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University of Florida Thesis Or Dissertation Formatting STUDIES IN HETEROCYCLIC SYNTHESIS By LONGCHUAN HUANG A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 2010 1 © 2010 Longchuan Huang 2 To my parents Fayun Huang and Miaorong Zhu, to my brother Jiajia Huang, and to my dear friends for their unconditional love and support 3 ACKNOWLEDGMENTS I would like to express my gratitude to my advisor, Professor Alan R. Katritzky, for his consistant support and guidance, which were essential for me to complete my studies. His overall knowledge of science, not just chemistry, and his strong devotions to science and education is extremely impressive. His mentorship has guided me through many challenges as a graduate student, and I will always remain appreciative and thankful for the opportunity working with him. I would especially like to thank Dr. C. Dennis Hall for his constructive and helpful suggestions for my research and for his kindness and patience with reading and correcting my writing over and over again. Also, I want to thank Dr. John Reynolds, Dr. Ion Ghiviriga, Dr. Weihong Tan and Dr. Fazil Najafi for their time as members of my committee. Their knowledge, advice, and support have been a valuable and cherished resource during my graduate career. This work would not have been possible without the hard work of my coworkers with whom I have interacted: Dr. Rajeev Sakhuja for his expertise in both chemistry and as a group leader; Dr. Prahbu Mohapatra for the teamwork on the synthesis of 1,3,4- oxadiazoles in Chapter 3. My thanks must go to Dr. Yuming Song, Ms. Reena Gyanda and Ms. Ling Wang who all have contributed to the triazole-polymer project described in Appendix. I would like to thank all of the present and past members of the Katritzky research group. I have made some great friends and enjoyed their company during the past four years. Their friendship and support have made this period of my life more pleasant and memorable. 4 TABLE OF CONTENTS page ACKNOWLEDGMENTS .................................................................................................. 4 TABLE OF CONTENTS .................................................................................................. 5 LIST OF TABLES ............................................................................................................ 9 LIST OF FIGURES ........................................................................................................ 10 LIST OF SCHEMES ...................................................................................................... 12 LIST OF ABBREVIATIONS ........................................................................................... 16 ABSTRACT ................................................................................................................... 20 CHAPTER 1 INTRODUCTION TO BENZOTRIAZOLE CHEMISTRY .......................................... 21 1.1 Benzotriazole .................................................................................................... 21 1.1.1 Structure and Isomerization ..................................................................... 21 1.1.2 Synthesis of Benzotriazoles .................................................................... 23 1.2 Activation Ability of the Benzotriazole Ring ....................................................... 24 1.2.1 As a Proton Activator or an Anion Stabilizer ............................................ 24 1.2.2 As a Leaving Group ................................................................................. 25 1.2.3 As an Ambient Anion-Directing Group ..................................................... 26 1.2.4 As a Radical Stabilizer or a Radical Precursor ........................................ 26 1.2.5 As an Anion Precursor ............................................................................. 27 1.3 N-Acylbenzotriazoles in Heterocyclic Synthesis ............................................... 27 1.3.1 Preparation of N-Acylbenzotriazoles ....................................................... 27 1.3.2 N-Acylbenzotriazoles for N-, S- , C- and O- Acylation ............................. 28 1.3.2.1 Selective synthesis of S-acyl and N-acylcysteines ......................... 29 1.3.2.2 Selective synthesis of S-acylglutathiones and N- acylglutathiones ...................................................................................... 29 1.3.2.3 Synthesis of N-Cbz-protected (α-aminoacyl)methylenepyridines and -quinolines ....................................................................................... 30 1.3.2.4 Synthesis of S-acylisotripeptides ................................................... 30 1.3.2.5 Synthesis of azo-dye labeled amino acids and amines .................. 31 1.3.2.6 Synthesis of chiral O-(α-protected-aminoacyl)steroids ................... 31 1.3.2.7 Synthesis of pyridin-2-ylmethyl ketones ......................................... 32 1.3.2.8 Synthesis of 1-(benzotriazol-1-yl)alkyl- ethers and esters .............. 33 1.3.2.9 Bt-mediated C-acylation ................................................................. 33 1.3.3 Expansion of the Scope for N-Acylbenzotriazole Applications in Heterocyclic Synthesis .................................................................................. 34 5 2 EFFICIENT SYNTHESES OF NAPHTHOQUINONE DIPEPTIDES ....................... 35 2.1 Introduction ....................................................................................................... 35 2.1.1 Background ............................................................................................. 35 2.1.2 Interaction of Quinones and Amino Acids in Nature ................................ 39 2.1.3 Application of Quinone-Amino Acid Conjugates ...................................... 39 2.1.4 Literature Preparative Methods for Quinone-Amino Acid Conjugates ..... 40 2.2 Results and Discussion ..................................................................................... 43 2.2.1 Reaction of Naphthoquinone-Amino Acid Conjugates ............................. 43 2.2.2 Reaction of Thio-substituted Benzoquinone with Amino Acids ................ 47 2.2.3 Preparation of Benzotriazole Activated Benzoquinone-Amino Acid Conjugates .................................................................................................... 49 2.3 Conclusion ........................................................................................................ 49 2.4 Experimental Section ........................................................................................ 49 3 1,3,4-OXADIAZOLES FROM FUCTIONALIZED N-ACYLBENZOTRIAZOLES AND ACYLHYDRAZIDES ....................................................................................... 66 3.1 Introduction ....................................................................................................... 66 3.1.1 Oxadiazoles ............................................................................................. 66 3.1.2 Biologically Active 1,3,4-Oxadiazoles ...................................................... 66 3.1.3 Polymeric 1,3,4-Oxadiazoles ................................................................... 67 3.1.4 Luminescent Compounds, Dyes and Photosensitive Materials ............... 68 3.1.5 Other Miscellaneous Applications ........................................................... 69 3.1.6 Literature Preparative Methods for 1,3,4-Oxadiazoles ............................ 70 3.2 Results and Discussion ..................................................................................... 74 3.3 Conclusion ........................................................................................................ 75 3.4 Experimental Section ........................................................................................ 76 3.4.1 General Procedure for the Preparation of 1,3,4-Oxadiazole .................... 77 4 OVERVIEW OF N-HYDROXYAMIDOXIMES, N-AMINOAMIDOXIMES AND HYDRAZIDINES ..................................................................................................... 81 4.1 Introduction ....................................................................................................... 81 4.2 Structure and Configuration .............................................................................. 83 4.2.1 N-Hydroxyamidoximes ............................................................................ 83 4.2.2 N-Aminoamidoxime ................................................................................. 85 4.2.3 Hydrazidines ............................................................................................ 85 4.3 Preparative Methods ......................................................................................... 86 4.3.1 N-Hydroxyamidoximes and Their Derivatives .......................................... 86 4.3.1.1 From oximidoyl chlorides and hydroxyamines ............................... 86 4.3.1.2 From amidoximes and hydroxyamine ............................................ 87 4.3.1.3 From nitrile oxides and hydroxyamines .......................................... 87 4.3.1.4 Miscellaneous preparative methods for di-O-alkyl derivatives of N-hydroxyamidoximes ............................................................................ 88 4.3.2 N-Aminoamidoximes and Their Derivatives ............................................. 89 4.3.2.1 From oxime chlorides or amidoximes ............................................
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