This dissertation has been microfilmed exactly as received 6 7-10,880 COOK, Francis Bernard, 1936- ALKALINE DEOXIDATION OF CYCLOPROPYLCARBINOL, CYCLOBUTANOL, AND ALLYLCARBINOL AND THE MECHANISMS OF BASE-CATALYZED DECOMPOSITION OF TOSYLHYDRAZONES IN PROTONIC SOLVENTS. The Ohio State University, Ph.D., 1967 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan ALKALINE DEOXIDATION OF CYCLOPROPYLCARBINOL, CYCLOBOTANOL, AND ALLYLCARBINOL AND THE MECHANISMS OF BASE-CATALYZED DECOMPOSITION OF TOSYLHYDRAZONES IN PROTONIC SOLVENTS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Francis Bernard Cook, B.S., M.S. The Ohio State University 1967 Approved by Adviser Department of Chemistry DEDICATION To ray w ife, Marilyn 11 ACKNOWLEDGMEOTS I wish to express my appreciation to Professor Harold Shechter, who suggested these problems, for his support, guidance, and especially for the assistan ce, c r itic a l judgment, and time he has given in the preparation of this dissertation. I am grateful to the Department of Chemistry of The Ohio State University and the Ethyl Corporation for financial assistance afforded me during these investigations. The author wishes to thank Dr. I(. Greenlee for providing many of the chemical standards used in this research. H i VITA May 20, 1936 ................................ Born - Akron, Ohio 1958 ................................................... B.S., John Carroll University, Cleveland, Ohio 1960 ................................................... M.S., John Carroll University, Cleveland, Ohio 1960-1961 ..................................... Teaching Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio 1961-1963 . ................................. Research Fellow, Department of Chemistry, The Ohio State University, Columbus, Ohio 1963-1964 ..................................... Ethyl Corporation Fellow, Department of Chemistry, The Ohio State University, Columbus, Ohio 1964-1967 ..................................... Research Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio IV CONTENTS Page ACKNOWLEDGMENTS..................................................................................................... i ü VITA ........................................................................................... iv TABLES........................................................................................................................ ix FIGURES.............................................................................................................................x i i i CHAPTER 1. INTRODXTION ...................................................................... 1 CHAPTER 2. HISTORICAL .......................................................................... 2 Alkaline Deoxidation ............................................... 2 CHAPTER 3. RESULTS AND DISCUSSION ............................................... 5 Cyclopropylcarbinol ............................................... 5 Cyclobutanol ................................................................. 11 Allylcarbinol ............................................. 17 CHAPTER 4. EXPERIMENTAL........................................................................... 24 General Procedure ...................................... .... 24 R e a g e n t s .......................................................................... 25 CHAPTER 5. INTRODIKTION........................................................................... 27 CHAPTER 6. HISTORICAL .................................. 30 Tosylhydrazones . ................................................... 30 CHAPTER 7. RESULTS AND DISCUSSION.................................................... 41 Cyclopropanecarboxaldehyde and Cyclopropanecarboxaldehyde-dj Tosylhydrazones .......................................... 41 CHAPTER 8. RESISTS AND DISCUSSION .................................................... 71 Trimethylacetaldehyde Tosylhydrazone . 71 CHAPTER 9 . RESIB.TS AND DISCUSSION..................................................... 84 Diisopropyl Ketone Tosylhydrazone ................... 84 Page CHAPTEB 10. BESŒ.TS AND DISCUSSION........................................... 94 Cyclopentanone Tosylhydrazone ................... 94 CHAPTER 11. BESILTS AND DISCUSSION........................................... 101 Cyclohexanone Tosylhydrazone ........................ 101 CHAPTER 12. BESILTS AND DISCUSSION................................. 106 Cyclobutanone Tosylhydrazone ........................ 106 CHAPTER 13. RESILTS AND DISCUSSION................................. 125 Acetone Tosylhydrazone ..................................... 125 CHAPTER 14. INTRODILTION......................................................... 131 Diazo Compounds ................................................... 131 CHAPTER 15. HISTORICAL............................................................. 132 Diazo Compounds ................................................... 132 CHAPTER 16. BESILTS AND DISCUSSION................................. 136 2-Dlazo-l-indanone ..................................... 136 2-Diazo-3-methyl-l-indanone ........................ 136 1-Diazo-l-phenylethane 137 CHAPTER 17. EXPERBIEWTAL........................................................ 140 General Procedure and Techniques . 140 Melting points .......................................... 140 Boiling points .......................................... 140 Elemental analysis ................................. 140 Infrared spectra ..................................... 140 Ultraviolet spectra . ................... 141 Near-infrared spectra ............................ 141 Nuclear magnetic resonance s p e c t r a .................................................. 141 Gas chromatography ....................... 141 Preparative gas chromatography . , 143 Mass s p e c t r a .................................... 144 Mass spectra analysis ....... 145 Product identification ...... 149 Hydrocarbon yield and composition . 150 Intermediates ................................................... 153 jgt-Toluenesulfonyl hydrazide (tosyl hydrazide) ..................................... 153 Cyclopropanecarboxaldehyde . 153 Cyclopropanecarboxaldehyde-dj . 154 VI Page Tosylhydrazones ................................................... 155 Cyclopropanecarboxaldehyde tosylhydrazone .......................................... 155 Cyclopropanecarboxaldehyde-dj tosylhydrazone .............................................. 156 Cyclobutanone tosylhydrazone .... 156 Cyclopentanone tosylhydrazone .... 156 Cyclohexanone tosylhydrazone .... 157 2,2-Dimethylpropanal tosyl­ hydrazone (Trimethylacetaldehyde tosylhydrazone) ..... ....................... 157 2,4-Dimethyl-3-pentanone tosylhydrazone (diisopropyl ketone tosylhydrazone) ............................ 158 Acetone tosylhydrazone ............................ 158 Acetophenone tosylhydrazone ................... 159 Ethylene glycol-dg .............................................. 159 Methanol-d]^ ............................................................ 161 2-Diazo-l-indanone . ..................................... 162 2-Diazo-3-methyl-l-indanone ....................... 162 1-Diazo-l-phenylethane ................... 163 Lithium salts of tosylhydrazones .... 163 Sodium salts of tosylhydrazones .... 164 Decompositions and Isomerization .... 165 Thermal decomposition of the lithium salt of tosylhydrazones . 165 Thermal decomposition of the sodium s a lt of tosylhydrazones . 166 Decomposition of cyclopropanecarbox­ aldehyde tosylhydrazone in ethylene g l y c o l - d g ......................................... 166 Thermal isomerization of bicycloD .1.0]butane to 1,3-butadiene . 168 Thermal isomerization of cyclobutene to 1,3-butadiene .............................................. 168 Hydrogen-Deuteriura Exchange in Salts of Tosylhydrazones, Diazo Com­ pounds and their A n a l y s i s ............................ 169 Hydrogen-deuterium exchange of lithium cyclopentanone tosyl­ hydrazone in ethylene glycol-d^ . 169 vu Page Hydrogen-deuterium exchange of lithium trimethylacetaldehyde tosylhydrazone in ethylene g l y c o l - d g ....................................................... 170 Hydrogen-deuterium exchange of lithium trimethylacetaldehyde tosylhydrazone in deuterium oxide tetrahydrofuran ............................ 172 Hydrogen-deuterium exchange of lithium cyclohexanone tosyl­ hydrazone in ethylene glycol-dg . 173 Hydrogen-deuterium exchange of lithium acetone tosylhydrazone in ethylene glycol-dn ............................ 174 Hydrogen-deuterium exchange of lithium acetone tosylhydrazone in deuterium oxide-tetrahydro- f u r a n .................................... 175 Hydrogen-deuterium exchange of lithium diisopropyl ketone tosylhydrazone in deuterium oxide-tetrahydrofuran ............................ 176 Hydrogen-deuterium exchange of 1-Diazo-l-phenylethane ............................ 177 Hydrogen-deuterium exchange of 2-Diazo-3-methyl-l-indanone .... 180 Hydrogen-deuterium exchange of 2-Diazo-l-indanone 180 Solvent abbreviations ............................ 181 R ea g en ts.............................................. 182 Gas chromatographic columns .... 182 APPEMDH I TABLES PDR MASS SPECTRA DEUTERIUM ANALYSIS . 183 II MASS SPECTRA ............................................................................... 214 III INFRARED SPECTRA..........................................................................