Ionic Liquids in Synthesis

Автор(ы):Wasserscheid P.
06.10.2007
Год изд.:2002
Описание: A book about ionic liquids? Over three hundred pages? Why? Who needs it? Why bother? These aren't simply rhetorical questions, but important ones of a nature that must be addressed whenever considering the publication of any new book. In the case of this one, as two other books about ionic liquids will appear in 2002, the additional question of differentiation arises - how is this distinctive from the other two? All are multi-author works, and some of the authors have contributed to all three books. Taking the last question first, the answer is straightforward but important. The other two volumes are conference proceedings (one of a NATO Advanced Research Workshop, the other of an ACS Symposium) presenting cutting-edge snapshots of the state-of-the-art for experts; this book is structured. Peter Wasserscheid and Tom Welton have planned an integrated approach to ionic liquids; it is detailed and comprehensive. This is a book designed to take the reader from little or no knowledge of ionic liquids to an understanding reflecting our best current knowledge. It is a teaching volume, admirable for use in undergraduate and postgraduate courses, or for private learning. Central to this tome is the use of ionic liquids for organic synthesis, and especially green organic synthesis, and this chapter is (appropriately) the largest, and the raison d'etre for the work. The book concludes with much shorter chapters on the synthesis of inorganic materials and polymers, the study of enzyme reactions, and an overview and prospect for the area.
Оглавление:
Ionic Liquids in Synthesis — обложка книги.
1 Introduction [1]
2 Synthesis and Purification of Ionic Liquids [7]
  2.1 Synthesis of Ionic Liquids [7]
    2.1.1 Introduction [7]
    2.1.2 Quatemization Reactions [9]
    2.1.3 Anion-exchange Reactions [12]
      2.1.3.1 Lewis Acid-based Ionic Liquids [12]
      2.1.3.2 Anion Metathesis [14]
    2.1.4 Purification of Ionic Liquids [17]
    2.1.5 Conclusions [19]
  2.2 Quality Aspects and Other Questions Related to Commercial Ionic Liquid Production [21]
    2.2.1 Introduction [21]
    2.2.2 Quality Aspects of Commercial Ionic Liquid Production [22]
      2.2.2.1 Color [23]
      2.2.2.2 Organic Starting Materials and other Volatiles [24]
      2.2.2.3 Halide Impurities [25]
      2.2.2.4 Protic Impurities [26]
      2.2.2.5 Other Ionic Impurities from Incomplete Metathesis Reactions [26]
      2.2.2.6 Water [27]
    2.2.3 Upgrading of Commercial Ionic Liquids [27]
    2.2.4 Scaling-up of Ionic Liquid Synthesis [28]
    2.2.5 HSE data [29]
    2.2.6 Future Price of Ionic Liquids [30]
    2.2.7 Intellectual Property Aspects Regarding Ionic Liquids [31]
  2.3 Synthesis of Task-specific Ionic Liquids [33]
3 Physicochemical Properties of Ionic Liquids [41]
  3.1 Melting Points and Phase Diagrams [41]
    3.1.1 Introduction [41]
    3.1.2 Determination of Liquidus Ranges [43]
      3.1.2.1 Melting points [43]
      3.1.2.2 Upper limit decomposition temperature [44]
    3.1.3 Effect of Ion Sizes on Salt Melting Points [45]
      3.1.3.1 Anion size [46]
      3.1.3.2 Mixtures of anions [47]
      3.1.3.3 Cation size [48]
      3.1.3.4 Cation symmetry [49]
      3.1.4.1 Imidazolium salts [50]
      3.1.4.2 Imidazolium substituent alkyl chain length [50]
      3.1.4.3 Branching [52]
    3.1.5 Summary [53]
  3.2 Viscosity and Density of Ionic Liquids [56]
    3.2.1 Viscosity of Ionic Liquids [56]
      3.2.1.1 Viscosity measurement methods [56]
      3.2.1.2 Ionic liquid viscosities [59]
    3.2.2 Density of Ionic Liquids [65]
      3.2.2.1 Density measurement [66]
      3.2.2.2 Ionic liquid densities [66]
  3.3 Solubility and Solvation in Ionic Liquids [68]
    3.3.1 Introduction [68]
    3.3.2 Metal Salt Solubility [70]
      3.3.2.1 Halometalate salts [70]
      3.3.2.2 Metal complexes [70]
    3.3.3 Extraction and Separations [72]
      3.3.3.1 Anionic extractants [73]
      3.3.3.2 Organic extractants [73]
    3.3.4 Organic Compounds [75]
    3.3.5 Conclusions [79]
  3.4 Gas Solubilities in Ionic Liquids [81]
    3.4.1 Introduction [81]
    3.4.2 Experimental Techniques [83]
      3.4.2.1 Gas solubilities and related thermodynamic properties [83]
      3.4.2.2 Stoichiometric technique [84]
      3.4.2.3 Gravimetric technique [85]
      3.4.2.4 Gas chromatography [85]
    3.4.3 Gas Solubilities [86]
      3.4.3.1 Water vapor [86]
      3.4.3.2 Other gases [88]
    3.4.4 Applications [89]
      3.4.4.1 Reactions involving gases [89]
      3.4.4.2 Gas separations [90]
      3.4.4.3 Extraction of solutes from ionic liquids with compressed gases or supercritical fluids [91]
    3.4.5 Summary [91]
  3.5 Polarity [94]
    3.5.1 Chromatographic Measurements [94]
    3.5.2 Absorption Spectra [96]
    3.5.3 Fluorescence Spectra [99]
    3.5.4 Refractive Index [99]
    3.5.5 Organic Reactions [100]
      3.5.5.1 Alkylation of sodium 2-naphthoxide [100]
      3.5.5.2 Diels-Alder reactions [100]
      3.5.5.3 Photochemical reactions [101]
    3.5.6 General Conclusions [102]
  3.6 Electrochemical Properties of Ionic Liquids [103]
    3.6.1 Electrochemical Potential Windows [104]
    3.6.2 Ionic Conductivity [109]
    3.6.3 Transport Properties [118]
4 Molecular Structure and Dynamics [127]
  4.1 Order in the Liquid State and Structure [127]
    4.1.1 Neutron Diffraction [127]
    4.1.2 Formation of Deuteriated Samples [128]
    4.1.3 Neutron Sources [129]
      4.1.3.1 Pulsed (spallation) neutron sources [129]
      4.1.3.2 Reactor sources [129]
    4.1.4 Neutron Cells for Liquid Samples [130]
    4.1.5 Examples [131]
      4.1.5.1 Binary mixtures [131]
      4.1.5.2 Simple salts [133]
    4.1.6 X-ray Diffraction [134]
      4.1.6.1 Cells for liquid samples [135]
      4.1.6.2 Examples [135]
    4.1.7 Extended X-ray Absorption Fine-structure Spectroscopy [139]
      4.1.7.1 Experimental [140]
      4.1.7.2 Examples [142]
    4.1.8 X-ray Reflectivity [145]
      4.1.8.1 Experimental set-up [146]
      4.1.8.2 Examples [146]
    4.1.9 Direct Recoil Spectrometry (DRS) [147]
      4.1.9.1 Experimental set-up [148]
      4.1.9.2 Examples [149]
    4.1.10 Conclusions [149]
  4.2 Quantum Mechanical Methods for Structure Elucidation [152]
    4.2.1 Introduction [152]
    4.2.3 Ion-pair Models and Possible Corrections [153]
    4.2.4 Ab Initio Structures of Ionic Liquids [154]
    4.2.5 DFT Structure of 1-Methyl-3-nonylimidazolium Hexafluorophosphate [155]
    4.2.6 Additional Information Obtained from Semi-empirical and Ab Initio Calculat]ions [156]
  4.3 Molecular Dynamics Simulation Studies [157]
    4.3.1 Performing Simulations [157]
    4.3.2 What can we Leam? [159]
  4.4 Translational Diffusion [162]
    4.4.1 Main Aspects and Terms of Translational Diffusion [162]
    4.4.2 Use of Translational Diffusion Coefficients [164]
    4.4.3 Experimental Methods [165]
    4.4.4 Results for Ionic Liquids [166]
  4.5 Molecular Reorientational Dynamics [168]
    4.5.1 Introduction [168]
    4.5.2 Experimental Methods [168]
    4.5.3 Theoretical Background [169]
    4.5.4 Results for Ionic Liquids [171]
5 Organic Synthesis [174]
  5.1 Stoichiometric Organic Reactions and Acid-Catalyzed Reactions in Ionic Liquids [174]
    5.1.1 Stoichiometric Organic Reactions [175]
      5.1.1.1 Molten salts as reagents [175]
      5.1.1.2 Reactions in chloroaluminate(III) and related ionic liquids [177]
      5.1.1.3 Reactions in neutral ionic liquids [181]
    5.1.2 Acid-Catalyzed Reactions [191]
      5.1.2.1 Electrophilic substitutions and additions [191]
      5.1.2.2 Friedel-Crafts alkylation reactions [196]
      5.1.2.3 Friedel-Crafts acylation reactions [203]
      5.1.2.4 Cracking and isomerization reactions [208]
  5.2 Transition Metal Catalysis in Ionic Liquids [213]
    5.2.1 Why use Ionic Liquids as Solvents for Transition Metal Catalysis? [217]
      5.2.1.1 Their nonvolatile natures [217]
      5.2.1.2 New opportunities for biphasic catalysis [218]
      5.2.1.3 Activation of a transition metal catalyst in ionic liquids [220]
    5.2.2 The Role of the Ionic Liquid [220]
      5.2.2.1 The ionic liquid as "innocent" solvent [221]
      5.2.2.2 Ionic liquid as solvent and co-catalyst [221]
      5.2.2.3 Ionic liquid as solvent and ligand/ligand precursor [222]
      5.2.2.4 Ionic liquid as solvent and transition metal catalyst [225]
    5.2.3 Methods of Analysis of Transition Metal Catalysts in Ionic Liquids [226]
    5.2.4 Selected Examples of the Application of Ionic Liquids in Transition Metal Catalysis [229]
      5.2.4.1 Hydrogenation [229]
      5.2.4.2 Oxidation reactions [232]
      5.2.4.3 Hydrofomiylation [234]
      5.2.4.4 Heck, Suzuki, Stille, and Negishi coupling reactions [241]
      5.2.4.5 Dimerization and oligomerization reactions [244]
    5.2.5 Concluding Remarks [252]
  5.3 Ionic Liquids in Multiphasic Reactions [258]
    5.3.1 Multiphasic Reactions: General Features, Scope, and Limitations [258]
    5.3.2 Multiphasic Catalysis: Limitations and Challenges [259]
    5.3.3 Why Ionic Liquids in Multiphasic Catalysis? [261]
    5.3.4 Different Technical Solutions to Catalyst Separation through the Use of Ionic Liquids [263]
    5.3.5 Immobilization of Catalysts in Ionic Liquids [266]
    5.3.6 Scaling up Ionic Liquid Technology from Laboratory to Continuous Pilot Plant Operation [270]
      5.3.6.1 Dimerization of alkenes catalyzed by Ni complexes [271]
      5.3.6.2 Alkylation reactions [275]
      5.3.6.3 Industrial use of ionic liquids [277]
    5.3.7 Concluding Remarks and Outlook [278]
  5.4 Multiphasic Catalysis with Ionic Liquids in Combination with Compressed CO2 [281]
    5.4.1 Introduction [281]
    5.4.2 Catalytic Reaction with Subsequent Product Extraction [282]
    5.4.3 Catalytic Reaction with Simultaneous Product Extraction [282]
    5.4.4 Catalytic Conversion of CO(?) in an Ionic Liquid/scCO(?) Biphasic Mixture [283]
    5.4.5 Continuous Reactions in an Ionic Liquid/Compressed CO(?) System [283]
    5.4.6 Concluding Remarks and Outlook [287]
6 Inorganic Synthesis [289]
  6.1 Directed Inorganic and Organometallic Synthesis [289]
    6.1.1 Coordination Compounds [289]
    6.1.2 Organometallic Compounds [290]
    6.1.3 Other Reactions [292]
    6.1.4 Outlook [293]
  6.2 Making of Inorganic Materials by Electrochemical Methods [294]
    6.2.1 Electrodeposition of Metals and Semiconductors [294]
      6.2.1.1 General considerations [294]
      6.2.1.2 Electrochemical equipment [295]
      6.2.1.3 Electrodeposition of less noble elements [297]
      6.2.1.4 Electrodeposition of metals that can also be obtained from water [300]
      6.2.1.5 Electrodeposition of semiconductors [303]
    6.2.2 Nanoscale Processes at the Electrode/Ionic Liquid Interface [305]
      6.2.2.1 General considerations [305]
      6.2.2.2 The scanning tunneling microscope [305]
      6.2.2.3 Results [306]
    6.2.3 Summary [316]
7 Polymer Synthesis in Ionic Liquids [319]
  7.1 Introduction [319]
  7.2 Acid-catalyzed Cationic Polymerization and Oligomerization [320]
  7.3 Free Radical Polymerization [324]
  7.4 Transition Metal-catalyzed Polymerization [326]
    7.4.1 Ziegler-Natta Polymerization of Ethylene [326]
    7.4.2 Late Transition Metal-catalyzed Polymerization of Ethylene [327]
    7.4.3 Metathesis Polymerization [328]
    7.4.4 Living Radical Polymerization [329]
  7.5 Preparation of Conductive Polymers [331]
  7.6 Conclusions [332]
8 Biocatalytic Reactions in Ionic Liquids [336]
  8.1 Introduction [336]
  8.2 Biocatalytic Reactions and their Special Needs [336]
  8.3 Examples of Biocatalytic Reactions in Ionic Liquids [339]
    8.3.1 Whole-cell Systems and Enzymes other than Lipases in Ionic Liquids [339]
    8.3.2 Lipases in Ionic Liquids [342]
  8.4 Conclusions and Outlook [345]
9 Outlook [348]
Index [356]
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