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Lonizable GROWN ETHERS for the SEPARATION of ALKALI

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Lonizable GROWN ETHERS for the SEPARATION of ALKALI lONIZABLE GROWN ETHERS FOR THE SEPARATION OF ALKALI AND ALKALINE EARTH METAL CATIONS: SYNTHESIS AND APPLICATIONS by SANG IHN KANG, B.S., 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 DCOTGR OF PHILOSOPHY December, 1983 ' }j'' ^Q ACKNOWLEDGMENTS . .7.fr. ' I wish to express my heartfelt gratitude and appreciation to my research supervisor, Professor Richard A. Bartsch, for his invaluable guidance and constant encouragement in completing this research. Special thanks are due to the other members of my committee, Professors John L, Kice, John N, Marx, Robert A. Holwerda and Purnendu K. Dasgupta, for their important suggestions. I aja deeply grateful to my colleagues, Doctors Eronislaw Czech, Gui-Suk Heo and Yung Liu, for their sincere cooperation. Finally, I express my loving appreciation to my wife. Young Hee, for her excellent preparation of the entire manuscript and beautiful inspiration she has provided for ray life and work. 11 CONTENTS ACKNOWLEDGMENTS ii LIST OF TABLES vii LIST OF FIGURES ix I. INTRODUCTION 1 General Background 1 Discovery of Crown Ethers 1 Nomenclature of Multidentate Ligands 3 Applications of Grown Ethers 6 Cation Gomplexation 6 Cation Lipophilization 9 Phase Transfer Catalysts 10 Ion Carriers 11 Parameters Controlling the Gomplexation of 13 Metal Cations by Multidentate Ligands lonophcre 14 Acyclic Multidentate Ligands 16 Macrocyclic Ligands 19 Macrobi- and Macrotricyclic Ligands 20 Identity of the Meteroatom 23 Identity of the Counter Anion 25 Solvent 27 Acyclic versus Cyclic Ligands 30 Additional Binding Site 34 Grown Ethers with a Pendant 36 Non-ionizable Group iii Grown Ethers with a Pendant 41 lonizable Group Carrier-Mediated Separation Techniques 47 Solvent Extraction 48 Bulk Liquid Membrane Transport ^ Liquid Surfactant Membrane Transport 55 Statement of Research Plan 51 II. EXPERIMENTAL SECTION 59 Apparatus and Materials 59 Apparatus 59 Materials 60 Preparation of 2-Bromosubstituted 66 Garboxylic Acids General Method 66 2-Broraohexanoic Acid 66 2-Bromooctanoic Acid 66 2-Bromodecanoic Acid 6"^ Synthesis of Grown Ether Garboxylic Acids 6^ General Method for the Preparation of 47-50 6^ 2-(sym-Dibenzo-16-crown-5-oxy) butanoic Acid 68 (47), mp 93-95°C, was synthesized in 40^ yield 2- (sym-Dibenzo-16- cr own-5- oxy)hexanoic Acid 68 (48), mp 9>95°G, was synthesized in 40^ yield 2-( sym-Dibenzo-16-crown-5-oxy)octanoic Acid 68 (42), mp 15,5-11,5^^^ was prepared in 2% yield 2- ( sym-Dibenzo-16- cr own-5- oxy)decanoic Acid 69 (^), mp 87-88°G, was obtained in 2% yield 2-(sym-Dibenzo-1^crown-^oxy)decanoic Acid (5I) 69 iv 2-(sym-Dibenzo- 19-crown-6-oxy)decanoic Acid (52) 10 2-(sym-Dicyclohexano-16- crown-5-oxy)- ?1 decanoic Acid (54) Separation Techniques 72 Competitive Liquid-Liquid Extraction 72 Competitive Bulk Liquid Membrane Transport 73 Competitive Liquid Surfactant Membrane Transport 73 Studies of the Synergistic Effect 15 System of sym-Dibenzo-16-crown-5 Methyl l6 Ether (42) and Neotridecanoic Acid System of sym-Dibenzo-16-crown-5 Methyl Eiher l6 (42) and Bis(2-ethylhexyl) Hydrogen Phosphate III. RESULTS AND DISCUSSION H Synthesis of Grown Ether Garboxylic Acids 11 Gomplexation of Alkali Metal Cations 81 lonizable Macrocyclic Gomplexing Agents 82 Variation of the Polyether Cavity Size 83 Variation of the Oxygen Basicity I07 Variation of the Lipophilic Group Size 112 Variation of ihe Lipophilic Group II7 Attachment Site Variation of the lonizable Group Identity 118 Nonionizable Organometallic Gomplexing Agents I34 lonizable Non-macrocyclic Gomplexing Agents I35 A Study of the Synergistic Effect I37 Conclusion 140 Gomplexation of Alkaline EariJi Metal Cations 141 Diionizable Acyclic Gomplexing Agents 143 Ethylene Oxide Unit Variation 143 Variation of the Lipophilic Group 148 lonizable Macrocyclic Gomplexing Agents 15^ Variation of the Grown Ether Cavity Size 153 Variation of the Oxygen Basicity 158 Variation of the Lipophilic Group Size 160 Variation of the lonizable Group I63 Conclusion 170 IV. SUMMARY 173 REFERENCES 181 VI LIST OF TABLES 1, Nomenclatures of Linear, Monocyclic and Bicyclic Ligands. 5 2, Comparison of Cation and Cavity Diameters. 8 3, Extraction of Picrates into Methylene Chloride 10 Containing Grown EiJier, 4, Log Ks Values for 1:1 Complexes in Methanol at 25°C, 20 5, Stability Constants of Alkali Metal Complexes with 21 15b-I5e in Water at 25°G. 6, Log Ks Values for the Reaction M"^ + L = ML"*" 23 (M , mei^al ion; L, 18-crown-6). 7, K ion-Transpcrt Rates (j ) of Dibenzo-18-crown-6 27 across Bulk Liquid Membrane at 25 ± 1°C. 8, Solvent Effect on Stability Constant. 29 9, Si^ability Constants for the 1:1 Complexes of 31 2+ Tetramines {±2 and 20) with Gu . + 2+ 10. Thermodynamic Quantities of K - and Ba - Complexes 32 of Peni:aethylene Glycol (21), Pentaethylene Glycol Dimethyl Ether (22), and 18-Grown-6 (j^) at 25°G, 11. Equilibrium Constants for the Reaction of Several 34 Metal Ions with Different Topological Macrocycles, I5d, 22, and 24. 12. Stability Constants for Complexes between 15-Crown-5 37 Lariat Ethers 27a-z and Sodium Chloride in Methanol at 25°C. 13. Acidity and Distribution Data for Grown Ether 45 Garboxylic Acids j6-40. 14. Effects of Dielectric Gonsi:ant on Extraction. 49 vii 15. Distribution Coefficient (D) and Synergistic Factor 51 (SF) for Extraction of the Alkali Metals by Grown Ethers (0.25 M) and Bis(2-ethylhexyl) Hydrogen Phosphate (0,125 M) in Benzene from Dilute Aqueous Solutions at pH 4.0, 16. Stability Constants for Gomplexation of K and Cs with 89 Dibenzo-21-crown-7 (82) and 21-Grown-7 (14) in Methanol at 25°C. 17. Selectivity Orders for Transport of Alkali Metal Ions 97 into an Organic Phase by Grown Ether Garboxylic Acids for Three Separation Techniques. 18. Extraction of Alkali Metal Cations by Lipophilic I06 Crown Ether Garboxylic Acids. 19. Stability Constants of Some 1:1 Metal-EDTA Complexes 142 in 0.1 M KCl at 20°G, 20. Lipophilicity Increments Tf^ for Several Groups X. 147 21. Polyether Cavity and Alkaline Earth Metal Ion 172 Diameters (A). viii LIST OF FIGURES 1. Sketches of "Sandwich" Complexes. 7 2. Salt Transport across a Liquid Membrane, 13 3. Schematic Topology of Assarted lonophores. 15 4. Stability Constants of Acyclic lonophcre-Cation 18 Complexes as a Function of the Ionic Radius. 5. Model for the Gaunter transport of Metal Cations 54 across a Liquid Membrane by a Grown Ether Garboxylic Acid. 6. Schematic Diagram of Batch Dispersed-Emulsion System. 56 7. Gomplexing Agents Utilized in Gomplexation of 62 Alkali and Alkaline Earth Metal Cations. 8,- Liquid Membrane Transport Cell with Dimensions 74 Given in Millimeters, 9. Solvent Extractions of Alkali Metal Ions by Grown 84 Ether Garboxylic Acids ^52« 10. Bulk Liquid Membrane Transport of Alkali Mei:al 92 Ions by Grown Ether Garboxylic Acids 5p-52. 11. Liquid Surfactant Membrane Transport of Alkali Metal 93 Ions by Grown Ether Garboxylic Acids 50-52. 12. Solvent Extractions of Alkali Metal Ions by Grown 98 Ether Garboxylic Acids ^ and 59. 13. Bulk Liquid Membrane Transport ajid Liquid Surfactant 100 Membrane Trajispcrt of Alkali Metal Ions by Grown Ether Garboxylic Acid ^. 14. Solvent Extractions of Alkali Metal Ions by Grown 102 Ether Garboxylic Acids 64-68. IX 15. Solvent Extraction, Bulk Liquid Membrane Transport, 109 and Liquid Surfactant Membrane Transport of Alkali Metal Ions by Crown EiJier Garboxylic Acid ^. 16. Solvent Extractions of Alkali Metal Ions by Grown 114 Ether Garboxylic Acids ^ and ^o 17. Bulk Liquid Membrane Transport of Alkali Metal 116 Ions by Grown Ether Garboxylic Acids ^ and ^o 18. Liquid Surfactant Membrane Transport of Alkali Metal 119 Ions by Grown Ether Garboxylic Acid ^. 19. Solvent ExtraciJ.ons of Alkali Metal Ions by Crown 121 Ether Garboxylic Acids 60, 61 and 6^0 20. Bulk Liquid Membrane Transport of Alkali Metal 124 Ions by Grown Ether Garboxylic Acids 60^, 61 and 63. 21. Solvent Extraction of Alkali Metal Ions by Grown 128 Ether Phosphonic Acid Monoethyl Ester _20. 22. Liquid Surfactant Membrane Transport of Alkali Metal I30 Ions by Grown Ether Phosphonic Acid Monoethyl Ester 70 at Different Source Phase Acidities. 23. Solvent Extraction and Liquid Surfaci^ant Membrane I32 Transport of Alkali Metal Ions by Bis(2-ethylhexyl) Hydrogen Phosphate (B2EHHP). 24. Solvent Extractions of Alkaline Earth Mei:al Ions 144 by Acyclic Polyether Dicarboxylic Acids 75-77° 25. Solvent Extractions of Alkaline Earth Metal Ions 149 by Acyclic Polyether Dicarboxylic Acids 78-80. 26. Bulk Liquid Membrane Transport of Alkaline Earth I52 Me1:al Ions by Acyclic Polyether Dicarboxylic Acid 21 27. Solvent Extractions of Alkaline Earth Metal Ions I54 by Grown Ether Garboxylic Acids 50-53. X 28. Bulk Liquid Membrane Transport of Alkaline Earth I56 Metal Ions by Grown Eiher Garboxylic Acids 50-52. 29. Liquid Surfactant Membrane Transport of Alkaline 157 Earth Metal Ions by Grown Ether Garboxylic Acids io-i2. 30. Solvent Extractions of Alkaline Earth Metal Ions 159 by Grown Ether Garboxylic Acids ^ and ^, 31. Solvent Extraction of Alkaline Earth Metal Ions 161 by Grown Ether Garboxylic Acid ^, 32. Solvent Extractions of Alkaline Earth Metal Ions 162 by Grown Ether Garboxylic Acids ^ and ^, 33. Solvent Extractions of Alkaline Earth Metal Ions 164 by Grown Ether Garboxylic Acids 60_ and 63. 34. Solvent Extractions of Alkaline Earth Metal Ions 166 by Grown Ether Phosphonic Acid MonoeiJiyl Ester 20 and Bis(2-ethylhexyl) Hydrogen Phosphate (B2EHHP). 35. Solvent Extraction of Alkaline Earth Metal Ions I69 by Grown Ether Garboxylic Acid 64p XI CHAPTER I INTRODUCTION General Background Discovery of Grown Ethers To probe the effects of multidentate phenolic ligands on the catalytic properties of vanadium compounds in the polymerization of 1 2 olefins, Pedersen * envisioned bis-2-(_o-hydroxyphenoxy)e1Jiyl eiJier (_!) as a quinquedentate ligand.
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