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The Synthesis of Heteromacrocycles Containing the 2,6-Pyridine Moiety

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The Synthesis of Heteromacrocycles Containing the 2,6-Pyridine Moiety Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1976 The yS nthesis of Heteromacrocycles Containing the 2,6-Pyridine Moiety. Joe Dean Sauer Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Sauer, Joe Dean, "The yS nthesis of Heteromacrocycles Containing the 2,6-Pyridine Moiety." (1976). LSU Historical Dissertations and Theses. 2938. https://digitalcommons.lsu.edu/gradschool_disstheses/2938 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. INFORMATION TO USERS This material was produced from a microfilm copy of the original document. While the most advanced technological means to photograph and reproduce this document have been used, the quality is heavily dependent upon the quality of the original submitted. The following explanation of techniques is provided to help you understand markings or patterns 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 thru an image and duplicating adjacent pages to insure you complete continuity. 2. When an image on the film is obliterated with a large round black mark, it is an indication that the photographer suspected that the copy may have moved during exposure and thus cause a blurred image. 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Xerox University Microfilms 300 North Zeeb Road Ann Arbor, Michigan 48106 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 76-25,281 SAUER, Joe Dean, 1948- THE SYNTHESIS OF HETEROMACROCYCLES CONTAINING THE 2,6-PYRIDINE MOIETY. The Louisiana State University and Agricultural and Mechanical College PntD,, 1976 Chemistry, organic Xerox University Microfilms , Ann Arbor, Michigan 48106 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. THE SYNTHESIS OF HETEROMACROCYCLES CONTAINING THE 2,6-PYRIDINE MOIETY A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Joe Dean Sauer B.S., Oklahoma Southwestern State College, 1970 May, 1976 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. to Carolyn ii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGMENT The author wpuld like to recognize and thank Dr. George R. Newkome for his uififlagging support and encouragement. More than that, the author deeply appreciates the example Dr. Newkome provides for his students in daily contact both in and out of the laboratory. The author wpuld also like to thank his family, especially his wife, Carolyn, for the understanding and help throughout the past years. Special thanks are also offered to Carolyn for her untiring work in preparing the preliminary drafts of this dissertation. Financial support was provided by Louisiana State University and the National Institute of Health throughout the span of this research. The writer gratefully acknowledges financial assistance from the Dr. Charles E. Coates Memorial Fund of the Louisiana State University Foundation, for expenses incurred in the publication of this dissertationr iii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS PAGE ACKNOWLEDGMENT .............................................. iii LIST OF TABLES ............... • ........................................................................ XV LIST OF ILLUSTRATIONS....................................... xviii A. Diagrams....................................... xviii B. F i g u r e s ....................................... xix C. S c h e m e s ....................................... xx ABSTRACT .................................................... xxiv I. INTRODUCTION....................................... 1 A. General Information .......................... 1 B. Literature Review of Macrocycles containing the 2,6-Pyridino Moiety ....................... 23 1. C-Macrocycles Containing a 2,6-Pyridino Moiety..................................... 23 2. N-Macrocycles Containing a 2,6-Pyridino Moiety..................................... 27 3. S-Macrocycles Containing a 2,6-Pyridino Moiety..................................... 27 4. C,O-Macrocycles Containing a 2,6-Pyridino Moiety. .............................. 28 5. C,N-Macrocycles Containing a 2,6-Pyridino Moiety..................................... 31 6. C,S-Macrocycles Containing a 2,6-Pyridino Moiety..................................... 34 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 7. C,N,O-Macrocycles Containing a 2,6-Pyridino Moiety....................................... 37 8. C,0,S-Macrocycles Containing a 2,6-Pyridino Moiety....................................... 38 9. C,N,S-Macrocycles Containing a 2,6-Pyridino Moiety....................................... 39 10. C,N,P-Macrocycles Containing a 2,6-Pyridino Moiety....................................... 40 11. C-Macrocycles Containing a 2,5-Pyridino Moiety....................................... 41 12. C,O-Macrocycles Containing a 2,5-Pyridino Moiety....................................... 43 13. C,S-Macrocycles Containing a 2,5-Pyridino Moiety....................................... 43 14. C-Macrocycles Containing a 3,5-Pyridino Moiety....................................... 44 15. C,N-Macrocycles Containing a 3,5-Pyridino Moiety....................................... 46 16. C,S-Macrocycles Containing a 3,5-Pyridino Moiety....................................... 46 17. C-Macrocycles Containing a 2,4-Pyridino Moiety....................................... 47 18. C,N-Macrocycles Containing a 2,4-Pyridino Moiety....................................... 50 19. C-Macrocycles Containing a 2,3-Pyridino Moiety....................................... 51 v Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 20. C,N-Macrocycles Containing a 2,3-Pyridino Moiety..................................... 53 21. C-Macrocycles Containing a 3,4-Pyridino Moiety..................................... 53 22. Collection of Literature Reviews on the Synthesis of Hetero-Macrocycles ......... 54 23. Literature References Pertaining to Nomenclature Systems for Heteromacrocycles 54 24. Review Bibliography ..................... 55 C. Proposed Research............................... 63 1. Part 1. Cyclic Pyridylketones. System III 63 2. Part 2. Cyclic Pyridyl Acetylenes and Cumulenes. System V ...................... 70 II. E X PERIMENTAL....................................... 75 A. General Information ........................... 75 B. Solvents ........................................ 75 C. Specific Reaction Procedures ................... 77 1. Methyllithium ............................. 77 2. 2-Bromo-6-pyridyllithium .................. 77 3. 6-Bromo-2-picolinic a c i d .................. 78 4. 6-Bromo-2-picolinoyl Chloride. Method A. Treatment of 6-Bromo-2-picolinic Acid with Thionyl Chloride .......................... 78 5. 6-Chloro-2-picolinic Acid. vi£ Halogen Exchange on 6-Bromo-2-picolinic Acid . 79 6. Transhalogenation of 2,6-Dichloropyridine. 79 vi Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 7. 2-Picolinoyl Bromide. Method A. Treatment of 2-Pyridinecarboxylic Acid with Thionyl Bromide ..................................... 80 8. 2-Picolinoyl Bromide. Method B. Treatment of 2-Picolinic Acid with Phosphorous Tribromide................................... 80 9. 2-Picolinamide.............................. 80 10. 2-Cyanopyridine ............................. 81 11. 6-Bromo-2-picolinoyl Bromide. Method B. Treatment of 6-Bromo-2-picolinic Acid with Thionyl Bromide ............................ 81 12. 6-Bromo-2-picolinoyl Bromide. Method C. Treatment of 6-Bromopicolinic Acid with Phosphorous Tribromide............... .
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