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A Kinetic Investigation of the Thermal and Acid-Catalyzed Decompositions

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A Kinetic Investigation of the Thermal and Acid-Catalyzed Decompositions This dissertation has been 65— 13,248 microfilmed exactly as received J O R D A N , David Milton, 1937- A KINETIC INVESTIGATION OF T H E THERMAL AND ACID-CATALYZED DECOMPOSITIONS OF ci-DIAZOACETOPHENONES. The Ohio State University, Ph.D., 1965 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan A KINETIC INVESTIGATION OF THE THERMAL AND AC ID-CATALYZED DECOMPOSITIONS OF a-DIAZOACETOPHENONES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University David Milton Jordan > B.A The Ohio State University 1965 Approved by Department of Chemistry ACKNOWLEDGMENT I wish to express my appreciation to Professor Harold Shechter for his suggestion of the research problem* for many helpful dis­ cussions in the course of the investigation* and for his assistance in preparation of this dissertation. I am grateful for financial support provided by the National Science Foundation and the Phillips Petroleum Company. ii VITA August 19, 1937 Born - Ashtabula, Ohio 1955 Graduated from Mount Pleasant High School, Wilmington, Delaware 1959 B.A., The College of Wooster, Wooster, Ohio 1959-1961 National Science Foundation Cooperative Fellow, Department of Chemistry, The Ohio State Uni­ versity, Columbus, Ohio 1961-1963 National Science Foundation Graduate Fellow, Department of Chemistry, The Ohio State Uni­ versity, Columbus, Ohio 1963-1964 Phillips Petroleum Company Fellow, Department of Chemistry, The Ohio State University, Columbus, Ohio 1964-1965 Research Fellow, Department of Chemistry, The Ohio State University, Columbus, Ohio MAJOR FIELD OF STUDY: Organic Chemistry iii CONTENTS Page ACKNOWLEDGMENT............................................ ii VITA ....................................................... ill TABLES................................................... vi FIGURES ................................................... vii INTRODUCTION............................................. 1 HISTORICAL................................................ 2 The Wolff Rearrangement ............... 2 Thermal Decomposition of a-Diazoacetophenone .... 6 Photolytic Decomposition of Diazoketones ...... 13 Copper-Catalyzed Decomposition of Diazoketones . 16 Reactions of Diazoketones with Bases ........ 19 Ac id-Catalyzed Decomposition of a-Diazoacetophenones ............. 19 Participation in Decompositions of ortho- Substituted a-Diazoacetophenones in Acetic A c i d .................................. 24 General Acid-Catalysis of a-Diazoacetophenone .... 26 DISCUSSION AND RESULTS .................................... 28 Discussion of the Kinetics of Decomposition of Substituted a-Diazeacetophenones in Acetic Acid...................................... 65 EXPERIMENTAL.............................................. 84 General Procedures and Techniques .......... 84 Melting and boiling p o i n t s .................... 84 Elemental analyses............................ gjj, Spectra determinations .............. ..... 84 Vapor phase chromatography .......... 84 Material for Kinetic R u n s .......................... 86 Syntheses of substituted benzoyl chlorides . 86 Synthesis of a-diazoacetophenones ....... 86 iv CONTENTS (Contd.) Page Materials Used for Kinetic Measurements................ 88 Cetane (hexadecane) .............................. 88 Tetraglyme ...................... 90 Quinoline ...... ............................ 90 n-Decanol .......... 90 Tenox B H A ........................................ 90 Tenox B H T ........................................ 90 Tri-n-butylamine.................................. 90 Cyclooctane...................................... 90 DABCO (1 >&-diazobicyclooctane.................... 91 Tri-n-propylamine................................ 91 Di-n-bu ty la m i n e .................................. 91 Di-n-propylamine.................................. 91 1-Chloronaphthalene .............................. 91 Acetic A c i d ...................................... 91 T o l u e n e ............................ 92 Procedure for Kinetic R u n s ........................... 92 Constant temperature bath . ..... 92 Thermal decomposition procedure . .............. 92 Reactions catalyzed by acetic a c i d .............. 97 Development of Solvent System for Thermal Decomposition.............................. 99 Product Studies....................................... 112 Products of Thermal Decomposition of a-Diazo­ acetophenone in Tripropylamine.................... 112 Products of Thermal Decomposition of a-Diazo­ acetophenone in Dipropylamine • 116 Products of Decomposition of a-Diazoaceto- phenone in Cyclohexene . ........................ 118 Product of Thermolysis of a-Diazoaceto- phenone in Cyclooctane and N»N- dimethylcyclohexylamine . 122 Product of Thermal Decomposition of a-Diazo­ acetophenone in Cyclooctane Containing l*^-Diazobicyclo[2.2.2]octane (DABCO) ....... 123 v TABLES Table Page 1* Average First Order Rate Constants (lO^sec*"1) for Thermal Decomposition of Substituted a-Diazoacetophenones ..... .................. 35 2. The Thermal Decomposition of Substituted a-Dia zoac etophenones in Tripropylamine.......... 3. Relative Rates of Thermal Decomposition of Substituted a-Diazoacetophenones and Benzazides.......................... 41 4. Products of Thermal Decomposition of a-Diazo­ acetophenone in Tripropylamine at 156° ........ 5? 5 . Acetic Acid-Catalyzed Decomposition of Substituted a-Dia zoacetophenones.............. 67 6. Relative Rates of Acetic Acid-Catalyzed Decompo­ sition of Substituted a-Diazoacetophenones .... 69 7* Preparation of Substituted Benzoyl Chlorides Z-CgH^COCl.................. 87 8* Preparation of Substituted a-Diazoacetophenones . 89 9« The Decomposition of a-Diazoacetophenone in Decanol-Quinoline-Tenox BHA (Yates and C l a r k ) .............................. 104 10. Decomposition of a-Diazoacetophenone in Cetane- Tributylamine at I3 0 .50 ........................ 108 11. Thermal Decompositions of a-Diazoacetophenones in Tripropylamine ................ 125 vi FIGURES Figure Page 1. An isokinetic relationship of activation parameters for thermal decomposition of substituted a-diazoacetophenones ............... ^7 2. Hammett relationship for thermal decompositions of meta- and para-substituted a-diazo­ acetophenones .................................. 50 3. Hammett relationship for acetic acid-catalyzed decomposition of meta- and para-substituted a-diazoacetophenones ............................ 71 4. Hammett relationship for acetic acid-catalyzed decomposition of meta- and para-substituted a-diazoacetophenones ............................ 72 5. Correlation of rates of thermal and acetic acid- catalyzed decompositions of substituted diazoacetophenones . ................ ..... 82 6. Modified reaction f l a s k .............. 93 7* Reaction vessel for acetic acid-catalyzed decomposition of diazoacetophenones ....... 98 8. Thermal decomposition of a-diazoacetophenone in c e t a n e .............................. 101 9. Thermal decomposition of a-diazoacetophenone in cetane at 1 1 9 ° ...................... 102 10. Thermal decomposition of a-diazoacetophenone at 1 3 0 . 5 ° .............................. 13*4- 11. Thermal decomposition of ortho-bromodiazo- acetophenone at 130.5° .......................... 135 12. Thermal decomposition of ortho-chlorodiazoO acetophenone at 130.50 .......................... 13& 13. Thermal decomposition of ortho-iododiazo- acetophenone at 110.9° .......................... 137 vii FIGURES (Contd.) Figure Page 14 • Thermal decomposition of ortho-methyldiazo- acetophenone at 130.50 .......................... 138 15• Thermal decomposition of ortho-methoxydiazo- acetophenone at 110.9° .......................... 139 16. Thermal decomposition of meta-methoxydiazo- acetophenone at I3O.50 .......................... 1^0 17. Thermal decomposition of meta-nitrodiazo- acetophenone at 1 3 0 .9 ° ........................... 1^-1 18. Thermal Decomposition of para-methoxydiazoaceto- phenone at 130 *3° 142 19* Thermal decomposition of para-nitrodiazo- acetophenone at 130 . 5 ° ....................... 143 20-29. Arrhenius plots ................................ 144-133 viii INTRODUCTION The primary object of this research was determination of the effects of structure on the kinetics of thermal decomposition of substituted a-diazoacetophenones (Wolff rearrangements). COCHN. Z Z represents electron-donating and withdrawing substituents in ortho- > meta-, and para-positions, The purposes of this investigation were to attempt Hammett and related correlations and to obtain information concerning the electrical requirements and reaction mechanisms of these systems. The study of steric acceleration and proximity effects in decomposition of ortho-substituted a-diazoacetophenones was em­ phasized. It was also of interest to compare the kinetics of the acetic acid-catalyzed decomposition of ortho-substituted a-diazoacetophenones •with the results of kinetic studies previously conducted on the acetic acid-catalyzed decomposition of meta- and para-substituted a-diazo- acetophenones (1), (1) (a) J. F. Lane and R. L. Feller* J. Am. Chem. Soc.* 22* ^230 (1951); (b) Y. Tsuno* T. Ibata, and Y. Yukawa, Bull. Chem. Soc. Japan* j2, 960 (1959); (c) Y. Yukawa and Y. Tsuno, ibid., ^2, 965 (1959). 1 HISTORICAL The Wolff Rearrangement In 1902 L. Wolff reported the conversion* by reaction with boiling water, of ethyl a-diazoacetoacetate (I) to the half ester of methyl malonic acid (II) and of 2-diazo-l-phenylbutane-l»3-dione
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