Thermal Rearrangements of Linear Carbon Chains: Theoretical and Experimental Studies John Mabry University of New Hampshire, Durham
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University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Winter 2003 Thermal rearrangements of linear carbon chains: Theoretical and experimental studies John Mabry University of New Hampshire, Durham Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation Mabry, John, "Thermal rearrangements of linear carbon chains: Theoretical and experimental studies" (2003). Doctoral Dissertations. 195. https://scholars.unh.edu/dissertation/195 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]. THERMAL REARRANGEMENTS OF LINEAR CARBON CHAINS THEORETICAL AND EXPERIMENTAL STUDIES BY JOHN MABRY B. S. HAMPTON UNIVERSITY, 1997 DISSERTATION Submitted to the University of New Hampshire in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Chemistry December, 2003 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. UMI Number: 3111508 Copyright 2004 by Mabry, John All rights reserved. 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 3111508 Copyright 2004 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. Dissertation Director Richard P. Johnson Professor of Chemistry ^^-H d w ard R. Jylaynef ProfesscSTrf Chemistry Chairperson of the Department of Chemistry 'Y Gary isman Profe f Chemistry Miller late Professor of Chemistry K Arthur Greenberg Dean of the College of Engineering and Physical Sciences Professor of Chemistry Robert J. Griffin Assistant Professor of Earth Sciences and Institute for the Study of Earth, Ocean, and Space / 0/3 h i Date Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. DEDICATION I dedicated t h i s dissertation to all single parent African-American mothers, and especially my mother, Barbara J. Mabry. My mother has been my pillar of strength and my source of wisdom. She instilled in my sisters and me, good work ethic, respect for others and ourselves, the importance of education, and to have faith in God. She encouraged us to set high goals and taught us how to effectively pursue them. She also taught us how to overcome barriers encountered in life. Being the ideal role model, she has always led by example. I consider her one of life’s true “warriors.” I thank you and t love you with all my heart. iii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENTS I would like to thank the people and organizations that have contributed to my success through this endeavor. Certainly, I could have not succeeded without the assistance of others. I have attempted to provide a list of some of those contributors. I would like to acknowledge my advisor, Professor Richard P. Johnson, for his guidance. I appreciate the excellent scientific training fhat I have received and guidance on becoming an effective educator. I consider him an outstanding mentor. i I I also would like to thank: Stefanie T. Mabry, James and Carol Mack, the UNH Chemistry Faculty, Amanda Burton Lapham and Jo Ann Moody of the New England Board of Higher Education, Reverend Robert Earls, Sr. and Saint John’s Baptist Church, Kathleen S. Gallagher and the University Instrumentation Center, Peg Torch and Cindi Rohwer of the Chemistry Office, Dr. Roger Beattie and the Office of the Vice President for Student and Academic Services, Dr. Harry Richards and the Graduate School, Dr. Arthur Greenberg and the College of Engineering and Physical Sciences, Bob Constantine and UNH Library Services, National Organization for the Professional Advancement of Black Chemists and Chemical Engineers (NOBCChE), Christian J. Kastrup, Susanne and David Lewis, Karelle S. Aiken, Wei-jun Niu, Martin G. Kociolek, Dhananjaya Nauduri, Mark Tetreau, Todd Ziemek, Chris and Angela Barnes, D. Nicole “Coley” Edwards. I would like to especially thank the Mabry, Mills, and Tucker families for their love, support, and prayers. iv Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS DEDICATION ............. iii ACKNOWLEDGEMENTS................. iv LIST OF SCHEMES............................. ix LIST OF FIGURES......................................... .............xiv LIST OF TABLES.............................................................. .....xvi ABSTRACT. ........ .........xvii CHAPTER PAGE GENERAL INTRODUCTION....................................................................................................1 I. PERICYCLIC AND DEHYDROPERICYCLIC REACTIONS................................2 Introduction to Pericyclic Reactions.. ........................................ 2 Electrocyclic Reactions ......................................................................... 6 Sigmatropic Shifts ..................................................................................9 Cycloadditions ......................................................................................13 Groups Transfers .................................... 24 Ene Reaction ........................................................................................ 26 Introduction to Dehydropericyclic Reactions.. ............ ...29 Dehydrobenzene Chemistry .................................... 29 /^-Benzene........................................ 30 m-Benzene ........... 34 o-Benzene ......................................................................... ......35 v Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. , Dehydro Diels-Alder Reactions, ............................................38 Enyne + Alkene Cycloaddition. .................... 40 Enyne + Alkyne Cycloaddition ........................... 42 Diyne + Alkene and Diyne + Alkyne .............. .49 Results and Discussion. ................. 52 Attempted Detection of Eneyne Cycloaddition ..................52 Conclusion. ............. 54 I II. CHEMISTRY OF C4H 2 .......................................................................................... 56 Introduction to High Temperature Gas Phase Chemistry of Alkynes, Arynes, and Aryl Radicals............................ 56 Secondary Reactions and Rearrangements ...................................... 63 High Temperature Chemistry of Arynes ...........................................6 6 Exocyclic Vinylidene Insertion Across a Bay Region ..... 6 8 Aryl Radicals and Radical Rearrangement .......................................70 Experimental Investigation of Thermal Rearrangements of Butadiynes ...........................................72 C4 H2 Chemistry................................. 78 Results and Discussion ....................................................................... 81 Synthesis and Thermolysis of 1,4-Diphenylbutadiyne (124) ....... 81 Synthesis and Thermolysis of Ditolyl-1,3-butadiyne (141)...................................................82 VI Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Synthesis o f13C Labeled Unsymmetrical Butadiyne . 8 8 Alternative Route to C1 -13C labeled j9 -tolylphenylbutadiyne (143) ........ 93 FVP Experiments of Doubly Labeled Diphenylbutadiyne (124) ..................... ....94 FVP Experiments of 13C Labeled p-Tolylphenylbutdiyne (160). .......... 98 Potential Reaction Mechanisms ....... .....102 Computational Studies ......................................................... 103 Conclusion. ............................ 109 III. CHEMISTRY OF C4 H4 .............................................................................................. 110 The Cyclopropylidene to Allene Rearrangement .................. .110 Thermal Rearrangements of Butatriene ....... 113 C4 H 4 Chemistry.................................................................................. 115 Results and Discussion ............................................................ ............ 125 Computational Results ................................. 125 Syntheses of Tetraarylbutatrienes .............. 130 Attempted Alternate Routes of Unsymmetrical Butatrienes 130 FVP Experiments of Allene, Butatriene, and Extended Cumulene Systems ........... 140 Conclusion ................ .144 vii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. IV. EXPERIMENTAL 145 V. APPENDICES........................................