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Part I Dif'ositive Carboniun Ions Part Ii PART I DIF‘OSITIVE CARBONIUN IONS PART II PEROXQYTRIFLUOROACETIC ACIDeBORON FLUORIDE AS A SOURCE OF POSITIVE HYDROXYL Thesis Ior Hm Degree OI DI'I. D. MICHIGAN STATE UNIVERSITY Charles Allen Buehler 1963 .-_ LIBRA R Y Michigan State niversity w... .. 5.22 62.25 pm<u v0.4, >.:m ”.53-. Edam 28.192. ABSTRACT PART I DIPOSITIVE CARBONIUM IONS PART II PEROXYTRIFLUOROACETIC ACID-BORON FLUORIDE AS A SOURCE OF POSITIVE HYDROXYL by Charles Allen Buehler The primary purpose of the first part of this thesis was to further investigate the scope of dipositive carbonium ionnchemistry. The aluminum chloride-catalyzed reaction of carbon tetrachloride with pentamethylbenzene (1-), was extended to the preparation of 3-halo (bromo land- chloro)-Z, 4, 5,6-tetramethylbenzotrichlorides and Z-chloro- 3, 4,5,6-tetramethy1benzotrichloride. « Each of these benzotrichloride derivatives dissolved in 100% sulfuric acid to form intensely red solutions and evolve hydrogen chloride. Hydrolysis of the colored solutions gave nearly quantitative yields of the corresponding 3- and 2-halotetramethylbenzenecarboxylic acids. By analogy with earlier work, the best explanation for these data is the formation of stable dicarbonium ions. -+ ' X The structure of these dipositive ions was investigated by ultraviolet, visible and proton magnetic resonance spectroscopy. [Charle s Allen Buehler Also investigated were the solutions of various benzophenone dichlorides (2,3, 4, 5-tetramethy1-, 3,‘5-dimethyl-, z, 4-dimethy1-, 4,4'-dime-thyl- and benzophenone dichloride itself) in sulfuric acid, with the hope of observing dicarbonium ions of the following type: c=© The benzophenone dichlorides were prepared by refluxing a solution of the corresponding ketone with phosphorus pentachloride in carbon tetrachloride. The visible, ultraviolet and proton-magnetic resonance spectra of these compounds in 100% sulfuric acid were similar regardless of the substitution. However, their spectra also compared favorably with the spectra of similarly substituted diphenyl- methylcarboniurn ions in the same solvent. The mono-ionization of these dichlorides in sulfuric acid was substantiated by their spectra and the production of only one mole of hydrogen chloride when a solu- tion of 2, 3,4, 5-tetramethylbenzophenone dichloride in sulfuric acid was swept with dry nitrogen, the phenyl apparently stabilizing the mono-ion more than the dicarbonium ion. The second part of this thesis .is concerned with the use of peroxytrifluoroacetic acid-boron fluoride as a potent source of positive hydroxyl. Synthetically, this reagent proved useful in preparing mesitol and .isodurenol from mesitylene and isodurene in excellent yields (88 and. 65%). The-reagent is, however, quite severe , and was found to bring about new and interesting side reactions in addition to electrOphilic replacement. Prehnitene gave, besides the expected prehnitol, Z, 2';.,3,' 3', 4, 4', 5, 5'-octamethyldiphenylmethane, 4, 5, 6, 6-tetramethyl- cyclohexa-Z, 4-dienone, 2, 3, 5-trimethylphenol, Z, 3, 6-trimethylphenol Charle s Allen Buehler and isodurenol as products of the reaction with peroxytrifluoroacetic acid-boron fluoride. Similarly, chloro- and nitromesitylene underwent hydride abstraction to form coupled materials of the following structure: X = C1, N02 The mechanism of these reactions is discussed in light of the known ability of peroxytrifluoroacetic acid to function ionically- (Z). The reactions of less substituted aromatics (such as benzene) with this reagent were extremely complex and gave largeamounts of intractable tar. - REFERENCES 1) H. Hart and‘R. w. Fish, J.-Am.-Chem. Soc., 333,. 5419 (1960) Z) R. D..Chambers,- P. .Goggin, and W.-K. -R.~ Musgrave, J. Chem. Soc. , 1804 (1959). PART I DIPOSIT IVE CAR BON IUM =IONS PART II PEROXYTRIFLUOROACETIC ACID-BORON FLUORIDE .AS A SOURCE OF POSITIVE HYDROXYL BY . Charles Allen- Buehler A THESIS ' Submitted to Michigan. State Univer sity in partial fulfillment of the requirements forrthe: degree of DOCT OR OF PHILOSOPHY Department of Chemistry 1963 ACKNOWL’ED GMEN T . The author~wishes to expresshis sincere appreciation and gratitude toProfessor' Harold Hart for-his inspiration, guidance and understanding. duringthe-course of this investigation. - Appreciation is extended to S. ’Meyerson for‘determining the mass spectra. - Apprec‘iation'is extended to the Petroleum Research‘Fund of theAmerican-Chemical Society for financial support from-September, 1961 through‘June, 1962 and to the National Science Foundation for financial support and ~‘aCoopera-tive Fellowship, June, 1962 through June, 1963. Appreciation'is also-extended to my friends, colleagues and loved-ones for their inspiration and guidance throughout my tenure at MichiganState University. Grateful appreciation is also extended tomy wife, . Millie, for- her patience and encouragement at all times. .*****s******* ii TABLE OF CONTENTS Page 'PART- I ((DIPOSIT'IVE CARBONIUM IONS ‘INTRODUCTION.I............. RESULTSANDDISCUSSION.. I. Trichloromethylbenzene Derivatives. A.Preparation................. ~B. Dicati‘on Formation'in 100% Sulfuric Acid 12 II. BenzophenoneDichlorides . 21 ‘AoPreparation'oo0000.00.ooooooo 21 B..Solutions of Benzophenone Dichlorides in ~Su1furic Acid . .32 III. Miscellaneous Experiments 49 EXPERIMENTAL........... 56 I. Trichloromethyl Compounds . 56 A.Synthesis ............ 56 ‘Preparation of Pentamethylbenzene 56 ‘Preparation of Isodurene. .. 57 ’Preparation of Prehnitene . 58 'Attempted Preparation of Trichloromethyl- -isodurene O O O O O O‘O O O O O O O O O O 58 ‘Preparation of Bromoprehnitene. 60 Attempted - Pr eparationi of Tr ichlor om ethyl- bromoprehnitene. 61 Preparation of Bromoisodurene . 63 Preparation of Trichloromethylbromoi-z isodurene..-............ 63 'Prepara ion of 3-Bromo-Z, 4, 5, 6-tetra- methylbenzoic acid . 66 Hydrolysis of Trichloromethylbromo- isodurene 66 iii TABLE OF CONTENTS - Continued Page Preparation of Chloroisodurene . 68 'Preparation of Trichloromethylchloro- isodurene. ._._.,.. 69 Preparation of 3-Chloro-2, 4, 5, 6-tetra- methylbenzoic acid . O 70 Hydrolysis of Trichloromethylchloro- isodurene ........... 73 Preparation of Chloroprehnitene. .A. 73 Preparation of Tric hloromethylchloro- prehnitene.......... ...... 76 - Hydrolysis of Trichloromethylchloro- prehnitene................ 76 ’Preparation of Trichloromethylprehnitene 79 ‘Preparation of Methoxyisodurene . 80 Attempted 'Preparation of 2, 4, 5, 6-‘I‘etra- methyl-3-methoxybenzotrichloride. 80 Attempted-Preparation of 2, 4, 6-Trimethoxy- benzotrichloride. 82 II. Benzophenone. Dichlorides .". .‘ . 83 A.Synthesis.................... 83 Attempts to Prepare 2, 3, 4, 5, 6-Penta- methylbenzophenone Dichloride. 83 Preparation of 2, 3, 4, S-Tetramethylbenzo- phenone.................. 85 *Preparation of Z, 3, 4, 5-Tetramethy1benzo- phenone Dichloride . ... 87 Hydrolysis of Z, 3, 4, 5-Tetramethy1benzo- phenone Dichloride . 88 Preparation of 1-(2, 3, 4, 5-tetramethylphenyl)- l-phenylethylene . 90 ’Preparation of 2,4-Dimethy1benzophenone . 91 - Preparation of 2, 4-Dimethylbenzophenone Dichloride................. 94 'Preparation of 4, 4'-Dimethy1benzophenone \Dichloride................. 94 'Preparation of 1, 1-Bis(p-tolyl)-ethylene . 94 ‘Preparation of 3, S-Dimethylbenzophenone . 98 %Preparation of 3, 5-Dimethy1benzophenone Dichloride................. 98 iv TABLE OF CONTENTS -- Continued Page Preparation of Benzophenone Dichloride. 100 'Preparation of 2, 4, 6-Trimethy1benzo- phenone.................... 100 Attempted Preparation of 2, 4, 6-Trimethyl- benzophenone Dichloride . 103 Hydrolysis of a Solution of 2., 4, 6-Trimethy1- benzophenone , , Phosphorus ' Pentachloride and Carbon Tetrachloride after Seventeen ‘HoursReflux................ 103 B. Quantitative Determination of Hydrogen‘Chlor- ide From the Reaction of 2, 3,4, 5-Tetra- .methyl benzophenone Dichloride with Sulfuric Acid...................... 107 111. Miscellaneous Experiments . 108 Preparation of 2, 3, 4, 5, 6-Pentamethylaceto- phenone............ ...... 108 'Preparation of 1-Chloro-1-(2, 3, 4, 5, 6- pentamethylphenyl)ethylene . 108 Hydrolysis of a 101% Sulfuric Acid-Solution of Chloro-(Z, 3, 4, 5, 6-pentamethy1pheny1)- ethylene.................. 112 Preparation of 1-(2, 3, 4, 5, 6-Pentamethy1- phenyl)acetylene . 112 Hydrolysis of Sulfuric Acid Solutions of 1-(2, 3, 4, 5, 6-Pentamethylpheny1)ac etylene 113 Hydrolysis of Sulfuric Acid Solutions of Phenylacetylene . 115 SulfuricAcid................... 115 Spectra...................... 116 SUMMARY O O O O O O O O O O O O O O O O O O O O O O O O O O O O 117 PART II PEROXYTRIFDUOROACETIC ACID-BORON FLUORIDE AS ASOURCE OF POSITIVE HYDROXYL INTRODUCTION O O O O O O O O O O O O O O O O O O O O O O O O O 12.0 RESULTSANDDISCUSSION. .. 123 TABLE OF CONTENTS - Continued Page EXPERIMENTAL . 138 I. Oxidatiens . 138 'A. Mesitylene 138 . Isodurene . 140' . ~ Pr ehnitene 141 . Chloromesitylene. 156 .-Nitromesity1ene. 163 mmoow . Benzene. 164 II. -Vapor-Phase Chromatography. 168 SUMMARY 169 ‘ LITERATURE CITED . 170 vi LIST OF TABLES TABLE Page .Proton magnetic resonance spectra of some halo- tetramethylbenzotrichlorides in. carbon tetrachloride. 8 .Ultraviolet absorption maxima of some trichloro- methyl compounds in cyclohwexane and n-hexane. 15 III. Ultraviolet and visible absorption maxima of some trichloromethylbenzenes in-100% sulfuric acid . 17 -IV.. Proton magnetic resonance spectra of some halotetra- methylbenzotrichlorides and their corresponding carboxylic acids in 100% sulfuric acid . 19 .Proton‘magnetic resonance spectra of substituted
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