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Synthesis, Study of Self-Assembly, and Trivalent Lanthanide Metal Ion Recognition Characteristics of Amphiphilic Acylpyrazolones and Amphiphilic Acylisoxazolones

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Synthesis, Study of Self-Assembly, and Trivalent Lanthanide Metal Ion Recognition Characteristics of Amphiphilic Acylpyrazolones and Amphiphilic Acylisoxazolones Western Michigan University ScholarWorks at WMU Dissertations Graduate College 12-2007 Synthesis, Study of Self-Assembly, and Trivalent Lanthanide Metal Ion Recognition Characteristics of Amphiphilic Acylpyrazolones and Amphiphilic Acylisoxazolones Venkat Reddy Guduru Western Michigan University Follow this and additional works at: https://scholarworks.wmich.edu/dissertations Part of the Chemistry Commons Recommended Citation Guduru, Venkat Reddy, "Synthesis, Study of Self-Assembly, and Trivalent Lanthanide Metal Ion Recognition Characteristics of Amphiphilic Acylpyrazolones and Amphiphilic Acylisoxazolones" (2007). Dissertations. 868. https://scholarworks.wmich.edu/dissertations/868 This Dissertation-Open Access is brought to you for free and open access by the Graduate College at ScholarWorks at WMU. It has been accepted for inclusion in Dissertations by an authorized administrator of ScholarWorks at WMU. For more information, please contact [email protected]. SYNTHESIS, STUDY OF SELF-ASSEMBLY, AND TRIVALENT LANTHANIDE METAL ION RECOGNITION CHARACTERISTICS OF AMPHIPHILIC ACYLPYRAZOLONES AND AMPHIPHILIC ACYLISOXAZOLONES by Venkat Reddy Guduru A Dissertation Submitted to the Faculty of The Graduate College in partial fulfillment of the requirements for the Degree of Doctor of Philosophy Department of Chemistry Western Michigan University Kalamazoo, Michigan December 2007 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. SYNTHESIS, STUDY OF SELF-ASSEMBLY, AND TRIVALENT LANTHANIDE METAL ION RECOGNITION CHARACTERISTICS OF AMPHIPHILIC ACYLPYRAZOLONES AND AMPHIPHILIC ACYLISOXAZOLONES Venkat Reddy Guduru, Ph.D. Western Michigan University, 2007 This research project focused on the separation of trivalent lanthanide metal ions by HPLC using amphiphilic acylpyrazolones and amphiphilic acylisoxazolones. The central hypothesis of our research project is that the nanoscale self-assembly nature of amphiphilic ligands (chelating lingads) can influence their metal ion recognition and separation. To test the central hypothesis, we have synthesized a family of novel amphiphilic ligands and employed them as model systems for the separation of trivalent lanthanide metal ions. Several novel intermediates such as 4-acylated, iV-acylated, O- acylated pyrazolones and isoxazolones, have been efficiently synthesized and fully characterized. CH3 CH3 /CH3 N =< Ph-Ny' ------ y s " ^ ' Yy Y ' ^vopeg 0 VOH 0 - , —* ^" OHY 0 Pyrazolone 4-Haloacylpyrazolone Amphiphilic acylpyrazolone Q ■■ ^ — °rW , 0 OH 0 OH 0 Isoxazolone 4-Haloacylisoxazolone Amphiphilic acylisoxazolone (R = Methyl, Pheny; R' = Valeroyl, Benzoyl; x = 750, 516, 913) Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. The trivalent lanthanide metal ion recognition efficacies of these amphiphilic ligands have been demonstrated through baseline separations of a mixture of light, middle, and heavy lanthanide metal ions by employing them in the aqueous mobile phase of high performance liquid chromatography (HPLC) with Ci 8 silica gel as the stationary phase. The complex separation mechanism is influenced by the chemical structure of 4- acylated amphiphilic ligands and their spontaneous self-assembly in the aqueous phase as well as on the stationary phase. Transmission electron microscopy (TEM) images of these amphiphilic ligands in the aqueous phase in the absence and presence of metal ions demonstrated several nanoscale structures such as spherical, dendritic, and linear (nano­ rods, nano-tubes, nano-fibers) structures. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. UMI Number: 3295562 INFORMATION TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. ® UMI UMI Microform 3295562 Copyright 2008 by ProQuest Information and Learning Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. ProQuest Information and Learning Company 300 North Zeeb Road P.O. Box 1346 Ann Arbor, Ml 48106-1346 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. © 2007 Venkat Reddy Guduru Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENTS I wish to profoundly thank my advisor, Dr. Subra Muralidharan, for accepting me as his student and giving me the opportunity to do research in his laboratory, under his guidance. I am greatly indebted to him for the freedom extended to me in every aspect of my work. This enabled me to work in an area that interested me, and effectively partition my time between my work and my family. Discussions with him were always thought provoking and exceedingly helpful. I shall never forget my advisor’s support when I was under stress after I finished my masters. In the same spirit, I want to thank the other members of my doctoral committee, Dr. Ekkehard Sinn, Dr. Sherine Obare, Dr. Yirong Mo, Dr. Muralidhar K. Ghantasala for their help and suggestions. I also wish to thank Dr. John Miller, graduate student advisor, for his valuable academic guidance towards my degree. I am sincerely thankful to the Office of Basic Energy Sciences, Department of Energy for their financial support to continue this project and the Department of Chemistry, WMU for providing me with the opportunity to pursue my graduate studies. I am extremely grateful to Dr. Hengli Ma for her help in HPLC work, and also wish to thank Dr. Srividhya Narayanan for her helpful guidance in my Ph.D. candidacy exam. I would also like to thank our research group for their congeniality. I thank Dr. Raymond Sung for his help and support in operating various departmental instruments. I am especially thankful to Dr. Robert Eversole for his help in providing me with an opportunity to get trained on transmission electron microscope. ii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Acknowledgements-Continued I am also thankful to Annie Dobs and Pam McCortney for their prompt help, not only in all administration related matters, but also in copying manuscripts and office supplies. I am very much thankful to my wife Chandana for being an understanding friend and excellent wife without whose company living would be meaningless. I am grateful to my parents and younger brother for their encouragement and emotional support throughout my stay in the United States. I wish to thank my cousin Dr. Srinivas Reddy G. for his professional and emotional help extended throughout the duration of my work. Last but not least, I also wish to thank my friends for their guidance, encouragement and constant support towards my Ph.D. degree. Venkat Reddy Guduru iii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS ACKNOWLEDGEMENTS........................................................................................ ii LIST OF TABLES...................................................................................................... x LIST OF FIGURES.................................................................................................... xiv LIST OF SCHEMES..................................................................................... xviii CHAPTER I. INTRODUCTION........................................................................................... 1 1.1. Lanthanides and the importance of their separation ................. 1 1.2. Recent developments in the field of lanthanide metal ion separation ........................................................................................ 3 1.3. Central hypothesis ......................................................................... 5 II. SYNTHESIS OF 4-HALO ACYL-3 -METHYL-1 -PHENYL-5- PYRAZOLONES AND THEIR AMPHIPHILIC DERIVATIVES 6 2.1. Introduction ............................................................................... 6 2.2. Chemical properties of acylpyrazolones .................................... 6 2.3. Synthetic approach, results and discussion ................................ 10 2.4. X-ray crystallographic analysis of acylpyrazolone ligands 13 2.5. X-ray diffraction data and their treatment .................................. 16 2.6. Synthesis of amphiphilic acylpyrazolone ligands ..................... 19 2.7. Experimental methods ................................................................. 20 2.7.1. General.............................................................................. 20 2.7.2. Instrumentation and characterization of compounds... 20 iv Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Table of Contents-Continued CHAPTER 2.7.3. 0-(Chlorovaleroyl)-3-methyl-l-phenylpyrazol-5- one (0 2 ) ........ 2 1 2.7.4. 4-(Chlorovaleroyl)-3-methyl-1 -phenylpyrazolin-5- ol (C2)................................................................................ 22 2.7.5. 0-(Bromovaleroyl)-3-methyl-l-phenylpyrazol-5-
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