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Addition Reactions and Photoisomerization of Cis,Trans-1,5-Cyclodecadiene

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Addition Reactions and Photoisomerization of Cis,Trans-1,5-Cyclodecadiene Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1970 Addition Reactions and Photoisomerization of Cis,trans-1,5-Cyclodecadiene. Hsin-hsiong Hsieh Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Hsieh, Hsin-hsiong, "Addition Reactions and Photoisomerization of Cis,trans-1,5-Cyclodecadiene." (1970). LSU Historical Dissertations and Theses. 1859. https://digitalcommons.lsu.edu/gradschool_disstheses/1859 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]. 71-6579 HSIEH, Hsin-Hsiong, 1936- ADDITION REACTIONS AND PHOTOISOMERIZATION OF CIS,TRANS-1,5-CYCLODECADIENE. The Louisiana State University and Agricultural and Mechanical College, Ph.D., 1970 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan ADDITION REACTIONS AND PHOTOISOMERIZATION OF CIS,TRANS-1,5“CYCLODECADIENE 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 Hsin-Hsiong Hsieh B.S., Taiwan Provincial Chung-Hsing University, i960 M.S., Louisiana State University, 1966 August, 1970 ACKNOWLEDGEMENT I wish to express my deepest appreciation to Professor James G . Traynham for his guidance, inspiration, and encouragement in performing this research and for his many suggestions in the preparation of this dissertation,, The financial support by the National Science Foundation for this research, a special final year graduate fellowship given to the author by the Petroleum Research Fund administered by the American Chemical Society, and the financial assistance for the preparation of this dissertation by the Dr. Charles E„ Coates Memorial Fund of the L.S.Uo Foundation denoted by George H. Coates are gratefully acknowledged. TABLE OF CONTENTS , Page ACKNOWLEDGEMENT . ................................................ ii LIST OF TABLES . ......................... vi LIST OF SCHEMES ................................... vii ABSTRACT ................. viii CHAPTER ........................... .................. I. INTRODUCTION ........................ 1 II. RESULTS AND DISCUSSION .................. ....... 10 Addition Reactions ........................... 10 Ionic Additions ............................ 1 0 Radical Additions..... ........................... 18 Ionic and Radical Additions...................... 30 Carbene Additions . ........................ 37 Photoisomerization of cis,trans-l,5-Cyclodecadiene . 43 Relative Reactivities of cis,trans- and cis,cis-1, 5-Cyclodecadienes..... ............. 49 III. E X P E R I M E N T A L .............. 54 A. Preparation of cis,trans-l,5“Cyclodecadiene .... 54 1. Ethoxydibutylaluminum.......................... 54 2. Nickel-bijs-l,5-Cyclooctadiene................. 55 3 . Preparation of cis,trans-l,5-Cyclodecadiene . 55 B. Ionic Additions of Reagents to cis,trans-1,5- Cyclodecadiene .................................. 56 1. Addition of Trifluoroacetic A c i d ............. 56 iv TABLE OF CONTENTS (Continued) Page 2. Addition of Mercuric Azide .......... 58 3® Addition of Acetonitrile ............. 60 k. Addition of Benzonitrile ........... 6l C. Radical Additions of Reagents to cis,trans-1,5- Cyclodecadiene . 62 1. Radical Addition of Chloroform ........ 62 2. Radical Addition of Bromotrichloromethane . 6k a. In Excess Bromotrichlorome thane ..... 6k b. In Methylene Chloride Solution ...... 6j 3® Radical Addition of Bromoform ............... 68 D. Ionic and Radical Additions of Reagents to cis, trans-l,5-Cyclodecadiene . ...................... 68 1. Additions of Molecular Chlorine ............. 68 a. In the Absence of Oxygen ............ 68 b. In the Presence of O x y g e n .......... 70 2. Additions of Iodobenzene Dichloride ........ 71 a. Iodobenzene Dichloride .......... 71 b. Addition of Iodobenzene Dichloride in the Presence of Oxygen ............... 71 c. Addition of Iodobenzene Dichloride in the Absence of Oxygen ................. J2 3 . Additions of Bromine Azide .......... J2 a. Preparation of Bromine A z i d e ............. J2 b. Ionic Addition of Bromine Azide ..... 73 c. Radical Addition of Bromine Azide .... 73 V TABLE OF CONTENTS (Continued) Page E. Additions of Carbenes to cis, trans-l,5-Cyclo- decadiene . ............................... 7^- 1. Methyleneation by Simmons-Smith Reaction . 7^ 20 Methyleneation by Diazomethane ........ 75 3« Addition of Dibromomethylene ......... 76 4. Addition of .Isopropylidenemethylene ...... 77 F. Photoisomerization of 1,5-Cyclodecadienes ..... 79 1. General Procedure ............... 79 2. Copper(l) Chloride Catalyzed Photoisomerization of cis, trans-l,5-Cyclodecadiene ....... 80 3. Photoisomerization of cis,trans-l,5-Cyclo- decadiene with Xylene Sensitizer .......... 81 4. Photoisomerization of cis,cis-l,5-Cyclodeca- diene with Xylene Sensitizer .............. 82 G. Thermal Rearrangement of cis,trans- and cis,cis-1,- 5-Cyclodecadienes .... .................. 82 H. Addition of Trifluoroacetic Acid to cis,cis-1,5- Cyclodecadiene ........ ...... .......... 82 I. Relative Rates of Additions of Trifluoroacetic Acid to cis, trans- and cis,cis-l,5-Cyclodecadiene . 83 IV. CONCLUSIONS ................. 8^ REFERENCES ..................... .......... 86 SELECTED BIBLIOGRAPHY ...................... 90 APPENDIX ........... .................................... 91 VITA .................................................... .. 92 LIST OF TABLES Table Page I. Thermodynamic Stabilities of Medium Ring Olefins ......... 2 II. Substituted cis-Decalins from Ionic Reactions of cis, - trans-l,5-Cyclodecadiene ................... 11 III. Product Distributions from the Reactions of Iodobenzene Dichloride with cis, trans-l,5-Cyclodecadiene jh IV. Product Distributions in Reactions Yielding 1,2-Addition Products with cis,trans-l,5-Cyclodecadiene............ 38 V. Product Distributions in Xylene-Sensitized Photoisomeri­ zation of cis, trans-l,5-Cyclodecadiene ............... ^7 VI. Product Distributions of the Thermal Rearrangement of cis,trans- and cis,cis-l,5-Cyclodecadiene to cis-1,2- Divinylcyclohexane . „ . .............. 50 vi LIST OF SCHEMES Scheme Page 1. (Mechanism of the addition of trifluoroacetic acid to cis, trans-l,5-cyclodecadiene)............ 12 2. (Mechanism of the addition of mercuric azide to cis, trans-1.5-cvclodecadiene) .... ................... 16 3. (Mechanism of the addition of alkylnitrile to cis,trans- 1 .5-cyclodecadiene . ............. ........ 18 4. (Radical addition of chloroform to cis,trans-l,5-cyclo- decadiene) ...... ................................ 20 5. (Mechanism of the radical additions of bromotrichloro- methane to cis,trans-l,5-cyclodecadiene) ....... 28 6. (Radical addition of iodobenzene dichloride to cis, trans-l,5-cyclodecadjene) . .......................... 36 7. (Addition of carbenes to cis,trans-l,5-cyclodecadiene) . yj 8. (Photoisomerization of c_is,trans-l,5-cyclod.ecadiene) . 48 9. (Thermal rearrangements of cis,trans- and cis,cjs- 1 .5-cyclodecadiene to cis-l,2 -divinylcyclohexane) . 50 10. (Mechanisms of the addition of trifluoroacetic acid to cis,trans- and cis,cis-l,5-cyclodecadiene) .... $2 vii ABSTRACT Ionic additions of reagents, such as trifluoroacetic acid, mer­ curic azide, acetonitrile, benzonitrile, molecular chlorine, iodobenzene dichloride, and bromine azide, to cis, trans-l,5-cyclodecadiene result in transannular cycloadditions to form substituted cis-decalins as products. The products from these reactions are consistent with stepwise or con­ certed mechanisms. The products obtained from the radical additions of halomethanes, molecular chlorine, iodobenzene dichloride, and bromine azide, which add to the diene by a stepwise mechanism, depend on the reagents and the conditions employed for the reactions. For poor trans­ fer agents such as chloroform, and under very dilute conditions, the addition occurs exclusively by transannular (1,6) G-C bond formation. However, when a large excess of bromoform was used,some 1,2-addition product was also isolated. Carbenes generated from diazomethane, bro­ moform, and 5 ,5-dimethyl-N-nitrosooxazolidone also added to the diene. In each case, the carbene added to the trans double bond in the diene in preference to the cis double bond. The stereochemistry of some of these adducts, and the mechanistic implications of these results are discussed. Finally, the cis,trans-1,5 -diene was photoisomerized to cis,cis-l,5-diene. The relative reactivities of these two isomeric dienes were compared by the Cope rearrangment and the addition of tri­ fluoroacetic acid. The differences between the thermal stabilities and the reactivities of these two isomers are discussed in terms of confor­ mational control of the transition states leading to the products. CHAPTER I INTRODUCTION This study deals with ionic, radical, and carbene additions to cis,trans-1 ,5-cyclodecadiene (i) and with the photoisomerization of the diene. lo 6 4 Interest in these reactions derives from observations reported in the recent literature. For example, ionic addition of reagents to the diene I resulted in the formation of mono- or disubstituted cis-deca-
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