COMPUTATIONAL STUDIES OF DISUBSTITUTED BICYCLO[m.m.m]ALKANE AND DISUBSTITUTED BICYCLO[8.8.n]ALKANES, SYNTHESIS OF 1,10- DIMETHYLBICYCLO[8.8.8]HEXACOSANE AND 1,10- DIHYDROXYBICYCLO[8.8.8]HEXACOSANE, AND PROGRESS TOWARDS THE SYNTHESIS OF A DISUBSTITUTED 1,10- Item Type text; Electronic Dissertation Authors Jones, Ian W. Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 04/10/2021 14:27:50 Link to Item http://hdl.handle.net/10150/193585 COMPUTATIONAL STUDIES OF DISUBSTITUTED BICYCLO[m.m.m]ALKANE AND DISUBSTITUTED BICYCLO[8.8.n]ALKANES, SYNTHESIS OF 1,10-DIMETHYLBICYCLO[8.8.8]HEXACOSANE AND 1,10-DIHYDROXYBICYCLO[8.8.8]HEXACOSANE, AND PROGRESS TOWARDS THE SYNTHESIS OF A DISUBSTITUTED 1,10-BICYCLO[8.8.8]HEXACOSANE MONOMER by Ian Willis Jones Copyright © Ian W. Jones 2008 A Dissertation Submitted to the Faculty of the DEPARTMENT OF CHEMISTRY In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY In the Graduate College of THE UNIVERSITY OF ARIZONA 2008 2 THE UNIVERSITY OF ARIZONA GRADUATE COLLEGE As members of the Dissertation Committee, we certify that we have read the dissertation prepared by Ian W. Jones entitled Computational Studies of Disubstituted Bicyclo[m.m.m]alkane and Disubstituted Bicyclo[8.8.n]alkanes, Synthesis of 1,10-Dimethylbicyclo[8.8.8]hexacosane and 1,10-Dihydroxybicyclo[8.8.8]hexacosane, and Progress towards the Synthesis of a Disubstituted 1,10-bicyclo[8.8.8]hexacosane Monomer and recommend that it be accepted as fulfilling the dissertation requirement for the Degree of Doctor of Philosophy ___________________________________________________________Date: 11/20/08 Eugene A. Mash Jr. ___________________________________________________________Date: 11/20/08 Henry K. Hall Jr. ___________________________________________________________Date: 11/20/08 Richard S. Glass ___________________________________________________________Date: 11/20/08 Dennis L. Lichtenberger ___________________________________________________________Date: 11/20/08 Zhiping Zheng Final approval and acceptance of this dissertation is contingent upon the candidate's submission of the final copies of the dissertation to the Graduate College. I hereby certify that I have read this dissertation prepared under my direction and recommend that it be accepted as fulfilling the dissertation requirement. ____________________________________________________________Date: 1/13/09 Dissertation Director: Eugene A. Mash Jr. 3 STATEMENT BY AUTHOR This dissertation has been submitted in partial fulfillment of requirements for an advanced degree at the University of Arizona and is deposited in the University Library to be made available to borrowers under rules of the Library. Brief quotations from this dissertation are allowable without special permissions, provided that accurate acknowledgement of source is made. Requests for permissions for extended quotation from or reproduction of this manuscript in whole or in part may be granted by the copyright holder. SIGNED: Ian W. Jones 4 ACKNOWLEDGEMENTS I would like to acknowledge the following individuals: Dr. Eugene Mash for allowing me the opportunity to study and to be the first worker on the bicycle polymer project; Dr. Yasunari Monguchi for instructing me in correct organic lab technique and for the synthesis of 1,10-Dimethylbicyclo[8.8.8]hexacosane; Dr. Dennis Lichtenberger for teaching me the basics of computational chemistry in CHEM518; Dr. Matt Lynn for helping with computational computer questions; Dr. Hank Hall for his assistance concerning the polymer chemistry; and Ms. Karen Ragan for her assistance with the synthesis of 1,10-cyclooctadecanedione. 5 DEDICATION I would like to dedicate this document to my family for their continued support during my time in graduate school, and my friends and colleagues that have made the time in Tucson enjoyable and memorable. 6 TABLE OF CONTENTS LIST OF FIGURES………………………………………………………….………………………………….……………………..7 LIST OF SCHEMES…………………………………………………………..………………………………...….………………10 LIST OF TABLES……………………………………………………………………………………………………………………..13 LIST OF GRAPHS……………………………………………………………………………..…………….……..……………….15 ABSTRACT…………………………………………………………………………………………………..………………………..18 CHAPTER 1: INTRODUCTION TO BICYCLES AND IN,OUT ISOMERISM…………………..….….….……19 CHAPTER 2: CONFORMATIONAL STUDIES OF BRIDGEHEAD DISUBSTITUTED BICYCLO[m.m.m]ALKANE AND BRIDGEHEAD DISUBSTITUTED BICYCLO[8.8.n]ALKANE SYSTEMS………………………………………………………………………………………………………………………33 CHAPTER 3: SYNTHESIS AND CHARACTERIZATION OF MODEL BICYCLES……….…..…………....….80 CHAPTER 4: INTRODUCTION TO BICYCLE POLYMERS…………………………………….…………………..100 CHAPTER 5: SYNTHESIS AND CHARACTERIZATION OF BICYCLIC AND MONOCYCLIC MONOMERS……………………………………………………………………………………………………..……….112 CHAPTER 6: SYNTHESIS AND CHARACTERIZATION OF POLYMERS………………………………….…..143 CHAPTER 7: CONCLUSIONS AND FUTURE DIRECTIONS………………………………………………..…….149 APPENDIX A: NMR FOR 1,10-DIMETHYLBICYCLO[8.8.8]HEXACOSANE AND 1,10- DIHYDROXYIBYCLCO[8.8.8]HEXACOSANE……………………………………………………………..…….155 APPENDIX B: SELECTED SPECTRA FROM THE SYNTHESIS OF MONOCYCLIC DIOL MONOMER……………………………………………………………………………………………….………….…….176 APPENXIC C: SELECTED SPECTRA FROM THE SYNTHESIS OF BICYCLIC DIOL MONOMER…….184 REFERENCES……………………………………..…………………………………………………………………..…………..196 7 LIST OF FIGURES Figure 1.1: Examples of Monoterpenes Containing a Bicycle Unit…………………………………………..19 Figure 1.2: Possible Configurations and Relationships between Aliphatic Bicyclic Systems……..20 Figure 1.3: Homeomorphic Isomerism Observed in Bicyclo[8.8.8]hexacosane by Park and Simmons………………………………………………………………………………………………………………………………21 Figure 1.4: Interconversion of an in,out Structure to an Intertwined out,out Structure………….22 Figure 1.5: Natural Products Containing a Bicycle Core……………………………………………………………23 Figure 1.6: Natural Products Possessing in/out Configurations……………………………………..………..23 Figure 1.7: Structures and Configurations of Known Bicyclo[m.m.m]alkanes……………………..…..25 Figure 1.8: Experimental Observation of All Three Isomers of Bicyclo[6.5.1]tetradecane 1-5….28 Figure 1.9: Bridging Interior Hydride Observed in the Bicyclo[4.4.4]tetradecane Cation 1-12…30 Figure 1.10: Cartoon of Poly-accordions………………………………………………………………………….………31 Figure 2.1: Labels Used to Designate Distance and Angle Parameters…………………….….…………..36 Figure 2.2: Determining Orientation of Methyl Groups…………………………………………………….…….36 Figure 2.3: Different Gauche Angles For 1,10-Dimethylbicyclo[m.m.m]alkane………….…………….40 Figure 2.4: Three Structural Features of Interest…………………………………………………………..………..42 8 LIST OF FIGURES - Continued Figure 2.5: Global Minimum Structures and MMFF Energies for Dimethylbicyclo[m.m.m]alkanes…………………………………………………………………………………………..43 Figure 2.6: Global Minimum and Lowest Energy In,Out Isomers of 1,11-Dimethylbicyclo[9.9.9]nonacosane……………………………………….………………………………………44 Figure 2.7: Global Minimum Structure for 1,10-Dihydroxybicyclo[8.8.8]hexacosane……….……..59 Figure 2.8: Correlation of Unit Cell and MMFF Structures……………………………………………………….61 Figure 2.9: Global Minimum Structures for 1,10-Dimethylbicyclo[8.8.n]alkanes…………………….62 Figure 2.10: Directionality of Terminal Methyl Groups……………………………………………………..……66 Figure 2.11: Conformers Containing the Largest and Smallest Bite Angle within the Odd Numbered Dimethylbicyclo[8.8.n]alkane Family…………………………………………………………………..67 Figure 2.12: Conformers Containing the Largest and Smallest Bite Angle within the Even Numbered Dimethylbicyclo[8.8.n]alkane Family………………………………………………………………….68 Figure 3.1: Model Compounds 3-1 and 3-2……………………………………………………………….…………….80 Figure 3.2: Structure of 3-2 Observed in the Crystal………………………………………………..……………..91 Figure 3.3: Conformers of 3-1 Observed in the Crystal………………………………………..………………….92 Figure 4.1: Reaction of Monomer 4-1 into Oligomer 4-2………………….………………………………….100 9 LIST OF FIGURES - Continued Figure 4.2: Synthesis of Bicyclo[1.1.1]pentane Polymer 4-4……………………………………..……………101 Figure 4.3: An Example of an Alternating Co-polymer Containing the Bicyclo[1.1.1]pentane Core……………………………………………………………………………………………………………………….…………..101 Figure 4.4: Polyamide Bicyclo[1.1.1]pentane………………………………………………………………..……….103 Figure 4.5: Example of a Bicyclo[2.2.2]octane Polyester 4-19……………….……………….………………103 Figure 4.6: Monomers Based on Bicyclo[8.8.8]hexacosane Core……………………………………..……105 Figure 4.7: Initial Nylon 10 Copolymers to be Investigated……………………………………………..…….106 Figure 5.1: The Three Monomer Targets……………………………………………………………………………….112 Figure 6.1: Four Activated Sebacic Acid Derivatives…………………………………………………………….……….145 Figure 7.1: The Two Model Compounds 7-1 and 7-2………………………….…………………………………….…..152 Figure 7.2: Three Diol Monomers for Polyurethanes……………………………………………………………….…..153 10 LIST OF SCHEMES Scheme 1.1: Synthesis of Bicyclo[6.5.1]tetradec-1(2)-enes 1-4 in and 1-4 out………………………..26 Scheme 1.2: Hydrogenation to Yield Bicyclo[6.5.1]tetradecanes 1-5………………………………………27 Scheme 1.3: Synthesis of Bicyclo[4.4.4]tetradecane 1-11………………………………………….……………29 Scheme 3.1: Synthesis and Separation of Acyclic Isomers……………………………………………………….82 Scheme 3.2: Synthesis of Bicyclo[8.8.8]hexacosane Isomers………………………………………..…………83 Scheme 3.3: Synthesis of 1,10-Dihydroxybicyclo[8.8.8]hexacosane………………………………………..84 Scheme 3.4: Retrosynthetic Analysis