University of Windsor Scholarship at UWindsor Electronic Theses and Dissertations Theses, Dissertations, and Major Papers 1-1-1964 Part I. Attempted synthesis of cyclopropanone. Part II. A new ether synthesis. Ralph F. A. Jobin University of Windsor Follow this and additional works at: https://scholar.uwindsor.ca/etd Recommended Citation Jobin, Ralph F. A., "Part I. Attempted synthesis of cyclopropanone. Part II. A new ether synthesis." (1964). Electronic Theses and Dissertations. 6034. https://scholar.uwindsor.ca/etd/6034 This online database contains the full-text of PhD dissertations and Masters’ theses of University of Windsor students from 1954 forward. These documents are made available for personal study and research purposes only, in accordance with the Canadian Copyright Act and the Creative Commons license—CC BY-NC-ND (Attribution, Non-Commercial, No Derivative Works). Under this license, works must always be attributed to the copyright holder (original author), cannot be used for any commercial purposes, and may not be altered. Any other use would require the permission of the copyright holder. Students may inquire about withdrawing their dissertation and/or thesis from this database. For additional inquiries, please contact the repository administrator via email ([email protected]) or by telephone at 519-253-3000ext. 3208. PART I ATTEMPTED SYNTHESIS OP A CYCLOPROPANONE PART II A NEW ETHER SYNTHESIS BY RALPH:P.A. JOBIN A Thesis Submitted to the Paculty of Graduate Studies through the Department of Chemistry in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy at the University of Windsor . Windsor, Ontario 1964 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 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Further reproduction prohibited without permission. ABSTRACT Part I- Attempts to synthesize a, cyclopropanone derivative from the reaction of triphenylmethyl sodium and some alpha-halo- ketones are reported. The reactions of 3-bromo-3-methyl-2- hutanone, 2-methyl-2,4-dimethyl-3-pentanone, methyl-l-bromo- cyclohexyl ketone, and 1-bromo-l, 1,3,3-tetraphenylacetone with triphenylmethyl sodium as well as 3-bromo-3-methyl-2- butanone and 1-bromo-l, 1,3,3-tetraphenylacetone with dimsyl- sodium were investigated. 3-bromo-3-methyl-2-butanone and 1-bromo-l,1,3,3-tetraphenylacetone when treated with tri­ phenylmethyl sodium gave a considerable amount of the reduc­ tion product. Elimination was also observed when 3-bromo-3- methyl-2-butanone and 2-bromo-2,4-dimethyl-3-pentanone were treated with triphenylmethyl sodium. Although a cyclopro­ panone derivative was not obtained, a better insight into the general reaction of alpha-haloketones and base was realized. Part II A new synthesis of ethers from triaryl and benzhydryl alcohols has been found. Thus, triphenyloarbinol and benz- hydrol when reacted with iodine in the presence of some aliphatic alcohols yield the corresponding ethers. This procedure has proven more convenient than known methods. Cinnamyl alcohol was also found to be amenable to this synthetic procedure, while benzyl alcohol did not yield the ii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Ill the desired products, when subjected to the same reaction conditions. The course of the reaction involves, iodine as a true catalyst which generates a carbonium ion from the trityl and benzhydryl systems. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENTS The author wishes to express his deep gratitude and appreciation to Dr. K.G. Rutherford for his guidance and his patient advice. Most sincere thanks are also due to the National Research Council of Canada who sponsored this study in pant. The author also wishes to thank Dr. R.J. Thibert for his valuable suggestions and criticism in the preparation of this thesis. IV Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS Page ABSTRACT ....................... ...................... 11 ACKNOWLEDGEMENTS ......... ,................... Iv LIST OP TABLES ....................................... vll LIST OF FIGURES ...................................... vlll Chapter Part I I. INTRODUCTION ................................ 1 The Cyclopropanone Structure ............. 1 The Favorskll Reaction ..... 2 History of Cyclopropanones ............... 15 II. DISCUSSION OF EXPERIMENTAL RESULTS ....... 21 III. EXPERIMENTAL ................................ 33 Preparation of Triphenylmethyl sodium .... 33 3-Bromo-3-methyl-2-butanone ....... 35 Tetraphenylacetone ............... 36 Bromotetraphenylacetone ............... 38 3-Bromo-2-butanone ....................... 39 Methyl cyclohexyl Ketone ................. 39 Methyl 1-bromocyclohexyl ketone ......... 4l Dimsylsodium ............................. 42 Reaction of Methyl bromoisopropyl Ketone with Sodium Triphenylmethyl ....... 43 Reaction of l-Bromo-l,l,3,3-tetraphenylace- tone with Sodium Triphenylmethyl .... 46 Reaction of Dimsylsodium with 3-Bromo-3- methyl-2-butanone ........ 48 Reaction of Dimsylsodium with l-Bromo-1,1,3^ 3-tetraphenylacetone .......... 49 Chapter Part II I. INTRODUCTION ................... 50 Alkylation of Hydroxy Compounds with Halogen Compounds .................. 50 Alkylation of Hydroxy Compounds with Alkyl Sulfates ...... 54 V Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Vi TABLE OF CONTENTS (cont'd) Chapter Page Dehydration of Alcohols ...... 56 Interaction of Grignard Reagents with <X-haloketones ....... 57 II. DISCUSSION OF EXPERIMENTAL RESULTS ...... 60 III. EXPERIMENTAL ...... 66 TrlphenylmethyT methyl ether .............. 66 Triphenylmethyl ethyl ether ............ 66 TrlphenyTmethyT n-propyl ether ...... 67 Triphenylmethyl Isopropyl ether ........... 68 Triphenylmethyl benzyl ether ............ 68 Benzhydryl methyl ether ....... 69 Benzhydryl ethyl ether .............. 70 Benzhydryl n-propyl ether ................. 70 Cinnamyl methyl ether ......... 71 Titration of Iodine ...... ■ 72 BIBLIOGRAPHY ..................................... 73 VITA AUCTORIS ..................................... 78 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIST OP TABLES Table P ag e Part I 1. Reaction of 3-Bromo-3-methyl-2-butanone under Conditions of the Pavorskii Reaction ... * 23 Part II 1. Summary of the Ethers Prepared by the New Ether Synthesis ................................... 63 vii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. LIST OF FIGURES Figure Page Part I 1. Resonance Stability of 2,3-Diphenylcyclopro- panone .......... 2 2. Pavorskii Rearrangement of Monohaloketones ... 2 3. Pavorskii Rearrangement of Dihaloketones ..... 3 4. Pavorskii Rearrangement of Trihaloketones .... 3 5. Loftfield Mechanism of Pavorskii Rearrangement 4 6. Cleavage of Unsymmetrical Cyclopropanone Intermediates ........................... 5 7,. Aston and Newkirk Pathway of Cyclopropanone Formation ........................ 7 8. Stereospecific Rearrangement of Epimeric 1- Chloro-l-acetyl-2-methylcyclohexanes .... 8 9. Pavorskii Rearrangement of 17-Bromo-3-acetoxy- pregnane-11,20“dlone with Methoxide ion . iO 10. Epoxyether Formation in Pavorskii Rearrange- n ment ........ 11 11. Reaction of Epoxyethers with Alkoxide Ion .... l2 12. Reaction of Ketene with Diazomethane k l4 ] 13. Reaction of Ketene with C Diazomethane ..... l6 14. 1,1-Diphenyl-2-keto-4-ethoxy Furan ........... 19 15. Reaction of Diazomethane with Ketene Acetal .. 22 16. Pavorskii Reaction of Bromo isopropylmethyl Ketone with Alkoxide Ion ................ 23 17. Mono-<2C-haloketone ............ 26 18. Conversion of p-Keto Acid .................. 30 19. Decarboxylation of a p-Keto Acid ............. • 30 20. Formation of Tetraphenylacetone ......... 31 viii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Ix LIST OP FIGURES (cont'd) . Figure Page 21. Dimerization of Diphenylketene .......... 32 Part II 1. The Williamson Synthesis ...................... 50 2. Reaction of Triphenylmethyl Chlorides with Alcohols .......... 51 3. Alkylation of Hydroxy Compounds by Alkyl Sulfates ...... 54 4. Reaction of Dimethyl Sulfate with Allylic Alcohols ........................ 54 5. Reaction of Dimethyl Sulfate with Chloro- hydrins .................. 55 6\ Alkylation of Phenolic Aldehydes to Alkoxy Aldehydes