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REACTIONS of HALOCYCLOPROPANES. The This dissertation has been microfilmed exactly as received 69-11,652 HOUSER, Charles W., 1934- REACTIONS OF HALOCYCLOPROPANES. The Ohio State University, Ph.D., 1968 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan REACTIONS OF HALOCYCLOPROPANES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School o f The Ohio State U niversity By Charles W. Houser, B.A. ******** The Ohio State U niversity 1968 Approved hy /Adviser Department of Chemistry Dedicated to Jane and Brian i l ACKNOWLEDGMENTS The author wishes to express sincere appreciation to Professor Harold Shechter for the inception of this problem and for his helpful discussions throughout the course of this research. His editorial guidance during preparation of this manuscript is also gratefully acknowledged. National Science Foundation and Petroleum Research Fund are thanked for their financial assistance to this research. The author owes a special debt of gratitude to his wife, Jane, for her patience and encouragement during completion of this work. i i i VITA October 20, 1934 Born - Parkersburg, West Virginia 1954-1958 U. S. Marine Corps 1962 B.A., David Lipscomb College, Nashville, Tennessee 1962-1965 Teaching Assistant, The Ohio State University, Columbus, Ohio I965-I968 Research Associate, The Ohio State University, Columbus, Ohio iv CONTENTS Page ACKNOWLEDGMENTS.......................................................................................................... i i i VITA .......................................................................... iv TABLES ..................................................................................................... .................. STATEMENT OF PROBLEM ............................................................................................ 1 PART I INTRODUCTION.............................................................................................................. 7 DISCUSSION........................................................................................................................ 19 Syntheses of polyhalogenated cyclopropanes ........................................ 19 Thermal reaction s o f halocyclopropanes ...................................................... 22 Electrophilic reactions of halocyclopropanes with metal acetates ............................................................................................ 27 Reactions of halocyclopropanes with bases ........................................ 28 PART II INTRODUCTION .............................................................................................................. 46 Displacement reactions of 2,2-dichlorocyclopropylmethyl derivatives ................................................................................................. 46 DISCUSSION........................................................................................................................ 60 Displacement reactions of electronegatively substituted cyclopropylmethyl derivatives .......................................................... 60 EXPERIMENTAL..............................................................................................................• 77 Preparation of 3-bromo-l,l-dichloro-2,2-dimethylcyclopropane . j8 Preparation of l,l,3-trichloro-2,2-dimethylcyclopropane . 79 Preparation of l,l-dibromo-2,2-dichloro-3,3-diraethyl- cyclopropane ................................................................................ 79 Preparation of l,l,2,2-tetrachloro-3-phenylcyclopropane. 80 Preparation of methyl 2,2-dichloro-trans-3-phenylcyclo- propanecarboxylate ......................................................................................... 8l v CONTENTS (Contd.) Page Preparation of 2-(bromomethyl)-l,l-dichlorocyclopropane . 8l Preparation of l,l,2-trichloro-2-(chloromethyl)- cyclopropane ................................................................................................ 82 Preparation of (2,2-dichlorocyclopropyl)methyl acetate .... 82 Preparation of (2,2-dichlorocyclopropyl)methanol .......................... 83 Preparation of (2,2-dichlorocyclopropyl)methyl p-toluene- s u lf o n a t e ..................................................................... T .............................. 83 Attempted preparation of (2,2-dichlorocyclopropyl)- metbylamine .................... ..... 84 Preparation of (2,2-dichlorocyclopropyl)methylamine .................. 85 Preparation of 2,2,3,3-tetrachlorospiro(cyclopropane-l,9'- f lu o r e n e ) ......................................................................................................... 85 Preparation of methyl 2,2-dichlorocyclopropanecarboxylate . 86 Preparation of l,l-dichloro-2-cyanocyclopropane ........................... 87 Preparation of l,l,2,3-tetrachloro-2-(chloromethyl)cyclo- p ro p a n e ............................................................................................................. 87 Preparation of 2,2-dichlorocyclopropanecarboxaldehyde d ie th y l a c e ta l ............................................................................................ 88 Preparation of 2,2-dichlorocyclopropanecarboxaldehyde 2,4-dinitrophenylhydrazone ................................................................. 88 Thermal reaction of 3-kromo-l,l-dichloro-2,2-dimethyl- cyclopropane ................................................................................................ 89 Thermal reaction of l,l,3" ‘trichloro-2,2-dimethylcyclopropane . 89 Thermal reaction of l,l,2,2-tetrachloro-3-phenylcyclopropane . 89 Thermal reaction of 2,2,3j3-tetrachlorospiro(cyclopropane- l ,9'-fluorene) ............................................................................................ 90 Attempted thermal reaction of 2-(bromomethyl)-l,l- dichlorocyclopropane .............................................................................. 90 Attempted thermal reaction of l,l,2-trichloro-2-(chloro- me thy l) cyclopropane ................................................... ........ 90 Reaction of l,l,3-trichloro-2,2-dimethylcyclopropane vith alcoholic potassium hydroxide ..................................................... 91- Reaction of l,l,3-trichloro-2,2-dimethylcyclopropane vith lithium piperidide .............................. 92 Reaction of 1,1,3-trichloro-2,2-dimethylcyclopropane vith potassium jt-butoxide ...................................................................... 93 Reaction of 3"’bromo-l,l-dichloro-2,2-dimethylcyclopropane vith n-butyllithium .......................................................................... 93 Attempted reaction of l,l,3-trichloro-2,2-dimethylcyclopro- pane with sodium h yd rid e ............................................................. 94 Reaction of l,l,2,2-tetrachloro-3_phenylcyclopropane vith sodium h yd rid e ....................................... 94 Hydrolysis of 2,3j3-trichloro-l-phenylcyclopropene ...................... 95 Reaction of 2,3>3“trichloro-l-phenylcyclopropene vith toluene catalyzed by aluminum chloride ........................................ 96 vi CONTENTS (Contd.) Page Reaction of methyl 2,2-dichloro-trans-3-phenylcyclo- propanecarboxylate with methanolic potassium hydroxide . 96 Reaction of l,l,3-trichloro-2,2-dimethylcyclopropane vith sodium ..................................................................................................... 97 Reaction of l,l,3~trichloro-2,2-dimethylcyclopropane with magnesium and methyl iodide .................................................................. 98 Attempted reaction of l,l,3 -trichloro-2,2-dimethylcyclo- propane and l,l-dichioro-3-bromo-2,2-dimethylcyclo- propane vith zinc in a lco h o l ............................................................. 99 Reaction of 3-hromo-l>-dichloro-2,2-dimethylcyclopropane vith silver acetate ............................................... 100 Reaction of 2-(bromomethyl)-l,l-dichlorocyclopropane with sodium methoxide ............................................................................... 100 Reaction of 2-(bromomethyl)-l,l-dichlorocyclopropane with potassium t-butoxide . ............................................................. 101 Attempted reaction of 2 -(bromomethyl)-l,l-dichlorocyclo- propane with sodium hydride .................................................................. 101 Reactions of 2-(bromomethyl)-l,l-dichlorocyclopropane with sodium cyanide ................................................................................................. 102 Reaction of 2-(bromomethyl)-l,l-dichlorocyclopropane vith piperidine ................................................................................................. 102 Reaction of 2-(bromoraethyl)-l,l-dichlorocyclopropane with triphenylphosphine ........................................................................................ 103 Attempted oxidation of 2-(bromomethyl)-l,l-dichlorocyclo- propane with dimethyl sulfoxide ...................... 10*i- Reaction of 2-(bromomethyl)-l,l-dichlorocyclopropane with benzene and aluminum chloride .................................................................. 10^ Reaction of 2-(bromomethyl)-l,l-dichlorocyclopropane with silver acetate ................................................................................. 106 Solvolysis of (2,2-dichlorocyclopropyl)methyl £-toluene- sulfonate in acetic a c id .............................................................. 106 Reaction of (2,2-dichlorocyclopropyl)methylamine
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