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SYNTHESIS of NOVEL CROWN ETHER COMPOUNDS and Lonomer MODIFICATION of NAFION

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SYNTHESIS of NOVEL CROWN ETHER COMPOUNDS and Lonomer MODIFICATION of NAFION SYNTHESIS OF NOVEL CROWN ETHER COMPOUNDS AND lONOMER MODIFICATION OF NAFION by JONG CHAN LEE, 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 DOCTOR OF PHILOSOPHY Approved August, 1992 L3 ACKNOWLEDGEMENTS I am deeply indebted to Dr. Richard A. Bartsch for his constant encouragement and patience throughout my graduate career. His diligent pursuit of excellence in science inspired me to perform research for the love of it. I would like to thank Drs. Robert D. Walkup, Allan D. Headley, Dennis C. Shelly, Bruce R. Whittlesey. John N. Marx for their willingness to provide help and advice. I would also like to thank friendly co-workers. Dr. T. Hayashita, Marty Utterback, John Knobeloch, Zuan Cong Lu, J. S. Kim, and Dr. Joe McDonough for the wonderful times in the laboratory. I would like to thank Dow Chemical Company U. S. A. and Texas Advanced Technology Program for much of the funding of this research project. I would like to extend gratitude to my wonderful parents and sisters for their support throughout the years that I have spent abroad. Most importantly, I thank my wife Sun Yong without whose endless love and patience none of this would have been possible. 11 TABLE OF CONTENTS ACKNOWLEDGEMENS ii LIST OF TABLES xi LISTOFHGURES xii I. INTRODUCnON 1 Crown Ether Background 1 Cation Complexation by Crown Ethers 2 Synthesis of Monobenzo and Dibenzocrown Ethers 4 Lariat Ethers 1 0 Chromogenic Crown Ethers 1 3 Acyclic Polyether Compounds 1 5 Nafion® lonomer Membrane 1 7 Statement of Research Goal 2 0 II. RESULTS AND DISCUSSION 2 2 Crown Ethers with Aromatic Rings as Part of the Polyether Ring 2 2 Benzo and Dibenzocrown Ethers-Cesium Effect 2 2 1.3-Xylyl Crown Ethers 4 1 Crown Ethers with Pendant Groups 4 3 Pyridyl Crown Ethers 4 3 Crown Ether Xanthates 5 4 Methoxy Crown Ethers 5 7 Chromogenic Crown Ethers 5 9 Acyclic Polyether Carboxylic Acids 6 0 111 Chemical ModiHcaiton of Nafion® lonomer Membrane.. 65 Summary 8 3 III. EXPERIMENTAL PROCEDURES 8 5 Instrumentation and Reagents 8 5 General Procedure for the Preparation of Benzo- and Dibenzocrown Ethers 8 6 Monobenzo-12-crown-4 (30) 8 7 Monobenzo-14-crown-4 (39)..... 8 7 Monobenzo-15-crown-5 (6) 8 7 Monobenzo-18-crown-6 (7) 8 7 Monobenzo-21-crown-7 (8) 8 7 Mono[4(5)-tert-butylbenzo]- 21-crown-7 (41) 8 8 Dibenzo-12-crown-4 (54) 8 8 Dibenzo-13-crown-4 (52) 8 8 Dibenzo-14-crown-4 (51) 8 8 Dibenzo-15-crown-5 (44) 8 8 Dibenzo-16-crown-5 (46) 8 9 unsvm-Dibenzo-18-crown-6 (45) 8 9 Dibenzo-19-crown-6 (47) 8 9 Dibenzo-21-crown-7 (48) 8 9 svm-Dir4(5)-tert-buttvlbenzol- 21 -crown-7 (49) ~ 8 9 l,8-Naphtho-16-crown-5 {S6) 9 0 l,8-Naphtho-19-crown-5 (57) 9 0 l,8-Naphtho-22-crown-7 (58) 9 0 IV o,o'-Biphenyl-17-crown-5 (59) 9 0 o,o'-Biphenyl-20-crown-6 (60) 90 o,o'-Biphenyl-23-crown-7 (61) 91 2,2'-Binaphtho-17-crown-5 (62) 91 2,2'-Binaphtho-20-crown-6 (63) 91 2,2'-Binaphtho-23-crown-7 (64) 91 N,N'-Ditosyl-4,I3-diazadibenzo- 18-crown-6 (69) 9 1 N-Tosylmonoazadibenzo-18-crown-6 (70) 9 2 2,3 -Pyridino-15 -crown-5 (71) 9 2 2,3-Pyridino-18-crown-6 (72) 9 2 2,3-Pyridino-21-crown-7 (73) 9 2 General Procedure for Preparation of 1,3-Xylyl Crown Ethers 76-78 9 2 l,3-Xylyl-18-crown-5 (76) 93 l,3-Xylyl-21-crown-6 (77) 93 l,3-Xylyl-24-crown-7 (78) 9 3 l,3-Bis(bromomethyl)benzene (74) 9 3 General Procedure for the Preparation of sym- (Hydroxy)(methyl)dibenzocrown Ethers 87 and 95 94 Procedure A 9 5 Procedure B 9 6 sym-(Hydroxv)(methvl)dibenzo-16-crown-5 (87) 95 svm-(Hydroxv)(methyl)dibenzo-14-crown-4 (95) 9 5 General Procedures for the Preparation of Pyridyl Substituted Crown Ethers Using Sodium Hydride 9 5 Syin-(2-Picolyloxy)dibenzo- 13-crown-4 (82) 9 6 5^III-(2-Picolyloxy)dibenzo- 14-crown-4 (83) 9 6 &XIIl-(Methyl)(2-picolyloxy)dibenzo- 14-crown-4 (98) 9 7 SXni-(2-Picolyloxy)dibenzo- 16-crown-5 (84) 9 7 fiyni-(Propyl)(2-picolyloxy)dibenzo- 16-crown-5 (91) 97 2-Picolyl dodecyl ether (104) 9 8 General Procedure for the Preparation of Pyridyl Substituted Crown Ethers Using Potassium Hydride 9 8 sym-(Methyn(2-piclyloxy)dibenzo- 16-crown-5 (90) 9 9 sym-(Decyn(2-picoyloxy)dibenzo- 16-crown-5 (92) 9 9 sym-(Propyn(benzvloxv)dibenzo- 16-crown-5 (103) 9 9 Sodium sym-Dibenzo-16- crown-5-oxyxanthate (105) 100 Methyl sym-Dibenzo-16- crown-5-oxyxanthate (107) 101 Methyl sym-Dir3(4)-tert-butvlbenzo1- 16-crown-5-oxyxanthate (108) 101 General Procedure for Preparation of svm (Alkyl)(methoxy)dibenzocrown Ethers 111-113 102 sym-(Methvn(methoxv)dibenzo- 16-crown-5 (111) 10 2 VI SXIII-(Propyl)(methoxy)dibenzo- 16-crown-5 (112) 102 &yiTi-(Decyl)(methoxy)dibenzo- 16-crown-5 (113) 103 General Procedure for Preparation of N-(2-Trifluoro-4,6-dinitrophenyl)-4'- Aminobenzocrown Ethers 114 and 116 103 N-(2-Trifluoro-4,6-dinitrophenyl)-4'- aminobenzo-14-crown-4 (116) 103 N-(2-Trifluoro-4,6-dinitrophenyl)-4'- aminobenzo-15-crown-5 (114) 104 N-(2-Trifluoro-4,6-dinitrophenyl)-5'- nitro-4'-aminobenzo-15-crown-5 (115) 104 General Procedure for the Preparation of Acyclic Polyether Secondary Alcohols 117, 119 and 120 1 05 1,3-Bis(ii-niethoyphenoxy)-2- propanol (117) 105 l,3-Bis(2.-methoxyphenoxy)-2- propanol (119) 105 l,3-Bis(a-methoxyphenoxy)-2- propanone (120) 106 General Procedure for the Preparation of Acyclic Polyether Tertiary Alcohols 121 and 122. 1 06 2-[(Q.-Methoxyphenoxy)methyl]-l- (fi.-methoxyphenoxy)-2-pentanol (121) 107 2-[(fi.-Methoxyphenoxy)methyl] -1 - (fl.-methoxyphenoxy)-2-dodecanol (122) 107 General Procedure for the Preparation of Acyclic Polyether Carboxylic Acids 123-127 108 Vll 1,3-Di(fi.-methoxyphenoxy)-2- (oxyacetoxy)propane (123) 1 0 8 1,3-Di(iTj.-methoxyphenoxy)-2- (oxyacetoxy)propane (126) 10 8 1,3-Di(p.-methoxyphenoxy)-2- (oxyacetoxy)propane (127) 109 4,4'-Bis[(ii-methoxyphenoxy)methyl]- 3-oxaheptanoic acid (124) 109 4,4'-Bis[(ii-methoxyphenoxy)methyl]- 3-oxatridecanoic acid (125) 1 09 3,9-Dioxa-6-(N-tosylaza)- undecane-l,ll-diol (146) 109 1,11 -Dimethoxy-3,9-dioxa-6- (N-tosylaza)undecane (147) 1 10 l,ll-Dimethoxy-3,9-dioxa-6- azaundecane (148) 1 10 N-Tosyldiethanolamine (137) 1 11 N-Tosylmonoaza-15-crown-5 (138) 1 11 Monoaza-15-crown-5 (130) 1 13 General Procedure for the Preparation of 4'-Nitrobenzocrown Ethers 139-144 113 4'-Nitrobenzo-12-crown-4 (139) 1 14 4',5'-Dinitrobenzo-14-crown-4 (143) 114 4'-Nitrobenzo-14-crown-4 (144) 1 14 4'-Nitrobenzo-15-crown-5 (140) 114 4'-Nitrobenzo-18-crown-6 (141) 115 4'-Nitrobenzo-21-crown-7 (142) 115 Vlll General Procedures for the Preparation of 4'-Aminobenzocrown Ethers 132-135 and 145 1 15 Procedure A 1 15 Procedure B 115 4'-Aminobenzo-12-crown-4 (132) 116 4'-Aminobenzo-14-crown-4 (145) 116 4'-Aminobenzo-15-crown-5 (133) 116 4'-Aminobenzo-18-crown-6 (134) 1 1 6 4'-Aminobenzo-21-crown-7 (135) 117 General Procedures for Modification of Nafion® 117 Membrane 1 1 7 Method A 1 17 Method B 117 Hydrolysis of Nafion® Sulfonyl Chloride Membranes 11 8 General Procedure for the Preparation ofDimesylates 118 Triethleneglycol dimesylate (34) 1 19 Tetraethyleneglycol dimesylate (36) 1 19 1,2-Bis[3-(mesyloxy)propyloxy] ethyleneglycol dimesylate (35) 119 Pentaethyleneglycol dimesylate (37) 119 Hexaethyleneglycol dimesylate (38) 1 20 Ethyleneglycol dimesylate (42) 1 20 IX Propyleneglycol dimesylate (43) 1 20 N-Tosyl-diethanolamine dimesylate (68) 1 20 REFERENCES 1 21 LIST OF TABLES 1. Cation Diameters and Cavity Sizes of Crown Ethers 3 2. Yields of the Benzo-18-crown-6 in Ring Closure Reactions with Different Alkali Metal Fluorides 1 0 3. Comparison of Yields for Benzo-12-crown-4 from Alternative Methods 27 4. Comparison of Yields for Monobenzocrown Ethers from Alternative Methods 2 9 5. Cyclization Yields for Dibenzocrown Ethers 3 2 6. Comparison of Cyclization Yields from Different Reaction Conditions 3 6 7. Comparison of Cyclization Yields for 54-56 from Differrent Reagent 3 8 8. Yields of Compounds 82-84 4 5 9. Yields of Compounds 90-92 and 98-100 4 9 10. Chemical Modification of Nafion® Membrane by Method 1 7 4 11. Conversion of Nafion® Membrane to the Sulfonyl Chloride Form Followed by Hydrolysis 7 5 12. Effect of Chlorination Time Upon Alkali-metal Cation Permeation 7 6 13. Chemical Modification of Nafion® Membrane with Monoaza-15- crown-5 by Method II 7 9 14. Influence of Coupling Agents upon Alkali-Metal Cation Permeation 8 1 XI LISTOFHGURES 1. The First Crown Ethers with Cyclic Hexaethers 1 2. Log Ks versus the Ratio of Cation Diameter to Cavity Size for Alkali Metal Complexed Dicyclohexano-18-crown-6 4 3. Synthetic Approaches for Cyclization Reactions 5 4. The Template Effect in the Synthesis of 18-crown-6 7 5. Complexation of Metal Ion by Lariat Ether 1 1 6. Carbon-pivot and Nitrogen-pivot Lariat Ethers 11 7.
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