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Reactions of Gem-Dihalides with Metals

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Reactions of Gem-Dihalides with Metals This dissertation has been 61-5124 microfilmed exactly as received SHANK, Raymond S., 1931- REACTIONS OF GEM-DIHAUDES WITH METALS. The Ohio State University, Ph.D., 1961 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan REACTIONS OF GEM-DTHALIDES WITH METALS DISSERTATION Presented In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By RAYMOND S. SHANK, B.Sc., M.Sc. The Ohio State University 1961 Approved by Adviser Department of Chemistry ACKNOWLEDGMENT T would like to express my deep appreciation to Professor Harold Shechter for proposing this study, for his helpful guidance and timely suggestions throughout its investigation, and for the many hours he so unselfishly gave during the preparation of this manuscript. The chemicals and gas chromatographic information furnished by Dr, Lester Friedman as well as the authentic hydrocarbons which were obtained from Dr. K. W. Greenlee, Dr. A. J_. Streiff, and Vincent Wiley for gas chromatographic comparisons are also acknowledged. The equipment supplied by, the discussions with, and the suggestions of fellow graduate students were helpful and appreciated. Finally, I am indebted to the Department of Chemistry for affording me the opportunity as a Teaching Assistant to obtain additional training and experience. I am also grateful for financial assistance furnished by funds made available from The Ohio State University Develop­ ment Fund, the Petroleum Research Fund of the American Chemical Society, and the National Science Foundation. ii CONTENTS PART I REACTIONS OP ZINC-COPPER COUPLE AND GEM-DIHALIDES IN PRESENCE OP UNSATURATED COMPOUNDS Page INTRODUCTION AND HISTORICAL .......................... 2 DISCUSSION............ 8 EXPERIMENTAL...................................... 16 General Information ................................ 16 M a t e r i a l s ...................................... 16 Gas Chromatography............................. 17 Intermediates. ..................... ....... 19 Zinc-Copper Couple ................................ 19 1.1-Diiodoethane .................................. 19 Reactions of Methylene Iodide, Zinc-Copper Couple, and O l e f i n s .......... 20 , General Procedure . ......... 20 Bicyclo[4.1,£>]heptane from Cyclohexene .......... 22 n-Hexylcyclopropane from 1-Octene ............ 23 1-Methyl-4-(1-methylcyclopropyl)cyclohexene from (+)-Limonene ......................... 26 2-0xabicyclo[4.1.0]heptane from Dihydropyran . 26 Unsuccessful Reactions of 1,1-Dihalides, Zinc- Copper Couple, and Unsaturated Compounds.... 27 Methylene Iodide, Zinc-Copper Couple, and Diphenylacet^lene. ......................... 27 Methylene Iodide, Zinc-Copper Couple and 2-Pentyne......................... ............. 28 Methylene Bromide and Zinc-Copper Couple.... 29 1.1-Dichloroethane, Zinc-Copper Couple, and Cyclohexene ........ ..... 29 1.1-Diiodoethane, Zinc-Copper Couple, and Cyclohexene ............................... 3° iii iv CONTENTS (Continued) PART II REACTIONS OP METALS AND GEM-DIHALIDES Page INTRODUCTION ....................................... 32 HISTORICAL................. 35 SUMMARY ........................................... 47 DISCUSSION......................................... 50 Preparation of gem-Dihalides ................... 50 Reactions of gem-Dlhalldes and Metals............ 56 EXPERIMENTAL .............................. 83 Special Techniques .............................. 83 Preparation of gem-Dlhalldes ................... 83 0(. -Bromobutyryl Bromide ..................... 83 oC -Bromobutyramide........................... 84 1.1-Dibromopropane ................ ..... 85 1.1-Dibromobutane ................ ..... 86 1.1-Dichlorobutane ............................ 88 1.1-Dichloropropan e ............................ 89 1.1-Dichloro-2,2-dimethylpropane (l,1-Di- chloroneopentane).......... 90 1.1-Dichlorocyclobutane .................... 91 1.1-Dichlorocyclopentane .................... 92 1.1-Dichlorocyclohexan e ........................ 94 1.1-Dlchlorocyclooctane..... ............... 96 R e a g e n t s .................................... 97 Sodium Dispersion................................ 99 Reactions of gem-Dihalides and Metals............ 100 General Technique ..... 100 Sodium. ..................... 100 Magnesium ............................. 101 Zinc-Copper Couple............ 102 V CONTENTS {Continued) Page Analytical Procedure . • . ............... 102 Gas Chromatography ............ 102 Yield of Products .................. 105 Reaction of 1,l-Dichloro-2,2-dimethylpropane with Metals ............................ 106 Reaction of 1,1-Dichlorocyclobutane with Metals. 108 Reaction of 1,1-Dichlorocyclopentane with S o d i u m ................... 110 Reaction of 1,1-Dichlorocyclohexane with Sodium. Ill Reaction of 1,1-Dichlorocyclooctane with Sodium. Ill Attempted Isomerizations with Sodium ............. 113 Cyclooctene .............................. 113 Bicyclo[5.1.0]octane ..... 113 Introduction to Tables ..................... 114 LIST OF TABLES Table Page 1. Reactions of Olefins with Methylene Iodide and Zinc-Copper Couple ..................... 9 2. Summary of Yields and Physical Properties of gem-Dlhalldes.............................. 51 3. Summary of Reactions of 1,1-Dibromoethane with M e t a l s ......................................... 57 4. Summary of Reactions of 1,1-Dihalopropanes with Metals ...................................59 5. Summary of Reactions of 1,1-Dihalobutanes with Metals.....................................65 6. Summary of Reactions of 1,l-Dichloro-2,2- Dimethylpropane with Metals....................69 7. Summary of Reactions of 1,1-Dichlorocyclo­ butane and Metals. ....................... 76 8. Reactions of 1,1-Dibromoethane with Metals . 115 9. G. P. C. Analyses of Products from Reactions of 1,1-Dibromoethane with Metals ........... 116 10. Reactions of 1,1-Dihalopropanes with Metals. 118 11. G. P. C. Analyses of Products from Reactions of 1,1-Dihalopropanes with Metals............ 119 12. Reactions of 1,1-Dihalobutanes with Metals . 121 13. G. P. C. Analyses of Products from Reactions of 1,1-Dihalobutanes with Metals ...... 122 14. Reactions of l,l-Dichloro-2,2-dimethylpropane with Metals. ........................... 125 vi vii LIST OP TABLES (Continued) Table Page 15. G. P. C. Analyses of Products, from Reactions of l,l-Dichloro-2,2-dimethylpropane with M e t a l s .......... 126 16. G. P. C. Analyses of High-Boiling Products from Reactions of 1,l-Dichloro-2,2-dimethyl- propane with Metals...................... 130 17. Reactions of 1,1-Dichlorocycloalkanes with Metals .............................. 132 18. G. P. C. Analyses of Products from Reactions of 1,1-Dichlorocyclobutane with Metals . 133 19. G. P. C. Analyses of Products from Reactions of 1,1-Dichlorocyclopentane and 1,1-Di­ chlorocyclohexane with S o d i u m .......... 137 20. G. P. C. Analyses of Products from Reaction of 1,1-Dichlorocyclooctane with Sodium . 139 21. G. P. C. Analyses of Products from Treatment of Blcyclo[5.1.0]octane with Sodium..... 142 LIST OP FIGURES Figure Page 1. Gas Chromatogram of Hydrocarbons from Re­ action of 1,1-Dibromoethane with M a g n e s i u m .............................. 117 2. Gas Chromatogram of Hydrocarbons from Re­ action of 1,1-Dichloropropane with M a g n e s i u m .............................. 120 3. Gas Chromatogram of Hydrocarbons from Re­ action of 1,1-Dichloropropane with S o d i u m ........................... 120 4. Gas Chromatogram of Hydrocarbons from Re­ action of 1,1-Dibromopropane with M a g n e s i u m ....................... 120 5. Gas Chromatogram of Hydrocarbons from Re­ action of 1,1-Dibromobutane with Zinc- Copper .................................. 124 6. Gas Chromatogram of Hydrocarbons from Re­ action of 1,1-Dichlorobutane with M a g n e s i u m ................... ........... 124 7. Gas Chromatogram of Hydrocarbons from Re­ action of 1,1-Dichlorobutane with S o d i u m ........................... 124 8. Gas Chromatograms of Hydrocarbons from Re­ actions of 1,l-Dichloro-2,2-Dimethyl- propane with Metals. .......... 128 9. Gas Chromatograms of Hydrocarbons from Re­ actions of l,l-Dichloro-2,2-Dimethyl- propane with S o d i u m ............ 129 10. Gas Chromatogram of High-Boiling Hydro­ carbons From Reaction of 1,1-Dichloro- 2.2-Dimethylpropane with Sodium. .... 131 11. Gas Chromatogram of High-Boiling Hydro­ carbons From Reaction of 1,1-Dichloro- 2.2-Dlmethylpropane with Sodium. 131 viii ix LIST OP FIGURES (Continued) Figure Page 12. Gas Chromatograms of Hydrocarbons from Re­ actions of 1,1-Dichlorocyclobutane with Metals....................... 135 13. Gas Chromatograms of Hydrocarbons from Re­ action of 1,1-Dichlorocyclobutane with M a g n e s i u m ................................ • 136 14. Gas Chromatogram of Hydrocarbons from Re­ action of 1,1-Dichlorocyclohexane with Sodium.................................... 138 15. Gas Chromatogram of Hydrocarbons from Re­ action of 1,1-Dichlorocyclopentane with S o d i u m . ....................... 138 16. Gas Chromatogram of Hydrocarbons- from Re­ action of 1,1-Dichlorocyclooctane with Sodium.................................... 141 17. Gas Chromatogram of Hydrocarbons from Re­ action of 1,1-Dichlorocyclooctane with Sodium.................................... l4l PART T REACTIONS OF ZINC-COPPER COUPLE AND GEM-DIHALIDES IN PRESENCE OF UNSATURATED COMPOUNDS 1 INTRODUCTION AND HISTORICAL Cyclopropane derivatives have received increased attention in the last few years from
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