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Xerox University Microfilms 300 North ZMb Road Ann Arbor, Michigan 40100 75-19,455 JAKES, Donald Richard, 1948- SEMIBULLVALENE AND HYPOSTROPHENE: SYNTHETIC AND CHEMICAL ASPECTS OP SOME FLUXIONAL MOLECULES. The Ohio State University, Ph.D., 1975 Chemistry, organic J Xerox University Microfilms , Ann Arbor, Michigan 48108 THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED. SEMIBULLVALENE AND HYPOSTROPHENE: SYNTHETIC AND CHEMICAL ASPECTS OF SOME FLUXIONAL MOLECULES DISSERTATION Presented in Partial Fullment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Donald Richard James, B.S. A * i t * * The Ohio State University 1974 Reading Committee: Approved by Dr. Gideon Fraenkel Dr* John Swenton ~ Adviser \5 Dr. Leo Paquette Department of Chemistry ACKNOWLEDGMENTS I wiBh to express my gratitude to the fine chemists associated with the Department of Chemistry at The Ohio State University for their assistance in my training, but particularly to Professor Leo Paquette who provided the guidance and drive to carry me through to the end. To my parents, who helped me through college, 1 say thanks. To my wife Elaine and daughter Jessica, who have aided and comforted me from beginning to end, I give my deepest appreciation. To Elaine, who typed my dissertation, I dedicate this manuscript and finally, I thank those agencies which provided me with financial support: The Ohio State University, The Goodyear Tire and Rubber Company, and my w ife . ii VITA December 3, 1948. Born - Frackville, Pennsylvania 1970 B.S., Urslnus College, Collegeville, Pennsylvania 1970-1973 Teaching A ssistant, The Ohio State University, Columbus, Ohio 1973-1974 Goodyear Tire and Rubber Company Fellow PUBLICATIONS "Rearrangements Attending Attempts to Form the lrDibenzosemibull- valenylcarblnyKl-Dibenzotrlcyclo[3.3.0.0 * ]octadienylcarbinyl) Cation." S.J.C ristol, G.C.Schloemer, D.R.James, and L.A.Paquette, J. Ore. Chem., 3J, 3852 (1972). "A Simple Route from Cyclopentadiene to Hypostrophene." L.A.Paquette, R.F.DavIs, and D.R.James, Tetrahedron L ett., 1615 (1974). "Equilibrium Displacements Resulting from Substitution of the Semibull- valene Nucleus." L.A.Paquette, D.R.James, and G.H.Birnberg, J. Amer. Chem. S o c .. in p re ss, 1974. "Direct and Indirect Trapping of Isomeric Monosubstituted Blcyclo[4.2.0]- octadienes with Triazolinediones. Photocyclization and Ag(I) Catalyzed Rearrangement of the Derived Adducts as a Route to Functionalized 9,10-Diazasnoutanes." L.A.Paquette, D.R.James, and G.H.Birnberg, ibid., in press, 1974. "Cheletropic ^2 + ^-2 + <j-2s Ejection of Nitrogen from 9,10-Diaza- snoutanes i s a Route to Monofunctionalized Semlbullvalenes. Ground State Substituent Effects on Equilibrium Displacements," D.R.James, G.H.Birnberg, and L.A.Paquette, ib id .. in preBS, 1974. FIELDS OF STUDY Major Field; Organic Chemistry i l l TABLE OF CONTENTS Page ACKNOWLEDGMENTS................................................................................... 11 V ITA ............................................................................................................. H I LIST OF TABLES....................................................................................... V LIST OF FIGURES........................................................................................ v i PART I. Rearrangement: of the 1-Dibenzosemibullvalenylcarbinyl Cation. Introduction ...................................................................... 1 R e su lts ...................... .............. 5 Discussion .......................................................................... 8 Experimental ...................................................................... 14 II.Equilibrium Displacements Resulting from Substitution of the Semibullvalene Nucleus. Introduction ...................................................................... 19 Results and Discussion ..................................... 34 Experimental ...................................................................... 80 III.Synthesis and Chemistry of Hypostrophene Introduction ...................................................................... 106 Results and Discussion ..... .......................... 112 Experimental ...................................................................... 133 REFERENCES................................................................................................. 153 iv I LIST OF TABLES Page Table I . A G ^ f o r Cope Rearrangem ents ................................. , 31 Table II. Results of Direct and Indirect Addlton of PTAD to Various Monosubstituted Cydooctatetraenes. 48 Table III. Results of Photochemical Cyclizations ........................ 51 Table IV. Results of Ag*-Catalyzed Rearrangements ................... 57 Table V. Physical Data for the 7,8-Diazatrlcyclo[4.2.2. 0 * ]deca-3,9-diene-7,8-dlcarboxamides .................. 87 Table VI. Physical Data for the 9,10-Diazabasketanes. 93 Table VII. Physical Data for the Diazasnoutanes. ..... 97 Table VIII. Variable Temperature Pmr Shift Data for 91-CH3 ± ; 92-CH3 ...................................................................... 102 Table IX. Variable Temperature Pmr Shift Data for 91-C6H5^ j»2-C6H5. ..................................................... 103 Table X. Variable Temperature Pmr Shift Data for 1 3 9 -C H .^ 140-CH3 .................................................................. 104 Table XI. Variable Temperature Pmr Shift Data for 139-Ff^:140-F ........................................................................... 105 v i LIST OF FIGURES Page Figure 1. Selected variable-temperature pmr spectra of l(5)-methylsemibullvalene (60 MHz, CS£ solution), 65 Figure 2. Selected variable-temperature pmr spectra of l ( 5 )-phenylsemibullvalene [100 MHz, CD.C1„~ Freon 11 solution (1:1)] ..................................................... 69 Figure 3. Selected variable-temperature pmr spectra of 2(4)-methylsemibullvalene (60 MHz, CLCl, sol­ ution at 80° and 99 ; CS„ solution at +52 and b elo w ) ................................................................................... 73 Figure 5. Selected variable-temperature pmr spectra of 2(4)-fluorosemibullvalene (60 MHz, CS 2 s o lu tio n ) . 74 Figure 5. Alcohols synthesized from hypostrophene. ..... 127 vi Part I: Rearrangement of the 1-Dibenzoaemiballvalenylcarblnyl Cation. Introduction The 8emibullvalene molecule (1), a structurally compressed homotro- pilidlne, undergoes Cope rearrangement with the lowest known activation energy for this type of reaction.* The highly fluxional character of this hydrocarbon results in the rapid equilibration of carbon atoms 2 and 4 , 6 and 8, and 1 and 5 (3 and 7 remain unchanged). A reactive functionality such as, for example, a -CHj* group at could consequently 3 experience exchanges between and C,. before its ultimate involvement in chemical reaction. Thus the observable experimental results with such intermediates may not be easily rationalizable due to multicenter reactivity, i.e ., the presence of two reactive intermediates in com­ petitive self-annihilation. The differences in hybridization and chemical environment at various positions in semibullvalene would govern in large part the percentage of reaction occurring from each substituent position. The semibullvalene molecule thus provides an interesting case for study of the effects of hybridization on reactivity. In order to understand the possibly complex nature of reactions t pursuant to generation of unstable semibullvalene Intermediates, we were led to study first certain nonfluxional model compounds.

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