This dissertation has been 65—5677 microfilmed exactly as received SMITH, James Allbee, 1937- REARRANGEMENT AND FRAGMENTATION REACTIONS OF CYCLOPROPYLMETHYLIDENES. The Ohio State University, Ph.D., 1964 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan REARRANGEMENT AND FRAGMENTATION REACTIONS OP CYCLOPROPYLMETHYLIDENES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy In the Graduate School of The Ohio State University By James Allhee Smith, B.S. In Chemistry ****** The Ohio State University 1964 by Adviser Department of Chemistry ACKNOWLEDGMENTS I am Indebted to Professor Harold Shechter for suggesting this problem and for his guidance and instruo tion. I also wish to acknowledge the assistance of Dr. T. Page, Battelie Memorial Institute, in the inter­ pretation of some of the nuclear magnetic resonance spectra. I am grateful for the financial aid given by Union Carbide Corporation, Du Pont Company, and the National Science Foundation, ii VITA October 20, 1937 Born - Detroit, Michigan 1955 Graduated from Pontiac High School, Pontiac, Michigan 1959 B.S. in Chemistry, University of Michigan, Ann Arbor, Michigan 1959-1960 Teaching assistant. Department of Chemistry, The Ohio State University, Columbus, Ohio 1961-1963 National Science Foundation Cooperative Fellow, Department of Chemistry, The Ohio State University, Columbus, Ohio 1963-1964 Union Carbide Corporation Fellow, Department of Chemistry, The Ohio State University, Columbus, Ohio iii CONTENTS Page I. INTRODUCTION AND HISTORICAL................. 1 II. SUMMARY ............................... II III. DISCUSSION.................................. 13 IV. EXPERIMENTAL ............................... 59 GENERAL PROCEDURES AND TECHNIQUES........ 59 Melting points....................... 59 Boiling points.............. 59 Elemental analysis................... 59 Infrared spectra..................... 59 Ultraviolet spectra.................. 50 Near-Infrared spectra................ 60 Nuclear magnetic resonance spectra... 60 Gas chromatography................... 60 Preparative gas chromatography....... 62 INTERMEDIATES............................ 62 p-Toluenesulfony1 hydrazlde (tosyl hydrazlde)............... 62 Trlmethylsulfoxonlum Iodide.......... 63 1 -Phenyl -1 -cyanocy c lopr opane......... 63 Cyclopropyl ketone........ «..........63 2,2,4,4-Tetramethylcyclohutanone 63 2,2-Dlmethylcyclopropyl methyl ketone ...... 64 Phenyl 1-phenylcyclopropyl ketone.... 65 1-Phenylcyclopropanecarhoxaldehyde... 66 Blcyclo [4.1.0] -2-heptanone........... 67 o(,2-Dlmethylcyclopropanemethanol 68 Methyl 2-methylcyclopropyl ketone.... 69 Cyclopropanecarboxaldehyde ..... 71 1-Phenylcyclopropanecarboxaldehyde-d. 71 Cyc lopr opane carboxaldehyde-d......... 72 Tosy Ihydrazone s ...................... 73 Cyclopropyl methyl ketone tosy Ihydrazone............... 73 Cyclopropyl ketone tosyl- hydrazone......... 73 Iv CONTENTS (contd.) Page Cyclopropyl phenyl ketone tosyIhydrazone .......... .. 73 1-Phenylcyclopropanec arhoxal- dehyde tosyIhydrazone.... .. 74 2,2-Dlmethylcyclopropyl methyl ketone tosyIhydrazone.... .. 75 2,2,4,4-TetramethyIcyclo- hutanone tosyIhydrazone .. .. 75 BIcyclo[4.1.0]-2-heptanone tosyIhydrazone .......... .. 76 Methyl 2-methylcyclopropyl ketone tosyIhydrazone.... .. 76 Cyclopropanecarboxaldehyde tosyIhydrazone .......... .. 77 Cyclopropanecarboxaldehyde-d tosyIhydrazone .......... .. 77 1-Phenylcyclopropanecarbox­ aldehyde -d tosyIhydrazone .. 77 Phenyl 1-phenylcyclopropyl ketone tosylhydrazone .... .. 78 Sodium salts of tosylhydrazones: general procedures ...... .. 78 Lithium salt of cyclopropanecarbox aldehyde-d tosylhydrazone .. 79 PRELIMINARY DECOMPOSITIONS .......... .. 79 Thermal decomposition of cyclopropyl ketone tosylhydrazone In N-methyIpyrrolIdone with sodium methoxlde............. 79 Thermal decomposition of cyclopropyl ketone tosylhydrazone with sodium methoxlde In other solvents..................... 8l Thermal decomposition of the sodium salt of cyclopropyl ketone tosylhydrazone at atmospheric pressure ........... ......... 82 Thermal decomposition of the silver salt of cyclopropyl ketone tosylhydrazone at atmospheric pressure .................... 83 Thermal decomposition of the silver salt of cyclopropyl ketone tosylhydrazone In dlglyme .... 83 CONTENTS (contd.) Page Ultraviolet irradiation of the sodium salt of cyclopropyl ketone tosylhydrazone in several media 84 VACUUM PYROLYSES OP SODIUM SALTS OP TOSYLHYDRAZONES ................ 84 General techniques................... 84 Vacuum pyrolysis of the sodium salt of cyclopropyl ketone tosylhydrazone.................. 85 Reactions of 1-cyclopropyl- cyclohutene8Y Hydroboration ............. 87 Diimide reduction............. 87 Brown catalytic hydrogena- tion 88 Permanganate oxidation ...... 89 Vacuum pyrolysis of the sodium salt of cyclopropanecarbox­ aldehyde tosylhydrazonô......... 90 Pyrolysis of the sodium salt of cyclopropanecarboxaldehyde tosylhydrazone at atmospheric pressure 9^ Thermal decomposition of Cyclo­ propane carboxaldehyde tosyl­ hydrazone in diethyl Carbitol .. 91 Thermal decomposition of cyclo­ propanecarboxaldehyde tosyl­ hydrazone in diethyl Carbitol with insufficient sodium m e t h o X i d e 9^ Thermal decomposition of cyclo­ propanecarboxaldehyde tosyl­ hydrazone in diethyl Carbitol with excess sodium methoxide.... 93 Thermal decomposition of the sodium salt of cyclopropane­ carboxaldehyde tosylhydrazone in diethyl Carbitol ........... 9^ Thermal decomposition of the sodium salt of cyclopropane­ carboxaldehyde tosylhydrazone in diethyl Carbitol with 10^ ethylene glycol ............... 94 Vi CONTENTS (contd.) Page Thermal decomposition of the sodium salt of cyclopropane­ carboxaldehyde tosylhydrazone In diethyl Carbitol with 1.25J^ water ... «.......................95 Thermal decomposition of the sodium salt of cyclopropane­ carboxaldehyde tosylhydrazone In ethylene glycol.............. 95 Vacuum pyrolysis of the lithium salt of cyclopropanecarbox­ aldehyde -d tosylhydrazone....... 96 Vacuum pyrolysis of the sodium salt of 1-phenylcyclopropane­ carboxaldehyde tosylhydrazone ... 96 Vacuum pyrolysis of the sodium salt of 1-phenylcyclopropane­ carboxaldehyde -d tosylhydrazone.. 97 Vacuum pyrolysis of the sodium salt of 2,2-dimethyIcyclopropyl methyl ketone tosylhydrazone .... 98 Vacuum pyrolysis of the sodium salt of methyl 2-methylcyclopropyl ketone tosylhydrazone. .....99 Vacuum pyrolysis of the sodium salt of bIcyclo[4.1.0]-2-heptanone tosylhydrazone..................101 Vacuum pyrolysis of the sodium salt of cyclopropyl methyl ketone tosylhydrazone ............... 103 Vacuum pyrolysis of the sodium salt of cyclopropyl phenyl ketone tosylhydrazone ................ 104 Pyrolysis of cyclopropyIdlazo- phenylmethane.............. 104 Vacuum pyrolysis of the sodium salt of phenyl 1-phenylcyclopropyl ketone tosylhydrazone. ........105 Pyrolysis of dlazonhenyl(l- phenylcyclopropyl)methane ..... 106 Vacuum pyrolysis of the sodium salt of 2,2,4,4-tetramethylcyclo- butanone tosylydrazone ........ 107 High dilution vapor phase de­ composition of 2,2,4,4-tetra- methyldlazocyclobutane ........ 107 vll CONTENTS (contd.) Page STANDARDS...............................109 Dlcyclopropylcarblnol............... 109 Dicyclopropylmethylmethyl ether .... 109 REAGENTS AND SOLVENTS................... 110 APPENDIX I Tables..................................... 112 II Infrared Spectra............................124 III Nuclear Magnetic Resoneuice Spectra...........137 IV Ultraviolet Spectra........................ 162 V Near-Infrared Spectrum..................... I65 VI Gas Chromâtogramst ...................... l6? viii TABLES Table Page 1 Vacuum pyrolysis of the sodium salt of cyclopropyl ketone tosylhydrazone...... .. 113 2 Vacuum pyrolysis of the sodium salt of cyclopropanecarboxaldehyde tosylhydrazone .. 114 3 Pyrolysis of the sodium salt of cyclopro­ panecarboxaldehyde tosylhydrazone at atmospheric pressure................... ..1 1 5 4 Decomposition of cyclopropanecarboxal­ dehyde tosylhydgazone In diethyl Oarbltol at loO ##@###*#####*####4 o • • • • .. 116 5 Decomposition of the sodium salt of cyclopropanecarboxaldehyde tosylhydra­ zone at 1 8 0..... ###### .. 117 6 Vacuum pyrolysis of the sodium salt of 1-phenylcyclopropanecarboxaldehyde tosylhydrazone ••••••••••••••••••••••••• .. 118 7 Vacuum pyrolysis of the sodium salt of 2,2,-dimethyIcyclopropyl methyl ketone tosylhydrazone «••••«•••••*••••••••••••« ..1 1 9 8 Vacuum pyrolysis of the sodium salt of methyl 2-methylcyclopropyl ketone tosylhydrazone ####**###*##*##*##*#**##« ..120 9 Vacuum pyrolysis of the sodium salt of blcyclo[4, 1.Q)-2-heptanone tosyl­ hydrazone a#*#*##***##*###****#*#*###*#* . .121 10 Vacuum pyrolysis of the sodium salt of cyclopropyl methyl ketone tosylhy­ drazone .............................. ..122 11 Vacuum pyrolysis of the sodium salt of 2,2,4,4-tetraraethyIcyclobutanone tosylhydrazone and decomposition of the Intermediate dlazo compound ........... 123 INFRARED SPECTRA Figure 1 2,2-Dlmethylcyclopropyl methyl ketone...... ..125 2 o(, 2 -Dlmethylcyc lopropaneme thanol............. 125 Methyl 2-methylcyc lopropyl ketone............ 125 I Dicyclopropylmethyl p-tolyl sulf one.......... 125 2 -Cyc lopropyl -1,3 -bu^d lene.................. 126 i 1 -Cyc lopropylcyc lobutene.................... 126 Ix INFRARED SPECTRA (contd.) Figure Page 7 1-Cyclopropyl-2-cyclobutand ................. 12? 8 Cyc lopropylcyc lobut ane............. 127 9 Cyclopropanecarboxyllc acid...................127