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INFORMATION to USERS This Manuscript Has Been Reproduced 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 primer. 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, prim 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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A Bell & Howell Intormaiion Company 300 North Zeeb Road Ann Arbor Ml 46106*1346 USA 313/761-4700 800.521-0600 EXPLORATORY PHOTOCHEMISTRY OF POLYFLUORINATED ARYL AZIDES IN NEUTRAL AND ACIDIC MEDIA DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in the Graduate School of The Ohio State University By Hongbin Zhai ***** The Ohio State University 1995 Dissertation Committee: Approved By Matthew S. Platz David J. Hart Christopher M. Hadad Advisor, ' Department of Chemistry UNI Number: 9534100 UMI Microfora 9S34100 Copyright 1995, by UMI Coapany. All rights reserved. This aicrofora edition is protected against unauthorized copying under Title 17, United States Code. UMI 300 North Zeeb Road Ann Arbor, MI 48103 To My Parents ii ACKNOWLEDGMENTS First, and foremost, I must express my heartfelt gratitude to Professor Matthew S. Platz, my advisor and mentor, for his endless guidance, encouragement, and patience as well as his friendship. Without his enlightenment, modem physical organic chemistry as a profound and recondite subject would remain awe-inspiring rather than enjoyable to me. I am greatly indebted to all members of the Platz group, both past and present, for making Columbus so wonderful a place to work and learn. Special thanks go to Jacek Michalak and John Toscano for their pertinent insight and help. This section would be incomplete without mentioning my close friend Fayang Qiu, whose wisdom and erudition I highly value. I am much obliged to my parents and my little sister, who extend their everlasting support and faith from across the Pacific. Finally, I offer my inestimable sincere acknowledgment to my wife, Yifan, also a great chemist, for her eternal understanding and love. iii VITA October 1,1966 Bom - Yangzhong, Jiangsu, P. R. China 1985 B.S. Beijing University Beijing, P. R. China 1988 M.S. Peking Union Medical College Beijing, P. R. China 1989 - 1995 Graduate Teaching and Research Associate The Ohio State University Columbus, Ohio PUBLICATIONS ‘The Photochemistry of Various p-Substituted Tetrafluorophenyl Azides in Acidic Media and the Formation of Nitrenium Ions.” Matthew S. Platz, Jacek Michalak, and Hongbin Zhai (manuscript in preparation). “The Exploratory Photochemistry of Polyfluorinated 2-Naphthylazide.” Hongbin Zhai and Matthew S. Platz (manuscript in preparation). “Mass Spectrometric Studies on Dibenzocyclooctadiene Ligand Compounds from Schisandraceae Plants.” Hongbin Zhai and Puzhu Cong Yaoxue Xuebao 1992, 25, 110. “Flameless Atomic Absorption Method for Direct Determination of Microamount of Rhodium in High-Purity Iridium.” Tongwen Wang, Hongbin Zhai, Xiyi Fang, Wanbai Zhang, and Saijun Li Guangpuxue Yu Guangpu Fenxi 1987, 7, 50. PRESENTATION “The Photochemistry of Various p-Substituted Tetrafluorophenyl Azides in Acidic Media and the Formation of Nitrenium Ions.” Matthew S. Platz, Jacek Michalak, and Hongbin Zhai. The 4th International Meeting on Pulse Investigation in Physics, Chemistry and Biology PULS’94, Lodz and Zakopane, Poland, September 10-16,1994. FIELD OF STUDY Major Field: Chemistry Studies in Organic Chemistry iv TABLE OF CONTENTS DEDICATION............................................................................................................................... ii ACKNOWLEDGMENTS...........................................................................................................iii VITA............................................................................................................................................... iv LIST OF TABLES.......................................................................................................................vii LIST OF FIGURES......................................................................................................................ix LIST OF SPECTRA................................................................................................................... xix CHAPTER I. INTRODUCTION.............................................................................................................1 Generation of Nitrenes ................................................................................................1 Nitrcne ..........................................................................................................................4 The Fluorine Effect .....................................................................................................6 Technical Considerations .........................................................................................19 n. EXPLORATORY PHOTOCHEMISTRY OF POLYFLUORINATED 2-NAPHTHYL AZIDE................................................................................................ 21 Introduction ...............................................................................................................21 Results and Discussion .............................................................................................30 III. PHOTOCHEMISTRY OF VARIOUS p-SUBSTITUTED TETRAFLUOROPHENYL AZIDES IN ACIDIC MEDIA AND THE FORMATION OF NITRENIUM IONS.................................................................... 53 Introduction ...............................................................................................................53 Results and Discussion ............................................................................................ 69 IV. DESIGN AND SYNTHESIS OF PHENYL AZIDE DERIVATIVES AS POTENTIAL ANTIVIRAL DRUGS FOR USE IN BLOOD STERILIZATION........................................................................................................117 Introduction ............................................................................................................. 117 Drug Design ............................................................................................................ 117 Synthesis ..................................................................................................................120 Results and Discussion ...........................................................................................123 V. BIOPHYSICAL AND BIOCHEMICAL STUDIES OF AZIDOPHENOTHIAZINE DERIVATIVES......................................................... 126 VI. EXPLORATORY PHOTOCHEMISTRY OF POLYFLUORINATED 4-AZIDOBIPHENYL...................................................................................................131 Introduction ............................................................................................................... 131 Results and Discussion ............................................................................................ 132 VD. A KINETIC STUDY OF THE REACTION OF SINGLET PENTAFLUOROPHENYL NITRENE WITH VARIOUS OLEFINS............... 144 Introduction ............................................................................................................... 144 Results and Discussion ............................................................................................ 145 Vm. INTERNAL TRIPLET PHOTOSENSITIZATION OF CARBONYL-BEARING PHENYL AZIDES.......................................................... 156 Introduction ............................................................................................................... 156 Synthesis ....................................................................................................................160 Results and Discussion ............................................................................................ 163 IX. EXPERIMENTAL.................................................................................174 LIST OF REFERENCES............................................................................................................220 APPENDIX A. MISCELLANEOUS SPECTRA AND DATA........................................................ 230 vi LIST OF TABLES TABLE PAGE 1. Formation of Nitrencs ..............................................................................................................2 2. Preparation of Aryl Azides ......................................................................................................3
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