scheme 8.7 Chemical structures of L-prolinate and L-prolinium ILs. [32–34]

Scheme 8.8 Asymmetric Michael addition reaction catalyzed by (a) [EtMIm][Pro], (b) [N1,1,...

Scheme 8.9 Diels–Alder reaction catalyzed by acidic chloroaluminate ILs. From Ref....

Scheme 8.10 Chemical structures of borenium ILs. [39]

Scheme 8.11 Asymmetric aza Diels-Alder reaction catalyzed by CILs. Diels–Alder reac...

Scheme 8.12 Markovnikov addition of imidazoles to vinyl esters over [BMIm][OH]. [41]

Scheme 8.13 Proposed Mechanism for the Markovnikov addition over [BMIm][OH]. From Ref. [41...

Scheme 8.14 Mechanism details for the Markovnikov addition of imidazole to vinyl acetate C...

Figure 8.1 Potential energy surface profiles for the Markovnikov addition along reaction ...

Scheme 8.15 The proposed mechanism. From Ref. [44], with permission from ELSEVIER.44

Scheme 8.16 Synthesis of linear thioethers catalyzed by [HMIm]Br. Reaction conditions: st...

Scheme 8.18 Illustration of Knoevenagel condensation reaction.

Scheme 8.19 Proposed mechanism of [THA][OAc] catalyzed the Knoevenagel reaction of aromati...

Scheme 8.20 [BMIm][Im]-catalyzed Knoevenagel condensations between aromatic aldehyde and a...

Scheme 8.21 Proposed reaction mechanism for synthesis of acrylonitrile and cyanoacrylate o...

Scheme 8.22 Chemical structures of guanidine-based IL with lactate anion. From Ref. [56], ...

Scheme 8.23 Proposed mechanism for synthesis of polysubstituted benzene over guanidine-bas...

Scheme 8.24 Direct aldol reactions catalyzed by [TMG][Lac]. From Ref. [57], with permissio...

Scheme 8.25 Reaction Mechanism for Self-Aldol Condensation of Cyclopentanone over the EAOA...

Scheme 8.26 Asymmetric aldol reaction catalyzed by trans-

l

-hydroxyproline-d...

Scheme 8.27 [OTf]-catalyzed RCM of diethers. Yields determined by 1H NMR /isolated yields...

Figure 8.2 Possible interaction geometries for 1,5-dimethoxypentane with (a) and with (...

Scheme 8.28 Possible reaction pathway of 1,5-dimethoxypentane RCM over to tetrahydropyran...

Scheme 8.29 [OTf]-catalyzed RCM of alkyloxy alcohols. Reaction conditions: alkoxy alcohol ...

Scheme 8.30 (a) Interaction figuration of 1,4-butanediol monomethyl ether with optimized ...

Chapter 9

Scheme 9.1 General chemical structure of polyesters.

Scheme 9.2 Illustration of four routes for PET depolymerization.

Scheme 9.3 Various IL-catalyzed methanolysis of PEF. From Ref. [12], with permission from...

Figure 9.1 Influences of reaction time and temperature on PET glycolysis over [BMIm]Cl. R...

Scheme 9.4 Possible degradation pathway of PET over [BMIm][OAc]. From Ref. [16], with per...

Scheme 9.5 Proposed mechanism for the glycolysis of PET over [Ch]3[PO4]. From Ref. [18], ...

Scheme 9.6 Chemical structures of typical AA anions. From Ref. [15], with permission from...

Scheme 9.7 Chemical structures of PIL from DBN and phenol derivatives. From Ref. [20], wi...

Scheme 9.8 Possible reaction pathway of PET glycolysis catalyzed by phenolate PIL. From R...

Figure 9.2 Effect of reaction temperature on the degradation of PET over [BMIm]2[CoCl4]. ...

Scheme 9.9 Proposed Mechanism for Degradation of PET over [BMIm]2[CoCl4]. From Ref. [21],...

Scheme 9.10 Chemical structure of (dimim)2. From Ref. [26], with permission from John Wile...

Scheme 9.11 The synergetic interaction of Brønsted and Lewis acid sites of IL on PE...

Scheme 9.12 Transformation of PLA to chemicals through different approaches. From Ref. [35...

Scheme 9.13 Alcoholysis of PLA over [HDBU][OAc] with 5mol% loading. From Ref. [37], with p...

Scheme 9.14 Proposed mechanism for alcoholysis of PLA catalyzed by [HDBU][OAc].From Ref. [...

Scheme 9.15 Possible reaction pathway of PLA methanolysis over [BMIm][FeCl4]. From Ref. [3...

Figure 9.3 (a) Effect of reaction temperature on hydrolysis conversion of PLA in [BMIm][O...

Scheme 9.16 Aminolysis of PLA with anilines over [N4444][Lac]/H2O. From Ref. [35], with pe...

Figure 9.4 Mechanism investigation. (a) Optimized geometries of [N4444][Lac] interacting ...

Scheme 9.17 Chemical structures of the acidic functionalized ILs. From Ref. [42], with per...

Scheme 9.18 Proposed mechanism for methanolysis of PHB over [MIMPS][FeCl4]. From Ref. [43]...

Scheme 9.19 PHB depolymerization to crotonic acid over [EMIm][OAc]. From Ref. [44], with p...

Scheme 9.20 Aminolysis of PSS (a) and PTG (b) with various amines over [HDBU][Suc]. Reacti...

Figure 9.5 DFT calculations for mechanism investigation. (a) Optimized geometries of [HDB...

Scheme 9.21 The proposed reaction mechanism for DS reacting with aniline over [HDBU][Suc]....

Scheme 9.22 Possible reaction pathway for [HDBU][LAc]-catalyzed hydrolysis of PC. From Ref...

Scheme 9.23 Possible mechanism for methanolysis of PC over [HDBU][Suc]. From Ref. [55], wi...

Scheme 9.24 Ammonolysis of PC with various anilines catalyzed by [N4444][Lac]. From Ref. [...

Scheme 9.25 Proposed reaction mechanism for decomposition of DPC with aniline over [N4444]...

Figure 9.6 Decomposition of PGA. Reaction conditions: PGA (1mmol), IL (2mmol), or NH4Br (...

Figure 9.7 High-temperature NMR experiments and DFT calculations. (a) 35Cl NMR spectra of...

Scheme 9.26 Proposed reaction pathway for decomposition of polyesters using H2 over the [B...

Scheme 9.27 Decomposition of various polyesters over [BMMIm]Br-Pd/C under the H2 atmospher...

Scheme 9.29 Depolymerization of nylon-6 over [PP13][NTf2]. From Ref. [62], with permission...

Scheme 9.30 Proposed reaction mechanism for the tandem cracking alkylation process of a po...

Scheme 9.31 The proposed reaction route of the simultaneous upcycling of PVC and PET. From...

Guide

Cover

Table of Contents

Title Page

Copyright

Preface

Acknowledgments

Begin Reading

Index

End User License Agreement

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Ionic Liquid Catalyzed Reactions

Green Concepts and Sustainable Applications

Zhimin Liu

Institute of Chemistry, Chinese Academy of Sciences

Yanfei Zhao

Institute of Chemistry, Chinese Academy of Sciences

Authors

Prof. Zhimin Liu

Institute of Chemistry

Chinese Academy of Sciences

Beijing, 100190

China

Dr. Yanfei Zhao

Institute of Chemistry

Chinese Academy of Sciences

Beijing, 100190

China

Cover Image: © Valenty/Shutterstock

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Preface

Ionic liquids (ILs), first reported by Paul Walden in 1914, are a class of molten salts entirely composed of organic cations and inorganic/organic anions, generally showing a liquid state under ambient conditions. Different from traditional molecular solvents, there exist multiple interactions in IL systems, including Coulomb interaction, hydrogen bonding, halogen bonding, Van der Waals force, hydrophilic/hydrophobic interaction, interactions, and coordination, which provide ILs with unique physicochemical properties, such as negligible vapor pressure, high thermal and chemical stability, versatile solvation ability, easy recyclability, wide electrochemical windows, and high tunability. Importantly, they can be designed with specific functions by judiciously selecting the combinations of cations and anions to meet requirements for diverse applications. Especially, many ILs have been designed with green features and have been considered an important kind of green solvents, showing promising applications in green chemistry. To date, various kinds of ILs, such as neutral ILs, acidic ILs, basic ILs, protic ILs, chiral ILs, reactive ILs, and ILs with strong hydrogen bonding abilities, have been synthesized through molecular design, which have been widely applied in many fields, such as extraction and separation, gas absorption, material preparation and processing, battery electrolytes, and chemical reactions.

In chemical reaction processes, ILs can serve as reaction media, catalysts/cocatalysts, or additives, showing wide applications based on their unique structures and properties. As the reaction medium, ILs show a unique solvent effect, which can not only dissolve the reactants effectively, but also facilitate better contact between the reactants and catalysts, thereby enhancing the mass and heat transfer during the reaction process. Furthermore, due to the special ionic microenvironment, they can also effectively activate the reactants, improve the catalyst activity, and stabilize the reaction intermediates, allowing the target reaction to proceed smoothly and thus regulating the product selectivity. The high designability of ILs provides them with catalytic activities for chemical reactions. In particular, the cooperative interaction derived from the cation and anion of the IL catalyst makes the IL catalyst show enhanced activity compared to conventional catalysts. For example, acidic and basic ILs have been reported to show improved performance for the reactions that can be catalyzed by the traditional acids and bases, and avoid the problems caused by the acid and base catalysts. In recent years, the chemical transformation of renewable and recyclable carbon resources (e.g. CO2, biomass, and plastic wastes) has attracted much attention due to the requirements for green and sustainable development. Task-specific ILs have shown promising applications in catalyzing the transformation of these renewable carbon resources into chemicals and fuels, and numerous researches have emerged. In particular, some CO2-reactive ILs have been designed to accomplish chemical transformations of CO2 under metal-free and mild conditions. The ILs with the capability to form strong hydrogen bonds can efficiently catalyze the water-involved reactions including dehydration, hydration, and hydrolysis through hydrogen bonding catalysis. Additionally, ILs have also been employed in catalyzing alkylation, oxidation, and other C-C, C-N or C-O bond formation reactions. As green media or green catalysts, ILs provide green approaches to achieve chemical reactions, which is an important part of green and sustainable chemistry. Therefore, it is of great significance to timely summarize the research progress in this field.

The book contains nine chapters. The Introduction (Chapter 1) covers the background of writing this book and description of various ILs that have been applied as catalysts/cocatalysts in chemical reactions. Chapters 2–4 summarize the recent advances in IL-catalyzed or promoted CO2 chemical transformations. The task-specific ILs, especially CO2-reactive ILs, can chemically capture CO2 and activate it, further achieving its transformation to chemicals under metal-free and mild conditions (Chapter 2). Since ILs can effectively tune the catalytic activity of metal catalysts, the IL–metal catalytic systems have emerged as a kind of efficient catalysts for the reductive transformation of CO2 coupled with hydrogen (Chapter 3). ILs can also be used as electrolytes, and the IL-based electrolytes have shown good performance for the electroreduction of CO2 (Chapter 4). Chapter 5 describes the IL-catalyzed chemical transformation of cellulose, hemicellulose, lignin, and their derivatives, with typical cases for the production of oxygen-containing chemicals, such as reducing sugars, 5-hydroxymethylfurfural, levulinic acid, vanillin, aromatic carboxylic acids, diethyl maleate, and so on. Chapter 6 introduces the research findings related to oxidations of various chemicals, including alcohols/aldehydes, organic sulfides, olefins, and amines, over IL catalysts with a discussion on the reaction pathway and catalytic mechanism of the IL catalysts. In Chapter 7, the progress on the water-involved chemical reactions over IL catalysts, including dehydrative esterification between carboxylic acids and alcohols, dehydrative etherification of alcohols, dehydrative alkenylation, dehydrative amidation, hydration reactions of alkynes, propargyl alcohols, nitriles, epoxides, and hydrolysis of esters/ethers, is described, with a discussion on the hydrogen bonding catalysis mechanism of IL catalysts. Chapter 8 introduces the other IL-catalyzed C-C, C-N and C-O formation reactions such as alkylation reaction, Michael addition, Diels–Alder reactions, Baylis–Hillman reactions, Markovnikov additions, Aldol condensation, and ring-closing C-O/C-O and C-O/O-H bond metathesis reaction, and the possible reaction mechanism is discussed as well. Besides the above chemical reactions, the decomposition of plastics including polyesters, polyamides, polyolefins, and mixtures of some plastics can be achieved under the catalysis of task-specific ILs, which is summarized in Chapter 9, with a focus on degradation strategies and catalytic mechanisms.

The applications of ILs in catalysis have been experiencing rapid development in the past decade, and a comprehensive review is thus necessary. This book is organized based on the following guidelines: (1) concentrating on the forefront of current research and striking to reflect the latest progress and developments; (2) a comprehensive review focusing on basic fundamental research with typical examples and data analysis. More especially, we put lots of effort into the basic knowledge of IL catalysis. Therefore, this book is particularly readable for beginners and graduate students who have just entered this field. We hope that by reading this book, they can understand the fundamentals of IL catalysis and therefore deeply explore applications of ILs in chemical reactions. Under the aforementioned guidelines, this book was mainly written by Professor Zhimin Liu and Dr. Yanfei Zhao at the Institute of Chemistry, Chinese Academy of Sciences (ICCAS). Dr. Huan Wang, who is currently working at Shaanxi University of Science and Technology, was involved in the writing of Chapters 5 and 7, while Dr. Ruipeng Li, working at Henan Normal University, participated in the drafting of Chapter 3. Both Drs. Wang and Li were former PhD students of Professor Zhimin Liu. We gained help from Dr. Jiaju Fu and doctoral students in our group, including Minhao Tang, Rongxiang Li, Yiding Wang, Wei Zeng, Yusi Wang, and Hui Zhang, who were dedicated to collecting references, drawing figures, and sorting and editing for the book. Here we also express our heartfelt appreciation to Dr. Lifen Yang and editors Priyadarshini Natarajan, Katrina Maceda, Kubra Ameen, Manoj Kumar, Mahesh Chandra Gaur, and Rajesh Venkatraman at Wiley for their great support for the publication of this book.

We hope that this book can provide beneficial help and inspiration for those who are working in chemistry, especially in green and sustainable chemistry, and can serve as a reference and text for undergraduates and graduate students, scientists and researchers who are majoring in chemistry and chemical engineering, as well as those interested in ILs. Due to the relatively wide range of topics covered in this book and the rapid development in the field of chemistry, as well as the limited knowledge and ability of the authors, we sincerely appreciate the criticism and comments from the readers.

Acknowledgments

The authors thank the financial support from the National Natural Science Foundation of China (grant Nos. 22121002, 22233006) and the Chinese Academy of Sciences (027GJHZ2022053MI).