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Xerox University Microfilms 300 North Zaab Road Ann Arbor, Michigan 48106 77-2364 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. You w ill find a good image of the page in the adjacent frame. 3. When a map, drawing or chart, etc., was part of the material being photographed the photographer followed a definite method in "sectioning" the material. It is customary to begin photoing at the upper left hand corner of a large sheet and to continue photoing from left to right in equal sections with a small overlap. If necessary, sectioning is continued again - beginning below the first row and continuing on until complete. 4. The majority of users indicate that the textual content is of greatest value, however, a somewhat higher quality reproduction could be made from "photographs" if essential to the understanding of the dissertation. Silver prints of "photographs" may be ordered at additional charge by writing the Order Department, giving the catalog number, title, author and specific pages you wish reproduced. 5. PLEASE NOTE: Some pages may have indistinct print. Filmed as received. Xerox University Microfilms 300 North Zaab Road Ann Arbor, Michigan 48106 77-2364 CARMODY, Michael John, 1950- THERMAL ISOMERIZATIONS OF cis-9,10- DIHYDRONAPHTHALENE DERIVATIVESt AND THERMAL AND SOLVOLYTIC CHEMISTRY OF TRICYCLO[4.2.0.02,5]0CTA-3,7-DIENE DERIVATIVES. The Ohio State University, Ph.D., 1976 Chemistry, organic Xerox University MicrofilmsAnn , Arbor, Michigan 48106 THERMAL ISOMERIZATIONS OF cls-9,10-DIHYDRONAPHTHALENE DERIVATIVES, AND THERMAL AND SOLVOLYTIC CHEMISTRY OF TRICYCLOL^.2*0.02,5]OCTA-3,7-DIENE DERIVATIVES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Michael John Carmody, B.S, # # # # * The Ohio State University 1976 Reading Committee: Approved by Leo A. Paquette Harold Shechter Robert J. Oullette c x . Advisor Department of Chemistry DEDICATION To Ann and Emily, my girls. ii ACKNOWLEDGMENTS The author would like to thank Dr. Charles Cottrell for the recording of all 13C and 1H (FT) pmr spectra, Including the variable temperature data in Part II. Mr. J, Michael Geckle is acknowledged for the LAOCOON treatments and patient instruction in the use of DNMR programs. In addition, the author expresses gratitude to all of his coworkers whose advice and criticism shaped the content of this manuscript as the experimental work and writing progressed. The growth of these coworkers into friends made the pursuit of knowledge emotionally as well as intellectually rewarding. Special thanks are accorded to Dr. Leo A. Paquette whose imagination and enthusiasm provided the impetus for this work and the authors development as an organic chemist. A great scientist who can relate to people on such a human level is rare indeed. Finally the author wishes to thank his wife, Ann, not only for typing the manuscript but also for the en­ couragement and understanding without which this work could not have been completed. iii VITA May 14, 1950 Born - Detroit, Michigan 1972 ...... B.S., University of Detroit, Detroit, Michigan 1972 - 1974 Teaching Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio 1974 - 1976 Research Assistant, Depart­ ment of Chemistry, The Ohio 'State University, Columbus, Ohio PUBLICATIONS L.A. Paquette and M.J, Carmody, "Thermal Isomerization Reactions of cis-9,10-Dihydronaphthalene Derivatives," J. Amer. Chem. Soc., ^1* 5941 (1975). L.A. Paquette and M.J. Carmody, "Thermally Promoted Ring Cleavage Reactions of Tetracyclo[4.3*0.02,5,07»9]non- 3-enes, Pentacyclo[5•3•0.02,0 ,03,5.0°,10]decanes, and Their Epoxide Counterparts," J. Amer. Chem. Soc.. submitted. L.A. Paquette, M.J. Carmody, J.M. Geckle, "DNMR Analysis of Ring Inversion in anti_-l ,5-Bis homo eye looct ate traenes, " Tetrahedron Lett,, in press. iv TABLE OF CONTENTS Page DEDICATION ......................................... 11 ACKNOWLEDGMENTS ................................ Ill VITA ................................................. lv LIST OF FIGURES . ................................... vll LIST OF ILLUSTRATIONS ............................ Vlii LIST OF TABLES .................................... ix THERMAL REARRANGEMENTS OF cls-9,10-DIHYDR0- NAPHTHALENE DERIVATIVES .............. 1 Introduction ............................ 2 Results ........................ ......... 15 r( Discussion .............................. 31 Experimental ............. 43 THERMAL REACTIONS OF TRICYCLO[4.2.0.02 »5]OCTA- 3.7-DIENE DERIVATIVES ................ 59 Introduction ........................ 60 Results .......................*......... 72 Discussion .............................. 97 Experimental ............................ 102 SOLVOLYTIC STUDIES OF TRICYCLOC4.2.0.02*53-OCTA- 3.7-DIENE DERIVATIVES ................. 115 v Introduction ........................ 116 Results ............................. 123 Discussion .......................... 133 Experimental ...................... 1^3 APPENDIX .................................... 160 REFERENCES .................................. 164 vi LIST OF FIGURES Figure Page 1 Variable temperature jjMR of 107 .... 88 2 Variable temperature NMR of 109 ...... 90 ^ ^ 3 Variable temperature NMR of 111 ..... 93 4 Energy profiles for ring inversion in 107 109 i H I ............................ 777 9* 5 Diagram of orbital splitting due to through bond interaction ............. 119 vii LIST OF ILLUSTRATIONS Scheme Page I Orbital symmetry allowed interconver­ sions on the ( C H ^ q energy surface ......................... 5 II Retro Dlels-Alder mechanism for rearrange­ ment of 13 and 35 ..................... 32 III Cope rearrangement mechanism for 13 and 35 ” ...... 34 IV [l.SlSigmatropic shift mechanism for rear­ rangement mechanism of 13 and 35 .... 35 V [10]Annulene mechanism for rearrangement of 13 and 35 ......................... ,39 VI Conversion of 132 to 142 138 “ w- “m viii LIST OF TABLES Table Page I Isomerization - Dehydrogenation Studies of 22 and 23 at 80° ..................... 19 II Isomerization - Dehydrogenation Studies of 13, 22, and 23 at 100°........... 22 III Vapor Phase Thermolysis of 42 ............ 26 IV Rate Constants and Activation Parameters for Thermal Rearrangement of 13 and 35 . • 26 ^ - V •S* V ^-H NMR Data for Tetracyclononanes ........ 75 VI 1H NMR Data for Pentacyclodecanes ....... 76 VII !3c NMR Data for 100 - 103 ................ 77 VIII Rate Constants and Activation Parameters for the Thermal^Rearrangement of Penta- cyclo[5* 3.0.02 , 6 . * 5 . o u,iu]aecanes .. o3 IX Rate Constants and Activation Parameters for the Thermal Rearrangement of the Tetracyclo[.3.0.o2»5.o3,5,o? >9 jnonenes and Related Compounds ................. 85 X Thermodynamic Data and Activation Para­ meters for the Ring Inversions In 107, 109, 111 ........................... 91 XI Rates of Acetolysis of 131 - 134 in Acetic Acid .......................... 125 XII Example of a Solvolytic Rate Calculation . 152 Ix THERMAL REARRANGEMENTS OF 9 ,10-DIHYDRONAPHTHALENE DERIVATIVES INTRODUCTION Monocyclic polyenes have held chemists' attention since * f~i s~ X Kekule's proposal for the structure of benzene in 1865 . The uniqueness of benzene's "aromatic sextet" was placed into 2 a more general context when Huckel published a quantum mechanically based theory which predicted enhanced stability for those monocyclic fully conjugated polyenes which contained a closed shell of *Jn + 2 electrons. The 4n homolog of benzene, cyclooctatetraene, had been synthesized by Wllstatter^ in 1911 and has been shown not to be blessed with such stability. The next higher ^n + 2 analog of benzene is cyclo- decapentaene ([10]annulene) which has proven, until recently, to be remarkably resistant to attempts by synthetic chemists to achieve it**^, Evidence for the transient existence of [10]annulene derivatives formed upon thermolysis of substi­ tuted cls-9,10-dlhydronaphthalenes is to be presented in the present section of this thesis. The name [10]annulene actually encompasses a variety of geometric isomers such as the all-cis 1, mono-trans 2 and di-trans 3. A discussion of aromatic properties, then is dependent on the structure and geometric and electronic 2 3 factors inherent to it. \ The questions of steric strain (in 3) and bond angle strain (in 1^) have been addressed by Mislow^ and \\ Burkoth , respectively. In MIslow's model each of the two internal 1,6 hydrogen atoms resides well within the van der Waals radius of the other in the planar form, thus demanding significant distortions from planarity. That considerable aromatic character can be retained in spite 1 5 of such distortions is evidenced by Allinger’s? recent synthesis of a substituted
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