SYNTHESIS OF NEW SEPARATING AGENTS FOR NUCLEAR MATERIALS by JAEWOOK NAM, B.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 Accepted August, 1998 ACKNOWLEDGMENTS First, I wish to express my deepest appreciation to Dr. Richard A. Bartsch, my supervising professor, for his guidance, encouragement, and professional advice throughout my graduate program at Texas Tech University. I would also like to thank to my doctoral committee members, Dr. David M. Bimey, Dr. Allan D. Headley, and Dr. John N. Marx, for their encouragement and advice. I wish to express my thanks to past and present members of the Bartsch Research Group, for their advice and friendship. Secondly, I am pleased to acknowledge support by the Nuclear Materials Technology Division of Los Alamos National Laboratory for the research on bifunctional anion-exchange resins for plutonium(rV) sorption and by the Chemistry Division of Argonne National Laboratory for the research on new cyclic polyether compounds for cesium ion extraction. Finally, I would like to give special thanks to my wife Seulhee for her love and support. Without her understanding and devotion, my study would not have been completed. I also wish to express special thanks to my aunt and uncle, Dr. Hee Sook Kim Chong and Dr. Key Ray Chong, for their love and support. I could not finish my acknowledgment without an expression of gratitude to my mother for her love and support. TABLE OF CONTENTS ACKNOWLEDGMENTS ii ABSTRACT xiv LIST OF TABLES xv LISTOFnOURES xvii LIST OF SCHEMES xviii CHAPTER 1. INTRODUCTION 1 1.1. Background for Nuclear Waste Management 1 1.2. Plutonium Separation by Ion-Exchange Resins 3 1.3. Cesium Separation by Cyclic Polyether Extractants 4 1.4. Statement of Research Goals 6 1.5. References 8 2. SYNTHESIS OF POLYMER-BOUND SEPARATING AGENTS 10 2.1. Results and Discussion 10 2.1.1. Synthesis of Bifunctional Anion-Exchange Resins 10 2.1.1.1. Trimethylammonium-Containing Bifunctional Anion-Exchange Resins 13 2.1.1.2. Pyridinium-Containing Bifunctional Anion-Exchange Resins 16 2.1.1.3. Trimethylphosphonium-Containing Bifunctional Anion-Exchange Resins 21 2.1.1.4. N-Methylpicolinium-Containing Bifunctional Anion-Exchange Resins 23 iii 2.1.2. Evaluation of Bifunctional Anion-Exchange Resins 25 2.1.3. Synthesis of Water-Soluble Poly(vinylpyridines) 30 2.1.3.1. Hydroxyethyl-Substituted Water-Soluble Polymers 31 2.1.3.2. 3-(Trimethylammonio)propyl-Substituted Water-Soluble Polymers 33 2.2. Chapter Summary 35 2.3. Experimental Procedures 36 2.3.1. Sources of Reagents 36 2.3.2. Purification of Reagents 36 2.3.3. General 36 2.3.4. General Procedure for the Synthesis of (co-Bromoalkyl)trimethylammonium Bromides 8-13 37 2.3.4.1. (3-Bromopropyl)trimethylammonium Bromide (8) 37 2.3.4.2. (4-Bromobutyl)trimethylammonium Bromide (9) 38 2.3.4.3. (5-Bromopentyl)trimethylammonium Bromide (10) 38 2.3.4.4. (6-Bromohexyl)trimethylammonium Bromide (11) 38 2.3.4.5. (7-Bromoheptyl)trimethylammonium Bromide (12) 38 2.3.4.6. (8-Bromooctyl)trimethylammonium Bromide (13) 39 2.3.5. Preparation of [2-(2'-Bromoethoxy)ethyl]- trimethylammonium Bromide (21) 39 2.3.6. General Procedure for the Synthesis of Poly[N-(co-Trimethylammonioalkyl) 4-Vinylpyridinium Dibromides] 14-19 40 2.3.6.1. Poly[N-(2-Trimethylammonioethyl) 4-Vinylpyridinium Dibromide] (14) 40 iv 2.3.6.2. Poly[N-(3-Trimethylammoniopropyl) 4-Vinylpyridinium Dibromide] (15) 40 2.3.6.3. Poly[N-(4-Trimethylammoniobutyl) 4-Vinylpyridinium Dibromide] (16) 40 2.3.6.4. Poly[N-(5-Trimethylammoniopentyl) 4-Vinylpyridinium Dibromide] (17) 41 2.3.6.5. Poly[N-(6-Trimethylammoniohexyl) 4-Vinylpyridinium Dibromide] (18) 41 2.3.6.6. Poly[N-(8-Trimethylammoniooctyl) 4-Vinylpyridinium Dibromide] (19) 41 2.3.7- Preparation of Poly[2-(N-2'-Trimethylammonioethoxy)ethyl 4-Vinylpyridinium Dibromide] (22) 41 2.3.8. Preparation of N-(2-Bromoethyl)pyridinium Bromide (23) 42 2.3.9. General Procedure for the Synthesis of N-(o>Bromoalkyl)pyridinium Bromides 25-28 42 2.3.9.1. N-(3-Bromopropyl)pyridinium Bromide (25) 43 2.3.9.2. N-(4-Bromobutyl)pyridinium Bromide (26) 43 2.3.9.3. N-(5-Bromopentyl)pyridinium Bromide (27) 44 2.3.9.4. N-(6-Bromohexyl)pyridinium Bromide (28) 44 2.3.10. Preparation of N-[2-(2'-Bromoethoxy)ethyl]pyridinium Bromide (29) 44 2.3.11. General Procedure for the Synthesis of Poly[N-co-(N'-Pyridinio)alkyl 4-Vinylpyridinium Dibromides] 30-34 45 2.3.11.1. Poly[N-2-(N'-Pyridinio)ethyl 4-Vinylpyridinium Dibromide] (30) 45 2.3.11.2. Poly[N-3-(N'-Pyridinio)propyl 4-Vinylpyridinium Dibromide] (31) 46 2.3.11.3. Poly[N-4-(^N'-Pyridinio)butyl 4-Vinylpyridinium Dibromide] (32) 46 2.3.11.4. Poly[N-5-(N'-Pyridinio)pentyl 4-Vinylpyridinium Dibromide] (33) 46 2.3.11.5. Poly[N-6-(N'-Pyridinio)hexyl 4-Vinylpyridinium Dibromide] (34) 46 2.3.12. General Procedure for the Synthesis of (O-Bromoalkyltrimethylphosphonium Bromides 35-39 47 2.3.12.1. (2-Bromoethyl)trimethylphosphonium Bromide (35) 47 2.3.12.2. (3-Bromopropyl)trimethylphosphonium Bromide (36) 47 2.3.12.3. (4-Bromobutyl)trimethylphosphonium Bromide (37) 47 2.3.12.4. (5-Bromopentyl)trimethylphosphonium Bromide (38) 48 2.3.12.5. (6-Bromohexyl)trimethylphosphonium Bromide (39) 48 2.3.13. General Procedure for the Synthesis of Poly[N-(co-Trimethylphosphonioalkyl) 4-Vinylpyridinium Dibromides] 40-43 48 2.3.13.1. Poly[N-(^2-Trimethylphosphonioethyl) 4-Vinylpyridinium Dibromide] (40) 49 2.3.13.2. Poly[N-(3-Trimethylphosphoniopropyl) 4-Vinylpyridinium Dibromide] (41) 49 2.3.13.3. Poiy[N-(4-Trimethylphosphoniobutyl) 4-Vinylpyridinium Dibromide] (42) 49 2.3.13.4. Poly[N-(5-Trimethylphosphoniopentyl) 4-Vinylpyridinium Dibromide] (43) 49 VI 2.3.14. General Procedure for the Synthesis of Poly[N-(Picolyl) 4-Vinylpyridinium Chlorides] 47-49 50 2.3.14.1. Poly[N-(2-Picolyl) 4-Vinylpyridinium Chloride] (47) 50 2.3.14.2. Poly[N-(3-Picolyl) 4-Vinylpyridinium Chloride] (48) 50 2.3.14.3. Poly[N-(4-Picolyl) 4-Vinylpyridinium Chloride] (49) 51 2.3.15. Preparation of Poly(N-Methyl 4-Vinylpyridinium Iodide) (50) 51 2.3.16. General Procedure for the Synthesis of Poly[N-(N'-Methylpicolinio) 4-Vinylpyridinium Diiodides] 51-53 52 2.3.16.1. Poly[N-(2-N'-Methylpicolinio) 4-Vinylpyridinium Diiodide] (51) 52 2.3.16.2. Poly[N-(3-N'-Methylpicolinio) 4-Vinylpyridinium Diiodide] (52) 52 2.3.16.3. Poly[N-(4-N'-Methylpicolinio) 4-Vinylpyridinium Diiodide] (53) 53 2.3.17. Preparation of Partially Substituted Poly[N-(2'-Hydroxy)ethyl 4-Vinylpyridine] 55 53 2.3.18. Preparation of Partially Substituted Poly[N-(2'-Hydroxy)ethyl 2-Vinylpyridine] 59 54 2.3.19. Preparation of Partially Substituted Poly[N-(3-Trimethylammonio)propyl 4-Vinylpyridinium Dibromide] 63 54 2.3.20. Preparation of Partially Substituted Poly[N-(3-Trimethylammonio)propyl 2-Vinylpyridinium Dibromide] 65 55 2.4. References 56 Vll 3. SYNTHESIS OF CYCLIC POLYETHER EXTRACT ANTS 58 3.1. Results and Discussion 58 3.1.1. Synthesis of Carbon Atom-Linked Side Arm Cyclic Polyethers 58 3.1.1.1. Preparation of Bis(l-hydroxyalkyl)- Substituted Crown Ethers 59 3.1.1.2. Preparation of Bis(2-hydroxyalkyl)- Substituted Crown Ethers 63 3.1.1.2.1. By Isomerization 64 3.1.1.2.2. By Oxymercuration-Demercuration 66 3.1.1.2.3. By Hydroboration-Oxidation 70 3.1.2. Synthesis of Oxygen Atom-Linked Side Arm Cyclic Polyethers 71 3.1.2.1. Elaboration of the Side Arm in a Catechol Derivative and Subsequent Cyclization 72 3.1.2.2. Cyclization of a Protected Catechol and Subsequent Deprotection and Elaboration of the Side Arm 74 3.1.2.3. Modification of Dibenzo-18-crown-6 and Subsequent Elaboration of the Side Arms 76 3.1.2.3.1. Synthesis of Dihydroxy-Substituted Dibenzo-18-crown-6 76 3.1.2.3.2. Synthesis of Di[(2-hydroxy)alkoxybenzo]- 18-crown-6 Involving Alkylation of Di(hydroxybenzo)-l 8-crown-6 79 3.1.2.3.2.1. Reaction with Epoxides 80 3.1.2.3.2.2. Reaction with Cyclic Sulfate Ester 83 3.1.2.3.2.3. Reaction with Benzyl Bromide 87 Vlll 3.1.2.3.3. Synthesis of Di[(2-hydroxyalkoxy)benzo]- 18-crown-6 Involving a Grignard Reaction 88 3.1.2.3.3.1. Grignard Reaction of an Acid Chloride Followed by Reduction 88 3.1.2.3.3.2. Grignard Reaction of an Aldehyde 91 3.2. Chapter Summary 95 3.3. Experimental Procedures 96 3.3.1. Sources of Reagents 96 3.3.2. Purification of Reagents 96 3.3.3. General 97 3.3.4. General Procedure for the Synthesis of Dibenzo-18-crown-6 Diketones 66-69 97 3.3.4.1. 4,4'(5')-Di[(butanoyl)benzo]-18-crown-6 (66) 98 3.3.4.2. 4,4'(5')-Di[(hexanoyl)benzo]-l8-crown-6 (67) 98 3.3.4.3. 4,4'(5')-Di[(decanoyl)benzo]-l8-crown-6 (68) 98 3.3.4.4. 4,4'(5')-Di[(2-ethylhexanoyl)benzo]-18-crown-6 (69) 99 3.3.5. General Procedure for the Synthesis of Dibenzo-18-crown-6 Diols 70-72 99 3.3.5.1. 4,4'(5')-Di[(l-hydroxybutyl)benzo]-18-crown-6 (70) 99 3.3.5.2. 4.4(5')-Di[(l-hydroxyhexyl)benzo]-18-crown-6 (71) 100 3.3.5.3.