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Polycyclic Polyamines: Synthesis and Conformational Analysis University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Spring 1982 POLYCYCLIC POLYAMINES: SYNTHESIS AND CONFORMATIONAL ANALYSIS VAN BRUCE JOHNSON Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation JOHNSON, VAN BRUCE, "POLYCYCLIC POLYAMINES: SYNTHESIS AND CONFORMATIONAL ANALYSIS" (1982). Doctoral Dissertations. 1318. https://scholars.unh.edu/dissertation/1318 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]. INFORMATION TO USERS This reproduction was made from a copy of a document sent to us for microfilming. While the most advanced technology has been used to photograph and reproduce this document, the quality of the reproduction is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help clarify markings or notations which may appear on this reproduction. 1.The sign or “target” for pages apparently lacking from the document photographed is “Missing Page(s)”. If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting through an image and duplicating adjacent pages to assure complete continuity. 2. When an image on the film is obliterated with a round black mark, it is an indication of either blurred copy because of movement during exposure, duplicate copy, or copyrighted materials that should not have been filmed. For blurred pages, a good image of the page can be found in the adjacent frame. If copyrighted materials were deleted, a target note will appear listing the pages in the adjacent frame. 3. When a map, drawing or chart, etc., is part of the material being photographed, a definite method of “sectioning” the material has been followed. It is customary to begin filming at the upper left hand comer of a large sheet and to continue from left to right in equal sections with small overlaps. If necessary, sectioning is continued again—beginning below the first row and continuing on until complete. 4. For illustrations that cannot be satisfactorily reproduced by xerographic means, photographic prints can be purchased at additional cost and inserted into your xerographic copy. These prints are available upon request from the Dissertations Customer Services Department. 5. Some pages in any document may have indistinct print. In all cases the best available copy has been filmed. University M icrofilms International 300 N. Zeeb Road Ann Arbor, Ml 48106 8227427 Johnson, Van Bruce POLYCYCLIC POLYAMINES: SYNTHESIS AND CONFORMATIONAL ANALYSIS University of New Hampshire Ph.D. 1982 University Microfilms International 300 N. Zeeb Road, Ann Arbor, MI 48106 PLEASE NOTE: In all cases this material has been filmed in the best possible way from tine available copy. Problems encountered with this document have been identified here with a check mark V . 1. Glossy photographs or pages______ 2. Colored illustrations, paper or print_____ 3. Photographs with dark background _____ 4. Illustrations are poor copy i / 5. Pages with black marks, not original copy______ 6. Print shows through as there is text on both sides of page______ 7. Indistinct, broken or small print on several pages S 8. Print exceeds margin requirements_____ 9. Tightly bound copy with print lost in spine______ 10. Computer printout pages with indistinct print______ 11. Page(s)___________ lacking when material received, and not available from school or author. 12. Page(s)___________ seem to be missing in numbering only as text follows. 13. Two pages numbered ___________ . Text follows. 14. Curling and wrinkled pages ______ 15. Other_________________________________ ____ ______________________________ University Microfilms International POLYCYCLIC POLYAMINES: SYNTHESIS AND CONFORMATIONAL ANALYSIS BY Van E Johnson B. S. (Chemistry), Southern Connecticut State College, 1977 A DISSERTATION Submitted to the University of New Hampshire in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Chemi stry May, 19 82 This dissertation has been examined and approved. (<9 € i • ^ v ^ v<_____________________ Dissertation Director, Gary R. Weisman Assistant..Professor of Chemistry ' W ^ y y v q —- JameAfD. Morrison Professor of Chemistry Kenneth K. Andersen Professor of Chemistry Charles W. Owens Professor of Chemistry Donald C. Sundburg // Assistant Professor erf Chemical Engineering Q m . n z i - ' Date / DEDICATION This dissertation is dedicated to my family. They are the reason. iii ACKNOWLEDGEMENTS Gary R Weisman has been throughout my graduate work a tireless teacher, enthusiastic researcher, invaluble resource, and a friend. I am grateful for his efforts on my behalf. I am, of course, grateful to the chemistry department for its financial and morale support. There are a number of individuals who deserve my special thanks including: Mike Coolidge - for setting up the computer programs and training me in their use, Rudy Seitz - for the use of the syringe pump, Kathy Gallagher - for training me on the FX90Q, Bill Dotchin and Dee Cardin for same day service on the mass spec, and CHN analyses. i v TABLE OF CONTENTS DEDICATION....................................................... iii ACKNOWLEDGEMENTS................................................. iv LIST OF FIGURES............. ..................................... vii LIST OF TABLES........ xiii ABSTRACT........... ............. ................................ xiv CHAPTER ONE-INTRODUCTION Efforts Towards the Synthesis/gf-;U5,9>13- tetraazatricycloC7.7.3.3 5 Mocosane .............. 1 Synthesis................................................ 6 Anticipated Properties....................................8 Complexation Properties.............................. 9 Electrochemical Properties. ..................... .10 Discussion............................................... 13 Synthesis........................................... 13 Classical Approach.............................. 16 Modified Classical.............................. 20 Cleavage Routes-Cleavage of Tetracyclic Bis-aminals................................ 2h Cleavage of a Tricyclic Orthoamide......... .... 26 CHAPTER TWO-TRICYCLIC ORTHOAMIDES.............................. 28 Discussion................ ^1 Synthesis...................................... ^1 Conformational Analysis of the Orthoamides................ lj-7 Introduction..................... ^7 Conformational Analysis of the Orthoformamides............ 55 Stereochemical Variation in the Orthoformamides ....55 Conformational Analysis of H-222........ 6b Conformational Analysis of H-322...... 67 Conformational Analysis of H-332........... 70 Conformational Analysis of H-333............. ..75 Conformational Analysis of the Orthoacetamides ........... 79 Introduction......................................... .79 Conformational Analysis of Me-222-............. 80 Conformational Analysis of Me-322.............. 83 Conformational Analysis of Me-332... .......... 8^ Conformational Analysis of Me-333. ......... 89 Conformational Analysis of the Orthopropionamides .....101 Introduction.............. 101 Conformational Analysis of Bt-222...... 102 Conformational Analysis of Et-322..... 103 Conformational Analysis of Et-332.............. 108 Conformational Analysis of Et-333.............. 115 v Structure Reactivity Relationships of the Orthoamides......................................128 Introduction.....................................128 Alkylation of the Ortho amides............... 129 Synthetic Applications of the Alkylation of H-333.................... 137 Hydrolysis................... ................... lUO Hydrolysis of H-222......................... 151 Hydrolysis of H-333..... «.................. 153 Acylation of H-333............................... 160 MM2 Calculations......................................l6U 222-Ring System.................................. 172 322-Ring System.................................. 172 322 Ortho formamides............. 173 322 Orthoacetamides......................... 173 322 Orthopropionamides................. .....173 332-Ring System.................................. 17^ 332 Orthoformamides.......... 17^ 332 Orthoacetamides......................... 175 332 Orthopropionamides...................... 175 333-Ring System. .............................. 176 333 Orthoformamides......................... 176 333 Orthoacetamides......................... 177 333 Orthopropionamides...................... 178 Conclusions......................................178 Evaluation of the Energy Trends in the Minimum Energy Ground States of the Orthoamides by MM2 ..................... 192 CHAPTER THREE-EXPERIMENTAL................................. 20k General Aspects.......................................20l+ Instrumental Aspects.............................. 2014- High Dilution Apparatus.......................... 205 Gel Permeation Chromatography.................... 207 Experimental .... 208 pKa Determinations............................... 211 DNMR.............................................211 Synthesis........................................213 APPENDIX 1: ^H NMR and IR Spectra of New Compounds.............. 2U3 APPENDIX
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