This dissertation has been microfilmed exactly as received 68-8844 KAUFMAN, Gary Martin, 1937- STUDIES OF BASE-CATALYZED DECOMPOSITIONS OF TOSYLHYDRAZONES. The Ohio State University, Ph.D., 1967 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan STUDIES OF BASE-CATALYZED DECOMPOSITIONS OF TOSYLHYDRAZONES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Gary Martin Kaufman, B.A. The Ohio S tate U n iv ersity 1967 Approved by Department of Chemistry Dedicated to my family, especially my wife, Sonya Louise i i ACKNOWLEDGMENT I wish to express my appreciation to Dr. Harold Shechter for his suggestion of this research problem, for his guidance and encouragement in the course of this work, and for his tire ­ less help in preparing this manuscript. I am grateful to the National Science Foundation and the Department of Chemistry of The Ohio State University for financial assistance. i i i VITA October 23, 1937 ......................Born - Heart/well, Nebraska 1955 ................................................ Graduated from Hastings High School Hastings, Nebraska I960 ............ B.A. in Chemistry, Hastings College, Hastings, Nebraska 1960-1961 . Teaching assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio 1962-1964. ....................................... Assistant instructor, Department of Chemistry, The Ohio State University, Columbus, Ohio 1964.-1967 .......................................Research fellow, Department of Chemistry, The Ohio State University, Columbus, Ohio iv CONTENTS . Page DEDICATION........................................................................................... i i ACKNOWLEDGMENT.................................................................................. i i i VITA ........................................................................................................ iv LIST OF TABLES........................................................ x i LIST OF FIGURES.............................................................................. x i i i INTRODUCTION ....................................................................................... 1 HISTORICAL ........................................................................................... 3 RESULTS AND DISCUSSION ................................................................. 6 CHAPTER 1. Preparation of Tosylhydrazones, Benzenesulfonylhydrazones, Methane- sulfonylhydrazones, and Their Sodium and Lithium Salts ............................ 6 2. Base-Catalyzed Thermal Decomposition of Tosylhydrazones ....................................... 12 3. Vacuum Pyrolysis of Lithium Salts of Tosylhydrazones ....................................... 22 4. Reactions of Tosylhydrazones with Various Bases in Selected Solvents . 35 5. Decompositions of Benzenesulfonyl- bydrazones and Methanesulfonylhydra- z o n e s ................................................................. 69 6. Thermolytic and Catalytic Reactions of Diazoalkanes ............................................ 77 EXPERIMENTAL....................................................................................... 109 General Procedures and Techniques Melting Points Boiling Points Elemental Analyses Infrared Spectra Gas Chromatography v CONTENTS (Cont.) Page Intermediates ..... ................................................ 113 ^-Toluene sulfonyl hy dr az ide Benzenesulfonylhydrazide Methane sulfonylhydraz ide 4-P henylbutyronitrile 4-Phenylbut anal Tosylhydrazones - General Techniques . 115 Kthanal tosylhydrazone Propanone tosylhydrazone Butanal tosylhydrazone 2-Methylpropanal tosylhydrazone 2-Butanone tosylhydrazone Cyclopropanecarboxaldehyde tosylhydrazone Pentanal tosylhydrazone 2-Methylbutanal tosylhydrazone 3-Methylbutanal tosylhydrazone 2.2-Dimethylpropanal tosylhydrazone Furfural tosylhydrazone 3-Pentanone tosylhydrazone 3-Methyl-2-butanone tosylhydrazone Cyclopentanone tosylhydrazone 3.3-Dimethyl-2-butanone tosylhydrazone Cyclohexanone tosylhydrazone Cycloheptanone tosylhydrazone Phenylacetaldehyde tosylhydrazone Acetophenone tosylhydrazone 2,2,5,5-Tetramethyltetrahydrofuran-3- one-tosylhydrazone 2-Phenylpropanal tosylhydrazone 3-Phenylpropanal tosylhydrazone 3-Phenylpropenal tosylhydrazone 1-Phenyl-2-propanone tosylhydrazone 4-Phenylbutanal tosylhydrazone 4-Phenyl-3-buten-2-one tosylhydrazone Benzophenone tosylhydrazone Phenyl cyclohexyl ketone tosylhydrazone 9-Fluorenone tosylhydrazone Diphenylacetaldehyde tosylhydrazone Dibenzyl ketone tosylhydrazone v i CONTENTS (Gout.) Page Benzenesulfonylhydrazones ................................... 127 Propanone benz enesulf onylhydr az one 2-Butanone benzenesulfonylhydrazone 2.2-Dimethylpropanal benzene- sulfonylhydrazone 3-Methyl-2-butanone benzenesulfonyl­ hydr azone s 3-Pentanone benzenesulfonylhydrazone 3.3-Dimethyl-2-butanone benzenesul- fonylhydrazone Methanesulfonylhydrazones ................................... 129 Propanone methanesulfonylhydrazone 2-Butanone methancsulfonylhydrazone 2.2-Dimethylpropanal methanesulfonyl- hydrazone 3.3-Dimethyl-2-butanone methanesul- fonylhydrazone p-Naphthalenesulfonylhydrazone ...................... 130 2-Butanone p-naphthalenesulfonyl­ hydr azone Lithium salts of tosylhydrazones, bcnzene- sulfonylhydrazones and methanesulfonyl­ hydrazones ...................................................................... 130 General techniques: via n-butyllithium . 130 Equipment Reagents Procedure General techniques: via lithium methoxide 136 Equipment Reagents Procedure Lithium salt of ethanal tosylhydrazone Lithium salt of propanal tosylhydrazone Lithium salt of propanone tosylhydrazone Lithium salt of butanal tosylhydrazone Lithium salt of 2-methylpropanal tosylhydrazone Lithium salt of_2-butanone tosylhydrazone Lithium salt of 2-butanone methanesulfonyl- hydrazone v ii CONTENTS (CONT.) Page Lithium salt of cyclopropanecarbox- aldehyde tosylhydrazone ....................................14-0 Lithium salt of pentanal tosylhydrazone ' Lithium salt of 2-methylbutanal tosylhydrazone Lithium salt of 3-methylbutanal tosylhydrazone Lithium salt of 2,2-dimethylpropanal tosyl­ hydrazone Lithium salt of 2,2-dimethylpropanal tosylhydra­ zone via lithium methoxide Lithium salt of 2,2-dimethylpropanal methane- su lf onylhydraz one Lithium salt of 3-methyl-2-butanone tosylhydra­ zone Lithium salt of cyclopentanont; tosylhydrazone Lithium salt of 3,3-dimethyl-2-butanone tosylhydrazone Lithium salt of 3,3-dimethyl-2-butanone tosylhydrazone via lithium methoxide Lithium salt of 3,3-dimethyl-2-butanone benzenesulfonylhydrazone Lithium salt of 3,3~dimethyl-2-butanone methanesulfonylhydrazone Lithium salt of cyclohexanone tosylhydrazone Lithium salt of phenylacetaldehyde tosylhydrazone Lithium salt of acetophenone tosylhydrazone Lithium salt of 2-phenylpropanal tosylhydrazone Lithium salt of 3-phenylpropanal tosylhydrazone Lithium salt of 3-phenylpropenal tosylhydrazone Lithium salt of l-phenyl-2-propanone tosylhydrazone Lithium salt of 4*phenyl-3-butene-2-one tosylhydrazone Lithium salt of benzophenone tosylhydrazone Lithium salt of phenyl cyclohexyl ketone tosylhydrazone Lithium salt of dibenzyl ketone tosylhydrazone Sodium salts of tosylhydrazones ....................................... 154 Sodium salt of 2,2-dimethylpropanal t osylhydr az one Sodium salt of 3,3-*dimethyl-2-butanone tosylhydraz one Sodium salt of tosylhydrazide v i i i CONTENTS (Cont.) Page Decomposition of Tosylhydrazones with Bases in Diethyl Carbitol ............................... 157 General techniques Equipment Reagents Procedure Decomposition of phenylacetaldehyde tosylhydrazone with n-butyllithium Decomposition of phenylacetaldehyde tosylhydrazone with sodium methoxide Decomposition of 1-phenylpropanone tosylhydrazone with sodium methoxide Decomposition of 2-phenylpropanal tosylhydrazone with n-butyllithium Decomposition of 2-phenylpropanal tosylhydrazone with sodium amide Decomposition of 2-phenylpropanal tosylhydrazone with sodium methoxide Decomposition of 3-phenylpropanal tosylhydrazone with n-butyllithium Decomposition of 3~phenylpropanal tosylhydrazone with sodium methoxide Decomposition of diphenylacetaldehyde tosylhydrazone with sodium methoxide Preparation of Diazoalkanes by Vacuum Pyrolyses of Lithium Salts of Tosylhydrazones ................................................ 169 General techniques Equipment Procedure - vacuum pyrolysis A nalysis of th e diazo compound Diazoethane 1-Diazopropane 1-Diazobutane Attempted preparation of cyclopropyl- diazomethane 1-Diaz o-2-methylpropane 1-Diazopentane 1-Diaz o-2-methylbut ane ix CONTENTS (Cont.) Page l-Diazo-3-methylbutane ....................................... i77 1-Diazo-2,2-dimethylpropane 2-Diazo-3,3-dimethylbutane 1-Diazo-l-phenylethane 1-Diazo-2-phenylpropane 2-Diazo-l-phenylpropane Phenylcyclohexyldi azomethane Diphenyldi az omethane 2-Diazo-l,3-diphenylpropane 1-Diazo-2-phenylethane and 1-diazo- 3-phenylpropane 2-Diazopropane, 2-diazobutane, diazocyclo- pentane and diazocyelohexane Attempted preparation of l-diazo-3- phenyl-2-propene and 2-diazo-4-~ phenyl“3-butene Pyrolysis of Salts of Tosylhydrazones Under Various Conditions ....................................... 185 General techniques Equipment Procedure Reactions of Diazo Compounds ....................................... 191 General techniques Equipment Procedure Gas Chromatography Standards ....................................... 193 Analytical samples Phenylcyclopropane