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Xerox University Microfilms, Ann Arbor,Michigan 48106 77-2525 VOLZ, William Edward, 1947- STRAINED ALICYCLIC HYDROCARBONS: SYNTHESIS, CHLOROSULFONYL ISOCYANATE ADDITIONS AND ELECTRONIC PROPERTIES. The Ohio State University, Ph.D., 1976 Chemistry, organic Xerox University Microfilms,Ann Arbor, Michigan 48106 STRAINED ALICYCLIC HYDROCARBONS: SYNTHESIS, CHLOROSULFONYL ISOCYANATE ADDITIONS AND ELECTRONIC PROPERTIES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University by William Edward Volz, B.S. ***** The Ohio State University 1976 ... Reading Committee: Approved by Dr. Leo A. Paquette Dr. Gideon Fraenkel Dr. John S. Swenton Adviser Department of Chemistry DEDICATION Monica, Tracy, and ACKNOWLEDGMENTS I am truly grateful to Professor Leo A. Paquette for his direction, encouragement and enthusiasm during this -work. The stimulating atmo­ sphere provided by the research group he has attracted is something that I am very proud to have experienced. I wish to thank my friend Mike Geekle for all of the nmr work he did for me. I especially value the companionship he gave me and my family. The photoelectron spectra and related molecular orbital calculations are courtesy of Professor Rolf Gleiter and Dr. Peter Bischof at the Tech- nischen Hochschule Damstadt, West Germany. I sincerely appreciate the sacrifices Monica, Tracy and Eric made to my education, and the confidence Monica, my parents and my parents-in-law had in me. I would also like to acknowledge The Ohio State University and the people of Ohio for their financial support. VITA October 15, 1947 ........... B o m - Des Moines, Iowa 1970 .......................... B. S., The Iowa State University, Ames, Iowa 1970-1974...................... Teaching Assistant, The Ohio State University, Columbus, Ohio 1974-1975 .................. Research Assistant, The Ohio State University, Columbus, Ohio PUBLICATIONS T. J. Barton, W. E. Volz, and J. L. Johnson, J. Org. Chem., 56? 5565 (1971). W. E. Volz, L. A. Paquette, R. J. Rogido, and T. J. Barton, Chem. Ind. (London), 771 (1974). L. A. Paquette, W. E. Volz, M. A. Beno, and G. G. Christoph, J. Am. Chem. Soc., 97, 2562 (1975). W. E. Volz and L. A. Paquette, J. Org. Chem., 4l, 57 (1976). L. A. Paquette and W. E. Volz, J. Am. Chem. Soc., 9 8, 2910 (1976 ). R. Gleiter, P. Bischof, W. E. Volz, and L. A. Paquette, J. Am. Chem. Soc., in press. iv TABLE OF CONTENTS Page DEDICATION................................................... ii ACKNOWLEDGMENTS ...................................................... iii VITA ......................................................... iv LIST OF FIGURES................. *........ vii LIST OF TABLES................................................ viii SECTION I - Reactions of Chlorosulfonyl Isocyanate with Homo- and Benzhomobarrelenes .................. 1 INTRODUCTION............................................. 2 RESULTS....... ......................................... 20 DISCUSSION.............................................. k-3 SECTION II - Reaction of Chlorosulfonyl Isocyanate with Barrelene, Benzobarrelene, and Dibenzobarrelene .... 54 INTRODUCTION ............................................ 55 RESULTS................................................. 59 DISCUSSION.............................................. 72 SECTION III - Synthesis of 1-Cyanosemibullvalenes via Chlorocyanation of Barrelene, Benzobarrelene, and Dibenzobarrelene............................ 83 INTRODUCTION............................................ 84 RESULTS................................................. 90 DISCUSSION.............................................. 102 v Page SECTION IV - Reactions of Chlorosulfonyl Isocyanate with Bicyclopentane and 1,3 -Dimethylbicyclobutane...... 113 INTRODUCTION............................................. Il4 RESULTS................................................. 118 DISCUSSION............................................... 129 SECTION V - Synthesis and Electronic Properties of Bicyclo- [4.1.1]octane, Bicyclo[4.1.l]oct-3-ene, and Bicyclo[i)-. 1. l]octa-2,^-diene..................... 135 INTRODUCTION.............................. 136 RESULTS................................................. 153 DISCUSSION....................................... 185 EXPERIMENTAL................................................. 203 REFERENCES................................................... 275 vi LIST OF FIGURES Figure Page 1 A lateral display of bond lengths and bond angles of 1-cyanosemibullvalene (190a) ....................... 93 2 A ventral display of bond angles of 1-cyanosemi- bullvalene (igOa) ............... ................ 94 3 Hie 60 MHz XH nmr spectrum (upfield region) of 2-aza- 1 .4-dimethyl-3 -oxo-bicyclo[2.2.0]hexane (229) ......... 128 4 A diagram of the symmetry elements for bicyclo- [4.1.1]octa-2,4-diene (255) ...... .................. 149 5 The 60 MHz % nmr spectrum of bicyclo[4.1. l]octa- 2.4-diene (233) in CDC13 ........................... 167 6 Hie ultraviolet spectrum of bicyclo[4.1.l]octa- 2.4-diene (233) in hexane.................. VJO 7 The photoelectron spectrum of bicyclo[4.1.l]octa- 2.4-diene (255.) ..................................... 174 8 The photoelectron spectrum of bicyclo[4.1.1]oct-3- ene (254) ........................................... 175 9 The photoelectron spectrum of bicyclo[4.1.1]octane (253) ........................................... 175 10 Orbital interaction diagram for bicyclo[4.1. l]octa- 2.4-diene (255) based upon perturbation theory ......... l8l 11 An illustration of the Fletcher-Powell computer optimized structures for 253 ? 254, and 255 ............. 183 vii LIST OF TABLES Table Page I Relative Rates for the Cyeloaddition of Chloro­ sulfonyl Isocyanate to Various Olefins in Dichloro- methane Solution corrected to 25° .................... 5 II Relative Rates for the Reaction of Chlorosulfonyl Isocyanate with 2-Ethylhexene-l in Solvents of Varying Polarity at 2 5 ° ............................. 5 III TO eV Mass Spectroscopic Fragmentation Patterns of Tricyclo[3.2.2.02’4 ]nona-6,8-diene (45) and anti-6,7- Dideuteriotricyclo[3.2. 2.02’ 4 ]nona-67B~-diene (50) ...... 23 IV Product Distribution After Chromatographic Separation of the CSI-Homobarrelene Adducts Formed at Various Reaction Times in Dichloromethane Solution (25°) ....... 24 V Eu(dpm) 3 Induced Chemical Shifts in the NMR Spectra of exo,anti-3-Aza-4-oxoquadricyclo[4.3« 2.02j5.07’9]- undec-10-ene (52) ................................... 26 VI Eu(fod) 3 Induced Chemical Shifts in the NMR Spectra of endo,anti-3-Aza-4-oxoquadricyclo[4.3.2.02?4.07j9]- undec-10-ene (53 ) ................................... 29 VII Eu(fod) 3 Induced Chemical Shifts in the NMR Spectra of syn(n)-4-Aza-5-oxopentacyclo[8.1.0.02}s.O3 ’8.07>9]- undecane (54) ....................................... 31 VIII Eu(fod) 3 Induced Chemical Shifts in the NMR Spectra of exo,anti-3-Aza-10,ll-benzo-4-oxoquadricyclo- [4.3.2.02’5.07 >9]undec-10-ene (58) ................... 37 XX Eu(fod) 3 Induced Chemical Shifts in the NMR Spectra of endo,anti-3-Aza-10,ll-benzo-4-oxoquadricyclo- [4.3.2.02’5.07’9]undec-10-ene (59) ................... 40 X Eu(fod)3 Induced Chemical Shifts in the NMR Spectra of exo-3-Aza-T,8-benzo-4-oxotricyclo[4. 2.2.02’5]deca- 7,9-diene (ill) ..................................... 64 viii Table Page XI 100 MHz N M R Data from Double Resonance Experiments for 8-Aza-2,3-benzo-9-oxotricyclo[5.3* 0 . 10]deca-2, 5- diene (112) ......................................... 67 XII 70 eV Mass Spectroscopy Fragmentation Pattern of 7,8- Benzo-anti-2-carbamyl-6-hydroxytricyclo[2.2.2.03 ’ 5 ] - oct-7-ene (114) ............... 88 XIII Variable Temperature 1H NMR Data (100 MHz) for 1(5)- Cyanos emibullvalene (190a 2 190b) in CD2C12-CF2C12 ..... 98 XIV Variable Temperature 1H NMR Data (100 MHz) for 1(5)- Cyanosemibullvalene (190a £ 190b) in C12C=CC12 . 98 XV -^H NMR Coupling Constant Data for Chloro Nitriles 191, 192, and 193,................................... 98 XVI 13C NMR Chemical Shifts for Cyanosemibullvalenes llg, 190, and 19ft ......................... lo2<- XVII Bond Lengths in Cyclopropane Derivatives ............. 105 XVIII Estimated Equilibrium constants and Free Energy Differences for 1 (5 )-Substituted Semibullvalenes (174 a 5* 174 b) Based on Chemical Shifts of H4, H6 and C4, C6 Relative to 4H and 1SNMR Data for Semi- bullvalene (174, R=H) at -l60°...................... 110 XIX Eu(fod) 3 Induced Chemical Shifts in the NMR Spectra of 6-Aza-7-oxobicyclo[3.2.0]heptane (225) Resulting from the Addition of Chlorosulfonyl Isocyanate to Bicyclopentane (224) ................................ 120 XX Eu(fod) 3 Induced Chemical Shifts in the NMR Spectra of 6-Aza-7-oxobicyclo[3*2.0]heptane (225) Resulting from the Addition of Chlorosulfonyl Isocyanate to Cyclopentene (227) 122 XXI Eu(fod) 3 Induced Chemical Shifts in the XH NMR Spectra of 2-Aza-l,4-dimethyl-3-oxobicyclo[2. 2.03- hexane (235 ) ........................................ 126 XXII Data from the 13C NMR Spectra of Bicyclo[4.1.1]- oetane (253.), Bicyclo[4.1. l]oct-3-ene (254), and Bicyclo[4.1.l]octa-2,4-diene (255) .................... 185 ix Table Page XXIII Chemical Shifts and Coupling Constants from the 1H NMR Spectra and Known or Estimated Dihedral Angles Between the Planes of the Double Bonds for some Cyclic, Bicyclic, and Tricyclic 1,3-Dienes............ 168 XXIV Data from the Ultraviolet Spectra of some Cyclic, Bicyclic, Tricyclic, and Spirocyclic Conjugated Dienes.......................... 171 XXV Comparisons of the Vertical Ionization
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