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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 |! I 75-19.486 RUSSELL, Ronald Keith, 1947- !• EQUILIBRIUM IMBALANCES OF SELECTED 2,8-ANNULATED SEMIBULLVALENES AND REARRANGEMENTS OF 2,8-TETRAMETHYLENESEMIBULLVALENE. The Ohio State University, Ph.D., 1975 Chemistry, organic Xerox University Microfilms, Ann Arbor, Michigan 4S1 os 1 THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED. EQUILIBRIUM IMBALANCES OP SELECTED 2,8-ANNULATED SEMIBULLVALENES AND REARRANGEMENTS OF 2,8-TETRAMETHYLENESEMIBULLVAIENE . DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Ronald Keith Russell, B. S. # * * # # The Ohio State University 1975 Reading Coiimiittee: Approved by Dr. Leo A. Paquette Dr. Melvin S. Newman Dr. John A. Secrist, III Adviser® Department of Chemistry DEDICATION To my wife Nancy ii ACKNOWLEDGMENTS A scientific research group is a society of men and women, each having a particular expertise. The group of people that I have been associated with for the past four years have influenced my research and life in some manner; to these people I extend my thanks. In particular, I am deeply indebted to Professor Leo A. Paquette for his guidance as a research advisor and as a friend. I would also like to thank Professor R, J. Ouellette for his help in the computer simulation work and Mr. M. Geckle for his generous donation of time and energy in discussing ray research and obtaining cmr spectra. I gratefully acknowledge financial support from The Ohio State University in the form of University and Dissertation Fellowships, from the Chemistry Department in the form of Teaching Associate posi­ tions, and from Professor Paquette in the form of Research Associate positions. iii VITA November 2k, 1 9 ^ 7 .............. Born - Howell, Michigan 1970 .......................... B.S., Magna cum Laude, Central Michigan University, Mt. Pleasant, Michigan 197 0-I9 7 I ..................... University Fellow, The Ohio State University, Columbus, Ohio 1 9 7 1 -1 97 3 ..................... Graduate Teaching Associate, Department of Chemistry, The Ohio State University, Columbus, Ohio 1973 .......................... Research Associate, Department of Chemistry, The Ohio State Univer­ sity, Columbus, Ohio 1 97 3 -1 97 4 ...... .............. Dissertation Fellow, Tlie Ohio State University, Columbus, Ohio 1974 .......................... Research Associate, Department of Chemistry, The Ohio State Uni­ versity, Columbus, Ohio PUBLICATIONS ''Structural Consequences of 2,8 Bridging of the Semibullvalene Nucleus,'' L. A. Paquette, R. E. Wingard, Jr., and R. K. Russell, J. Amer. Chem. Soc., 94, 4739 (1971). ''Carbon-1 3 Nuclear Magnetic Resonance Spectral Analysis of Semi­ bullvalene and Related Substances,'' E. Wenkert, E. W. Hagaman, L. A. Paquette, R. E. Wingard, Jr., and R. K. Russell, JCS Chem. Commun., 135 (1973). ''The Thermochemical Behavior of Semibullvalenes. Annulation Effects on the Course of Rearrangement,'' L. A. Paquette, R. K. Russell, and R. E. Wingard, Jr., Tetrahedron Lett., 1713 (1973)' iv "Population Analysis of 2,8-Pentaniethylenesemi'bullvalene. ■ Direct Observation of Individual Wondegenerate Valence Isomers," R. K. Russell, L. A. Paquette, L. G. Greifenstein, and J. B. Lambert, Tetrahedron Lett., 2855 (1975). "Directed Syntheses of the Isomeric DimethyIcyclooctatetraenes and a Study of Their Polarographic and Alkali Metal Reduction,'' L. A. Paquette, S. V- Ley, R. H. Melsinger, R. K. Russell, and M. Oku, J. Amer. Chem. Soc. , 9^6, 5806 (1974). "Equilibrium Imbalances Arising from 2,8-Bridging by Aliphatic Chains of the Semibullvalene Nucleus," R, E. Wingard, Jr., R. K. Russell, and L. A. Paquette, J. Amer. Chem. Soc., 9 6 , T4t4 (1974). "Isomerization Behavior of 2,8-Tetramethylenesemibullvalene under Thermal, Photochemical, and Metal Catalyzed Conditions. An Excited State Semibullvalene-Semibullvalene Rearrangement,'’ R. K. Russell, R. E. Wingard, Jr., and L. A. Paquette, J. Amer. Chem. Soc., 9 6 , 7483 (1974). FIELDS OF STUDY Major Field; Organic Chemistry TABLE OF CONTENTS Page DEDICATION................................................ 11 ACKNOWLEDGMENTS........................................... Ill VITA .................................................... Iv LIST OF FIGURES........................................... vll LIST OF ILLUSTRATIONS ...................................... vlll LIST OF TABLES............................................ X INTRODUCTION.............................................. 1 RESUI.HF. AND DISCUSSION PART I. Annulated Semibullvalenes........... l8 PART II. Rearrangements of 2,8-Tetraraethylene- semibullvalene ............................... 87 EXPERIMENTAL.............................................. 128 REFERENCES ................................................ 195 vl LIST OF FIGURES Figure ' Page 1 Hie proton magnetic resonance spectrum of penta- methylenesemibullvalene 71 as a function of temperature in CFgCls/CD^Clg ........................ 65 2 The 100 MIIz pmr spectrum of 2,8-trimethylene- semibullvalene (^) in CDCI3 at 500 Hz sweep width 85,86 3 The 100 MHz pmr spectrum of 2,8-tetramethylene- semibullvalene ( 6 ^ in CDCI3 at 500 Hz sweep w i d t h 85 4 The 100 MHz pmr spectrum of 2,8-pentamethylene- semibullvalene (7^) in CDCI3 at 5OO Hz sweep width .... 85 5 The 100 MHz pmr spectrum of oxasemibullvalene gj in CSg at 500 Hz sweep width 86 6 The 100 MHz pmr spectrum of thiasemibullvalene 13g in OS3 at 500 Hz sweep width ##**##*####*######*####*#*#* 86 7 Experiment (A,b ) and computer simulated (C,d ) partial 100-MHz pmr spectra of (a) the 1,2-tetramethylene- cyclooctatetraene-'rCNE adduct; (b) and (d) the 2,7-dg derivative 1^; and (C) the 2,8-d2 derivative 1 6 2 ..... 99 8 Pmr spectra (60 MHz) of (top) 2(4)-methylsemlbullvalene and (bottom) 1 ,2-tetramehylenesemibullvalene (172 ) in OS2 solution................................... I06 9 The 100 MHz pmr spectrum of l^J in CDCI3 at 1000 Hz sweep width .................... 127 10 The 100 MHz pmr spectrum of 203 in CDCI3 at 1000 Hz sweep w i d t h ............................. 127 11 The 100 MHz pmr spectrum of 190 in CDCI3 at 1000 Hz sweep width ....................................... 127 vii LIST OP ILLUSTRATIONS Scheme Page I Correlation of Transition State and Product in the pyrolysis of meso and racemic 3,4-Dimethyl-l,5- hexadienes (6) ..................... 5 II General Synthetic Approach to 2,8-Annulated Semi­ bullvalenes 3^ ...... 22 III Synthetic Approach to [4.3.2]Propella-2,4,10-triene (52) ............................................ 23 IV Synthetic Approach to 2,8-Trimethylenesemibullvalene (57) ............................................ 26 V Hydrolysis-Oxidation of ^ ......................... 28 VI Synthetic Approach to 2,8-Tetramethylenesemibull- valene (^) .................................. $4 VII Synthetic Approach to 2,8-Pentamethylenesemibull- valene (71) ...................................... 36 VIII Synthetic Approach to 8-Qxa[4.3»2]propella-2,^f,10- triene (86) ...................................... 40 IX Synthetic Approach to 8-0xa[4.3«2]propella-2,10- diene (92) ....................................... ^5 X Synthetic Approach to Oxasemibullvalene 2X • ......... 47 XI Synthetic Approach to l,3,5a,4,5,5a,6,7,7a,7b-Deca- hydropentalenofl,6-cdlpyran (99) ................... 50 XII Synthetic Approach to 8-Thia[^.3'2]propella-2,4,10- triene (3J^) ..................................... 51 XIII Synthetic Approach to Thiasemibullvalene 119 ......... 54 XIV Possible Mechanistic Pathways to Cyclooctatetraene (1 3 3) from
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