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SYNTHESIS. PROPERTIES, and APPLICATIONS of IONIC LIQUIDS SERGEI V. DZYUBA. M.S. a DISSERTATION in CHEMISTRY Submitted to The

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SYNTHESIS. PROPERTIES, and APPLICATIONS of IONIC LIQUIDS SERGEI V. DZYUBA. M.S. a DISSERTATION in CHEMISTRY Submitted to The SYNTHESIS. PROPERTIES, AND APPLICATIONS OF IONIC LIQUIDS by SERGEI V. DZYUBA. M.S. A DISSERTATION IN CHEMISTRY Submitted to the Graduate Faculty of Texas Tech University in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY Approved Chairperson of the Committee Accepted Dean of the Graduate School May, 2002 ACKNOWLEDGEMENTS Looking at all the things I have had a chance to do thus far, I realize that many of those things (or maybe all of them) might never have happened if for not the people who have been involved in my life. I feel privileged to acknowledge these individuals for what I am and have right now. Professor Richard A. Bartsch, my Ph.D. advisor, introduced me to the field of ionic liquids and made it a very challenging and enjoyable experience. I am in debt to him for his encouragement and guidance throughout my stay at Texas Tech University. It has been an honor of being mentored by Professor Bartsch. Professors David M. Bimey and Guigen Li, my Ph.D. committee members, have provided invaluable help in teaching and research. It has been a real pleasure of being taught and guided by them. Due to the interdisciplinary nature of my dissertation research, I was very fortunate to learn from and collaborate with members of various research groups. Professor Sindee L. Simon (Department of Chemical Engineering, TTU) was invaluable in introducing the principles of differential scanning calorimetry. I thank Professor Dominick J. Casadonte, Jr. (Department of Chemistry and Biochemistry, TTU) for sharing the DSC equipment. I would like to thank Dr. Sangki Chun (Department of Chemistry and Biochemistry, TTU) for performing extraction studies with ionic liquids. I like to acknowledge Mr. David W. Purkiss (Department of Chemistry and Biochemistry, TTU) for various 500 MHz NMR spectroscopy experiments. The contributions of Professor Edward L. Quitevis and Dr. Byung-Ryool Hyun (Department of Chemistry and Biochemistry, TTU) on intermolecular dynamics of ionic liquids are greatly acknowledged. Professor Robert W. Shaw and Ms. Shelly Wells (Department of 11 Chemistry and Biochemistry, TTU) are acknowledged for initiating the studies on ionic liquids as cryogenic solvents for biochemical processes. I want to thank Professor Robert A. Flowers, II (Department of Chemistry and Biochemistry, TTU) for help with the set­ up of Karl-Fisher apparatus and for a generous gift of ethylammonium nitrate. Professor Robin D. Rogers (Department of Chemistry, The University of Alabama) provided helpful suggestions in different aspects of ionic liquids. I want to express my deepest and warmest gratitude to my parents. I feel enormously blessed having them at every step of my life, and knowing that I can always rely on their love, support and understanding. HI TABLE OF CONTENTS ACKNOWLEDGEMENTS ii LIST OF TABLES xi LIST OF FIGURES xvi LIST OF SCHEMES xi CHAPTER I. ROOM-TEMPERATURE IONIC LIQUIDS - OLD NOVEL SOLVENTS: AN INTRODUCTION 1 1.1. Nomenclature of Ionic Liquids 7 1.2. Present Status of the Field of Ionic Liquids II 1.3. Statement of Research Objectives 13 1.4. References 14 II. SYNTHESIS OF IONIC LIQUIDS 17 2.1. Preparation of l-Alkyl(aralkyl)-3-alkyr-imidazoIium / J Halides 17 2.2. Preparation of N-alkyl(aralkyl)pyridinium and-quinolinium -y Halides 26 2.3. Synthetic Routes to C2v-symmetric 1,3-Dialkylimidazolium / '.^ Salts 28 2.4. Introducing Functional Groups into Imidazolium Ionic Liquids 30 2.5. Synthesis of Dicationic Salts 34 IV 2.6. Metathesis Reactions to Introduce Other Anions into Ionic Liquids 36 2.7. Preparation of Deuterated Ionic Liquids 38 2.8. Conclusions 41 2.9. Experimental Section 41 2.9.1. Materials 41 2.9.2. Physical and Analytical Methods 42 2.9.3. Synthesis of I-Alkyl(aralkyl)-3-methylimidazoIium Halides 1-10 42 2.9.4. Procedure for the Synthesis of 1-Substituted Imidazoles 14-20 42 2.9.5. Synthesis of l-Alkyl-3-alkyr-imidazolium and l-Aralkyl-3- alkyliimidazolium HaHdes 21-47 44 2.9.6. Synthesis of N-Alkyl(aralkyl)pyridinium Halides 51-54 50 2.9.7. Synthesis of N-Alkyl(aralkyl)quinolinium Bromides 55-56 50 2.9.8. Synthesis of Symmetric 1,3-Dialkylimidazolium Bromides 21 and 57-64 51 2.9.9. Synthesis of Ionic Liquids Containing Functional Groups 65-72 51 2.9.10. Synthesis of Symmetric Dicationic Ionic Liquids 73-75 53 2.9.11. Synthesis of Non-symmetric Dicationic Ionic Liquids 76-83 54 2.9.12. Synthesis of l-Alkyl-3-methylimidazolium Hexafluorophosphate [C„-mim]PF6 Room-Temperature Ionic Liquids 84-89 56 2.9.13. Synthesis of Deuterated Pyridine-Containing Room- Temperature Ionic Liquids 90 and 91 57 2.9.14. References 57 III. FINE-TUNING THE PHYSICAL PROPERTIES OF IONIC LIQUIDS 60 3.1. Phase Transition Temperatures of Ionic Liquids 63 3.1.1. Phase Transition Temperatures of l-Alkyl-3- methylimidazolium Hexafluorophosphate and Bis(trifluoromethyIsulfonyl)imide Ionic Liquids 64 3.1.2. Phase Transition Temperatures of l-Alkyl-3-alkyl'- imidazolium hexafluorophasphates 66 3.1.3. Phase Transition Temperatures of Symmetric 1,3-Dialkylimidazolium Hexafluorophasphate Ionic Liquids.... 70 3.1.4. Phase Transition Temperatures of l-Aralkyl-3- methylimidazolium Hexafluorophosphate and Bis(trifluoromethylsulfonyl)imide Ionic Liquids 72 3.2. Densities of Room-Temperature Ionic Liquids 74 3.2.1. Density of l-Substituted-3-methylimidazolium Room- Temperature Ionic Liquids 75 3.2.2. Influence of Temperature on the Density of Selected Ionic Liquids 77 3.3. Viscosities of Room-Temperature Ionic Liquids 78 3.3.1. Influence of Structure of l-AlkyI(aralkyl)-3- methylimidazolium Ionic Liquids on Dynamic Viscosity 79 3.3.2. Viscosity - Temperature Dependence for Room-Temperature Various Ionic Liquids 81 VI 3.4. Surface Tensions of Room-Temperature Ionic Liquids 83 3.5. Polarity of Room-Temperature Ionic Liquids 86 3.6. Conclusions 90 3.7. Experimental Section 93 3.7.1. Materials 93 3.7.2. Physical and Analytical Methods 93 3.7.3. Preparation of l-Alkyl-3-methylimidazolium Hexafluorophosphate and Bis(trifluoromethylsulfonyl)imide Ionic Liquids 94 3.7.4. Preparation of l-Aralkyl-3-methylimidazolium Hexafluorophosphate and Bis(trifluoromethyIsulfonyl)imide Ionic Liquids 95 3.7.5. Preparation of l-Alkyl-3-alkyl'-imidazolium Hexafluorophosphate Ionic Liquids 95 3.7.6. Preparation of Symmetric 1,3-DialkyHmidazoIium Hexafluorophosphate Ionic Liquids 102 3.7.7. Preparation of Ionic Liquids 155 - 157 Containing Functional Groups 102 3.8. References 103 IV. SPECTROSCOPIC STUDIES ON IONIC LIQUIDS 105 4.1. Nuclear Magnetic Resonance (NMR) Spectroscopy of Ionic Liquids.. 105 4.1.1. Influence of the Nature of Deuterated Molecular Solvents on the Chemical Shifts of Imidazolium-Containing Ionic Liquids. 106 4.1.2. Relative Assignment of the H(4)- and H(5)-Imidazolium Protons 107 Vll 4.1.2.1. Influence of the Nature of Deuterated Solvent 108 4.1.2.2. Influence of Concentration on the Relative Positions of the H(4)- and H(5)-Imidazolium Protons 108 4.1.2.3. Influence of Temperature on the Relative Positions of the H(4)- and H(5)-Imidazolium Protons 109 4.1.2.4. Influence of the Anion on the Relative Positions of the H(4)- and H(5)-Imidazolium Protons 109 4.1.2.5. Influence of the Imidazolium Cation Structure on the Relative Positions of the H(4)- and H(5)-Imidazolium Protons Ill 4.1.3. Influence of the Anion on the Chemical Shifts of the H(2)- Imidazolium Protons 112 4.1.4. Influence of Concentration on the Chemical Shifts Imidazolium Protons in Different Ionic Liquids 113 4.1.5. Influence of Elongation of the Alkyl Substituent (C„) in [C8-C„im]PF6 with n = 1-4 (88,110,118,164) and [(C6H5)2CH-C„im]NTf2 with n = 1-4 (165-168) Ionic Liquids on Chemical Shifts of the H(2)-, H(4)- and H(5)-imidazolium Protons 116 4.1.6. Influence of Temperature on the Chemical Shifts of [C8-mim]PF6 (88) Ionic Liquid 118 4.1.7. Influence of Concentration and Solvent on Anions of Several Ionic Liquid 119 4.1.7.1. Influence of Concentration and Solvent on the 'H NMR Chemical Shifts of CHjCOj" in [Cg- mim]CH3C02 Ionic Liquid (159) 120 viu 4.1.7.2. Influence of Concentration and Solvent on the '^F NMR Chemical Shifts of-N(S02CF3)2 and CFjCOj" in [Cg-mimJNTfj (101) and [C8-mim]CF3C02 (163) Ionic Liquids 120 4.2. Intermolecular Dynamics of Room-Temperature Ionic Liquids 121 4.3. Conclusions 124 4.4. Experimental Section 125 4.4.1. Materials 125 4.4.2. Physical and Analytical Methods 125 44.3. Preparation of [C8-mim]B(C6H5)4 (160) and [C8-mim]BF4 (161) Ionic Liquids 126 4.4.4. Preparation of [C8-mim]CH3C02 (159), [C8-mim]N03 (162) and [Cg-mim]CF3C02 (163) Ionic Liquids 127 4.4.5. Preparation of l-Benzhydryl-3-alkylimidazolium Bis(trifluoromethylsulfonyl)imide Ionic Liquids 128 4.5. References 129 V. APPLICATIONS OF ROOM-TEMPERATURE IONIC LIQUIDS: EN ROUTE TO DESIGNER SOLVENTS 131 5.1. Application of Room-Temperature Ionic Liquids in Competitive Alkali Metal Salts Extraction by a Crown Ether 131 5.2. Ionic Liquids as Solvents for Enzymatic Reactions: Enzyme- Catalyzed, Lactam-Ring Opening Reactions in Ionic Liquids 134 5.3. Diels-Alder Reactions in Ionic Liquids 139 5.4. Conclusions 143 5.5. Experimental Section 144 IX 5.5.1. Materials 144 5.5.2. Competitive Solvent Extraction of Alkali Metal Salts from Aqueous Solution into Ionic Liquids and Molecular Organic Solvents 145 5.5.3. Determination of Enzyme Activity in Ionic Liquids 145 5.5.4. Representative Procedure for the Diels-Alder Reaction in Ionic Liquids 145 5.6.
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