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Of Dibenzo[Fl,C] Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1994 Titanocene/Dna Binding and the Synthesis and Characterization of Bridged Cyclopentadienes for the Preparation of Novel Titanocenes. Tamara Renee Schaller Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Schaller, Tamara Renee, "Titanocene/Dna Binding and the Synthesis and Characterization of Bridged Cyclopentadienes for the Preparation of Novel Titanocenes." (1994). LSU Historical Dissertations and Theses. 5754. https://digitalcommons.lsu.edu/gradschool_disstheses/5754 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. INFORMATION TO USERS This manuscript has been reproduced from the microfilm master. UMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. 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 bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI 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. 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Ann Arbor, Ml 48106-1346 USA 313/761-4700 800/521-0600 Order Number 9502141 Titanocene/DNA binding and the synthesis and characterization of bridged cyclopentadienes for the preparation of novel titanocenes Schaller, Tamara Renee, Ph.D. The Louisiana State University and Agricultural and Mechanical Col., 1994 300 N. Zeeb Rd. Ann Arbor, MI 48106 TITANOCENE/DNA BINDING AND THE SYNTHESIS AND CH ARACTERIZATION OF BRIDGED CYCLOPENTADIENES FOR THE PREPARATION OF NOVEL TITANOCENES A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Tamara Renee Schaller B.S., University of Southern Mississippi, 1988 May 1994 To the Schaller family, my father, Edwin Perry my mother, Beverly Joyce my genius brother, Scott Anthony and the adopted member of my family and the love of my life, Marcus Alan Nauman ii ACKNOWLEDGMENTS This work has been achieved under the direction of Dr. Mark Lee McLaughlin. He has been present as more than just a spectator looking over my shoulder; he has been there as both a friend and a mentor. He became just as excited as I did with every successful reaction and every crystal grown. I will always stand in awe of his knowledge of organic chemistry which has motivated me to continuously strive in my search for knowledge. I would also like to express my deepest appreciation to those experts without whose invaluable assistance and enduring patience the characterization and study of these weird molecules would not have been possible: Dr. Frank Fronczek for the determination of the x-ray crystal structures of my "too big crystals" presented herein, Mr. Marcus Nauman and Dr. David Vargas for diligently teaching me the use of the NMR instrumentation, Mr. Jeff Corkren and Mr. Roily Singh for performing those many MS analyses, Mr. Christian Boussert and his assistant, Mr. Vincent Guerrini, for making the wonderful glassware without which much of this work would not have been possible, Dr. Ronald D. Snelling of the LSU Basin Research Institute for the use of the ICP, Dr. Steven M. Pomarico of Dr. Sue G. Bartlett's lab for the tritiated water, and Dr. Simon Chang for the use of the liquid scintillation counter. I am also thankful to the Project SEED program which provided two wonderfully talented high school students: Chris Frazier and Angelica Pearson. Additionally, I am especially grateful for the many other friendships I have made with the faculty, graduate students, undergraduates and staff at Louisiana State University. I will certainly never forget the experiences shared with my LSU family: Doris Culberson and Debbie Tipton, my sisters whose friendships I will cherish forever; Mark Erickson, Gabriel Garcia, Larry Morris, Cal Becker, Alfonso Davila, Guillermo Morales, Li Shui, Scott Cowell, Ralph Isovitsch, Travis Hipp, Scott Yokum and many others who were always there to give me a hard time just like a brother should (and being a good sister I gave it right back); Chad Nordgren, my "son" and all my other friends too numerous to mention but not forgotten. I will always remember the enjoyable conversations at lunch with Dr. Klaus Fischer and his wife Helga, who baked so many delicious cakes of which there was never a crumb left. Of course, I must thank the wonderful staff who made the red tape bearable: Mary Jane Peters, Mrs. Jean Stockner, Judy Walker, Barbara Marquette, Vera Abrams, Letty Saeidi-kh, John Hogan, Joanie Haigler, Cindy Elrod, Linda Temple, Vicki DiBenedetto, Benn Fowler, and Roya Hughes. Finally, I must thank my newest family for having faith in me attaining my Ph.D.: Dr. and Mrs. Robert V. Nauman, my "other" parents; Andrea and Larry Richard and their children; Suzy and Mark LeGrange; and Stephen Nauman. TABLE OF CONTENTS DEDICATION .................................................................................................... ii ACKNOWLEDGMENTS ................................................................................. iii LIST OF TABLES ............................................................................. ix LIST OF FIGURES .......................................................................................... xi LIST OF ABBREVIATIONS ........................................................................... xv ABSTRACT ...................................................................................................... xvii CHAPTER ONE. THE pH DEPENDENT BINDING OF THE ANTITUMOR ACTIVE TITANOCENE DICHLORIDE TO DNA TO FORM DNA-Cp2Ti OR DNA-CpTi ADDUCTS.............................. 1 1.1 Introduction ..................................................................... 1 1.2 Results and Discussion ........................................................................ 4 1.3 Conclusions ............................................................................................ 8 1.4 Experimental.......................................................................................... 8 1.4.1 Materials and M ethods.................................................................. 8 1.4.2 Synthesis of Tritiated Titanocene Dichloride............................ 9 1.4.3 Calculation of the Specific Activity of Tritiated Titanocene Dichloride.................................................................. 11 1.4.4 Complexation of Tritiated Titanocene Dichloride with DNA...................................................................................... 12 1.4.5 Preparation of the Tritiated Titanocene Dichloride Treated DNA Scintillation and ICP Samples........................... 14 CHAPTER TWO. THE SYNTHESIS AND CHARACTERIZATION OF BRIDGED CYCLOPENTADIENES .................................................. 15 2.1 Introduction .......................................................................................... 15 2.2 Retrosynthetic Analysis of the Novel Bridged Cydopentadienyl Ligands............................................................... 16 2.3 Forward Synthetic Routes in Preparing the Bridged Cydopentadienyl Ligands............................................................... 20 2.4 Results and Discussion ..................................................................... 22 v 2.4.1 Forward Synthesis Towards 5,6,11,12-Tetradehydro- dibenzo[fl,e]cyclooctene, 2.6 ........................................................ 22 2.4.1.1 Synthesis of Diene 2.4 via Route A ................................... 22 2.4.1.2 Attempted Synthesis of Diene 2.4 via Route B.............. 26 2.4.1.3 Synthesis of Diene 2.4 via Route C ................................... 29 2.4.1.4 Synthesis of Diene 2.4 via Route D and the Continued Synthesis to Form Diyne 2.6 ......................... 30 2.4.2 Synthesis of Dibenzo[fl,c]tricyclo[9.3.0.0 4'8]tetradeca- l(ll),4(8),5,12-tetraene, 2.17, from 5,6,11,12-Tetradehydro- dibenzo[fl,e]cyclooctene, 2.6, and 1,3-Cyclopentadiene 36 2.4.3 Attempted Synthesis of Dibenzo[fl,c]tricyclo[9.3.0.04/8]- tetradeca-l(ll),4(8),5,12-tetraene, 2.17, from Dibenzo- [fl,e]pentacyclo[12.2.1.l6/9.o2,13.o5,10]octadeca_
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