Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1971 The tS ereochemistry of Product Formation From Cyclohexyl Cation Intermediates. Stella Daisy Elakovich Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Elakovich, Stella Daisy, "The tS ereochemistry of Product Formation From Cyclohexyl Cation Intermediates." (1971). LSU Historical Dissertations and Theses. 1917. https://digitalcommons.lsu.edu/gradschool_disstheses/1917 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. 71-20,589' ELAKOVICH, Stella Daisy, 1945- THE STEREOCHEMISTRY OF PRODUCT FORMATION FROM CYCLOHEXYL CATION INTERMEDIATES. The Louisiana State University and Agricultural and Mechanical College, Ph.D., 1971 Chemistry, organic University Microfilms, A XEROX Company , Ann Arbor, Michigan THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. THE STEREOCHEMISTKy OF PRODUCT FORMATION FROM CYCLOHEXYL CATION INTEBMEDIAIES A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Stella Daisy Elakovich B.S., Texas Christian University, I966 January, I97I Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Acknowledgment The completion of this work could not have been accomplished without the constant encouragement, guidance, and reassurance given so freely by Professor James G. Traynham, director of this research. Financial support provided by the National Aeronautics and Space Administration and by Louisiana State University during the course of this work is gratefully acknowledged. Financial assistance for the preparation of this manuscript and for expenses incurred in the presentation of parts of this work at the Southeast-Southwest Combined Regional American Chemical Society Meeting given by the Charles E. Coates Memorial Fund of the Louisiana State University Foundation is also gratefully acknowledged. ii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Table of Contents Page Acknowledgment ................................................ il List of Figures.................................................. vii List of Schemes................................ viii List of T a b l e s ................................................ ix Abstract ...................................................... x Chapter I. Introduction ........................................ 1 II. Results and Discussion .............................. 5 A. Oxidative Decarboxylation Reactions ........... 5 B. Sulfenate Ester Reactions ..................... 11 G. Thermal Decomposition of Chlorocarbonates .... 2^ D. Tertiary Cyclohexyl Cations ..... ......... 2J III. Summary ....................................... 3^ IV. Experimental........................................ 39 A. G e n e r a l ....................................... 39 B. Anodic Oxidation of cis- and trans-4-t Butylcyclohexanecarboxylic A c i d ................ 39 1. Preparation of cis- and trans-h-t- Butylcyclohexanecarboxylic A c i d ............ 39 2. Anodic Oxidation of cis- and trans- 4 -^-ButyIcyclohexanecarboxylie A c i d ........ 40 C. Lead Tetraacetate Oxidative Decarboxylation of cis- and trans-4-Jt-Butylcyclohexane­ carboxylic A c i d ................................ 4$ D. Halodecarboxylation of cis- and trans-4-t- Butylcyclohexanecarboxylic A d i d ................ 45 iii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Page E. Chlorinelysis in Acetic Acid of cis- and trans-4-t-Butylcyclohexyl 2,4- Dinitrobenzenesulfenate ........................ 46 1. Preparation nf Isomerically Pure cis- and trans-4-t^Butylcyclohexanol ............ 46 2. Preparation of cis- and trans-4-t- Butylcyclohexyl 2,4- Dinitrobenzenesulfenate .................... 47 5* Chlorination in Acetic Acid of cis- and trans-4-t-Butylcyclohexyl 2,4- Dinitrobenzenesulfenate .................... 48 4. Preparation of 4-t-Butylcyclohexene . „ ^ ^ 50 5. Hydroboration of 4-t-Butylcyclohexene .... 51 6. Partial Hydrolysis of Isomeric Acetate M i x t u r e ...................................... 52 7. Chlorination in Acetic Acid of 4-^-Butylcyclohexene ........................55 F. Bromination in Acetic Acid of cis- and trans-4-t-Butylcyclohexyl 2,4- Dinitrobenzenesulfenate ........................ 55 1. Preparation of 4-^-Butylcyclohexyl Bromide . 55 2. Brominolysis in Acetic Acid of 4-jt- Butylcyclohexyl 2,4-Dinitrobenzenesulfenate. 54 5. Bromination in Acetic Acid of 4-^- Butylcyclohexene.......................... 56 G. Thermal Decomposition of 4-^- Butylcyclohexyl Chlorocarbonates .............. ^ 57 1. Preparation of cis- and trans-4-t- Butylcyclohexyl Chlorocarbonates ............ 57 2. Thermal Decomposition of 4-^- Butylcyclohexyl Chlorocarbonates ............ 58 H. Chlorodehydroxylation of 1 -Methyl-4-t- butylcyclohexanol .............................. 59 1. Preparation of l-Methyl-4-t- butylcyclohexanol........................ 59 iv Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Page 2. Chlorodehydroxylation of 1 -Methyl-4- Jt-butylcyclohexanol.......................... 60 5» Identification of the l-Methyl-4-^- butylcyclohexyl Chlorides .................. 61 I. Hydrochlorination of l-Methyl-4-^- butylcyclohexene ................................ 62 1. Preparation of l-Methyl-4-^- butylcyclohexene.................... 62 2. Hydrochlorination of l-Methyl-4-t- butylcyclohexene ............................ 65 J. Hydrochlorination of 4-t-Butyl-l- methylenecyclohexane.............................. 65 1, Preparation of 4-t-Butyl-l- methylenecyclohexane . ................... 65 2. Hydrochlorination of 4-t-Butyl-l- methylenecyclohexane......... 66 K. Miscellaneous Syntheses and Attempted S y n t h e s e s ............... 66 1. Attempted Chlorodehydroxylation of 4-^-Butylcyclohexanol........................ 66 2. Phthalate Derivative of trans-4-t- Butylcyclohexanol ................ ..... 67 5. Preparation of 4-t^Butylcyclohexanone .... 68 4. Hydrogenation of 4-jt-Butylcyclo- hexanone......................................68 5. Attempted Preparation of 3-^- Butylcyclohexyl Chloride.. ................... 69 6. Attempted Preparation of 4-t^- Butylcyclohexene.............................. TO Appendices I, Nmr Spectra of Cyclohexyl C o m p o u n d s .................. Tl Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Page II. Electrolysis of Carboxylic Acids .................... 7^ A. Introduction and General Procedure................. 7^ B. Hydrocinnamic acid a - d g .......................... 78 G. Bicyclo[5.1.0]hexane-«ço“é-carboxylic Acid and Bicvclof^.1.0Iheptane-exo-7" carboxylic Acid. .................. 81 D. 4-Cyclooctene-l-caruoxylicAc i d ................... 86 E. 2-PhenylcycIohexane-l-carboxylic A c i d .............91 Footnotes........................................................ 92 Selected Bibliography .......................................... 98 V i t a ............................................................ 99 Vi Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. List of Figures Page Figure 1 Electrolytic C e l l .................................. 2 Measurement of Relative Peak Widths at Half Height, AW , of TMS and l-Chloro-trans-l-methyl-4-t- bucylcyclohexane ...................................... 65 3 Measurement of Relative Peak Widths at Half Height, AWjj, of TMS and l-Chloro-cis-l-methyl-4-t- butylcyclohexane............................. .. 6k 4 Nmr Spectrum of trans-4-t-Butylcyclohexyl 2.4-Dinitrobenzenesulfenate ................ ..... 72 5 Nmr Spectrum of cls-4-t-Butylcyclohexyl 2.4-Dinitrobenzenesulfenate .......................... 73 6 Electrolytic C e l l .................................... 77 vii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. List of Schemes Page Scheme 1 Mechanism of Chlorlnolysls In Acetic Acid of Alkyl 2,^-Dinltrobenzenesulfenates .................. 12 vlil Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. List of Tables Page Table I Effect of Lithium Perchlorate on the Product Distribution from the Chlorlnolysls In Acetic Acid of cis- and trans-4-t-Butylcyclohexyl 2,4-Dlnltrobenzenesulfenates ............................... II Product Distribution from the Chlorlnolysls In Acetic Acid of cis and trans-4-t- Butylcyclohexyl 2,4-Dlnltrobenzenesulfenates ............. IJ III Product Distributions for the Brominolysis In Acetic Acid of cis- and trans-U-t- Butylcyclohexyl 2,4-Dlnltrobenzenesulfenates ............. 22 IV Stereochemistry of Product Formation from Secondary Cyclohexyl Cations ............................... 55 V Stereochemistry of Product Formation from Tertiary Cyclohexyl Cations