University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Spring 2002 Diels -Alder reactions of [60]fullerene with 1,2,4,5-tetrazines and additions to [60]fullerene- tetrazine monoadducts Mark Christopher Tetreau University of New Hampshire, Durham Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation Tetreau, Mark Christopher, "Diels -Alder reactions of [60]fullerene with 1,2,4,5-tetrazines and additions to [60]fullerene-tetrazine monoadducts" (2002). Doctoral Dissertations. 81. https://scholars.unh.edu/dissertation/81 This Dissertation is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. 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Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6* x 9* black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order. ProQuest Information and Learning 300 North Zeeb Road. Ann Arbor, Ml 48106-1346 USA 800-521-0600 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. DIELS-ALDER REACTIONS OF [60JFULLERENE WITH 1,2,4,5-TETRAZINES AND ADDITIONS TO [60]FULLERENE-TETRAZINE MONOADDUCTS BY Mark Christopher Tetreau B.S. Principia College, 1995 DISSERTATION Submitted to the University o f New Hampshire in Partial Fulfillment of the Requirements for the Degree o f Doctor o f Philosophy in Chemistry M ay, 2002 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. UMI Number: 3045341 — .. (f t UMI UMI Microform 3045341 Copyright 2002 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. This dissertation has been examined and approved. ration Director, Glen P. M iller, iate Professor o f Chemistry R. Richard P. Johnson, r o f Chemistry Roy P. Plaiialp. fessor o f Chemistry l (a Charles K. Zercher, Associate Professor o f Chemistry Robert Jerald, Professor o f Mechanical Engineering 5 , Date Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. D ED IC A TIO N This work is dedicated to my wife, Gillian, who is a constant reminder that “Love never faileth.” Without her love, support, and inspiration this work would not have come to fruition. iii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENTS I would like to express my sincere gratitude to my advisor, D r. Glen M ille r. His input and direction kept me on the road to success. I would also like to thank the rest of the faculty on my thesis committee, Dr. Zercher, Dr. Johnson, Dr. Planalp, and Dr. Jerard, for their comments, questions, corrections and suggestions during my stay at the University o f New Hampshire. In addition, I would like to thank Dr. Weisman and Dr. Wong, two gentlemen who, while not on my committee, provided valuable suggestions and instruction. Thanks goes out to the rest o f the faculty and staff o f the UNH chemistry department for their contributions, however small, to this work. I would like to gratefully acknowledge Dr. Vem Reinhold for providing the mass spectrometry data, and Dr. Alan Balch for providing crystallographic data. I must also thank Kathy Gallagher o f the UNH Instrumentation Center for her technical expertise in obtaining NMR spectra. I would be remiss if I didn’t thank the members o f the M iller Research Group with whom I had the pleasure o f working over the years. James Mack’s invaluable advice got me started in the early days, and Steve Mathieu kept it interesting. I want to thank Jon, Julie, and Ingyu for adding to the good working atmosphere in the M iller Group. Most importantly, I want to thank my family -the Lincolns, Holcombs, Moores, and Tetreaus- for their unceasing support o f this endeavour. iv Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS D E D IC A T IO N ............................................................................................................. iii ACKNOWLEDGEMENTS.......................................................................................... iv LIST OF FIGURES.....................................................................................................vii LIST OF SCHEMES....................................................................................................ix LIST OF NUMBERED STRUCTURES..................................................................... x iii ABSTRACT............................................................................................................ xv iii 1. INTRODUCTION ..................................................................................................... 1 1.1. [60]Fullerene.............................................................................................. 1 1.1.1. History and Physical Properties o f [60]Fullerene........................... 1 1.1.2. Chemistry of Cm ......................................................................... 10 1.2. 1.2.4,5-Tetrazines..................................................................................... 29 1.2.1 History and Physical Properties o f 1,2.4,5-Tetrazines................... 29 1.2.2 Chemistry of 1,2.4,5-Tetrazines.................................................... 37 2. RESULTS AND DISCUSSION ............................................................................... 59 2.1. Synthesis of 1.2.4.5-Tetrazines................................................................. 59 2.2. Reaction Between Cm and 1,2.4.5-Tetrazines........................................... 69 2.3 Hydration of CM-Tetrazine Monoadducts.................................................. 83 2.4 Addition of Primary Amines to CM-Tetrazine Monoadducts.....................1 ''•0 2.5 Reaction of Monoprotic Nucleophiles with CM-Tetrazine Monoadducts ............................................................................................ 119 2.5.1. Towards Formation of a "Holey" Fullerene...............................119 V Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 2.52. Addition o f Aliphatic Thiols to 1 6 .............................................. 121 2.5.3 Addition of Aromatic Thiols to 1 6 ............................................... 128 2.5.4 Addition o f Alcohols to CwTetrazine Monoadducts ................... 134 2.5.5. Addition o f Secondary Amines to Cm-Tetrazine Monoadducts ........................................................................................136 2.6. Other Reactions Involving Caj-Tetrazine Monoadducts............................ 138 2.6.1 Addition o f Electrophiles to C6o-Tetrazine Monoadducts ............ 138 2.6.2 Free Radical Addition to C6o-Tetrazine Monoadducts................. 143 2.6.3. Electrocyclic Additions to CtfrTetrazine Monoadducts ............ 146 2.7. Miscellaneous Reactions with Ceo ............................................................ 148 3. CONCLUSION AND FUTURE WORK ................................................................. 153 4. EXPERIMENTAL ...................................................................................................155 4.1. General Methods...................................................................................... 155 4.2. Solvents.................................................................................................... 156 4.3. Chromatography...................................................................................... 157 4.4 Reagents.................................................................................................... 158 4.5 Syntheses..................................................................................................