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Free Radical Additions to Cis-Cyclooctene and Cis-Cyclodecene

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Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1966 Free Radical Additions to Cis-Cyclooctene and Cis-Cyclodecene. Thomas Michael Couvillon Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Couvillon, Thomas Michael, "Free Radical Additions to Cis-Cyclooctene and Cis-Cyclodecene." (1966). LSU Historical Dissertations and Theses. 1115. https://digitalcommons.lsu.edu/gradschool_disstheses/1115 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]. This dlseerletlOBhas been mlorcfllmed wcactly «• recelTwl 66—6435 C O U V I L L O N , Th o m a s Michael, 1940- FREE RADICAL ADDITIONS TO CIS- CYCLOOCTENE AND CIS-CYCLODECENE. Louisiana State University, Ph.D., 1966 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan FREE RADICAL ADDITIONS TO CIS-CYCLOOCTENE AND CIS-CYCLODECENE 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 Thomas Michael Couvillon B.S., Louisiana State University, Baton Rouge, 1962 January, 1966 ACKNOWLEDGMENT The author wishes to express his deepest appreciation to Professor James G. Traynham for his guidance and encour­ agement In this work. He would also like to thank his wife, Kay, not only for her assistance In preparing this manuscript but for her dally encouragement over the past three years which made It possible for him to c.omplete this work. This author gratefully acknowledges the financial support given him from a grant by the Petroleum Research Fund (administered by the American Chemical Society) which supported a major portion of this work. He would also like to acknowledge the financial help In preparing this disser­ tation generously provided by the Dr. Charles E. Coates Memorial Fund of the L.S.U. Foundation donated by George H. Coates. He also must take this opportunity to thank his family, especially his mother and his mother-in-law, for their encouragement and assistance. 11 TABLE OP CONTENTS Chapter Page I. INTRODUCTION.................................. 1 II. RESULTS AND DISCUSSION........................ 10 A. Carbon Tetrachloride Additions.............. 14 B. Bromotrlchloromethane Additions ......... 18 C. Chlorinatlons of cls-Cyclooctene and cls- Cyclodecene .................................. 25 D. Kinetic and Energy Considerations .... 29 III. EXPERIMENTAL................................... 37 A. Photo-initiated Addition of Carbon Tetrachloride to cls-Cyclooctene........38 B. Basic Dehydrochlorination of Major Addition Products ......................... 41 C. Synthesis of 4-Chlorocyclooctanone. 46 D. Silver Nitrate Dehydrochlorination of Major Addition Products .................. 49 E. Identification of Minor Products in Carbon Tetrachloride Addition Reaction. 52 F. Thermally-initiated Addition of Carbon Tetrachloride to cls-Cyclooctene........56 G. Photo-initiated Addition of Carbon Tetrachloride in Benzene Solvent........58 H. Photo-initiated Addition of Bromo- trichloromethane to cls-Cyclooctene .. 59 I. Peroxide Initiated Addition of Trichloro- methanesulfonyl Chloride to cls- Cyclooctene .............................. 68 J. Photo-initiated Addition of Chloroform to cls-Cyclooctene....................... 74 iii iv Chapter Page K. Preparation of Chlorocyclooctane and 3-Chlorocyclooctene ........................ 76 L. Chlorination of cis-Cyclooctene ..... 78 M. Chlorination of cis-Cyclodecene .......... 80 N. Photo-initiated Addition of Carbon Tetrachloride to cis-Cyclodecene............82 IV S U M M A R Y ........................................... 85 REFERENCES ............................................... 89 A SELECTED BIBLIOGRAPHY.................................. 9^ VITA ...................................................... 95 LIST OP TABLES Table Page I. CORRELATION OP N.M.R. SPECTRA WITH POSITION OP SUBSTITUTION FOR CYCLOOCTANE DERIVATIVES . 12 II. PRODUCT DISTRIBUTION DATA FOR CC1.. ADDITIONS TO cis-CYCLOOCTENE................H .............. 13 III. PRODUCT DISTRIBUTION DATA FOR BrCCl, ADDITIONS TO cls-CYCLOOCTENE. .i........... 19 IV. PRODUCT DISTRIBUTION DATA FOR CHLORINATION OF cls-CYCLOOCTENE............................... 26 V. PRODUCT DISTRIBUTION DATA FOR CHLORINATION OF cis-CYCLODECENE............................... 26 v LIST OF FIGURES Figure Page 1. Proton Decoupling Experiments on 1-Bromo- 2-trichloromethylcyclooctane in Acetone-dg. 65 2 . Proton Decoupling Experiments on 1-Bromo- 2-trichloromethylcyclooctane in Benzene-dg. 66 Vi ABSTRACT Free radical additions to cis-cyclooctene and cis-cyclodecene were investigated to determine if trans- annular additions accompany such reactions. Both normal and transannular additions occur> depending mainly upon the nature of the addend. Photo- and thermally-initiated additions of carbon tetrachloride give principally an isomeric mixture of l-ehloro-4-trichloromethylcyclooctanes. The transannular nature of these products was proven by selective dehydrochlorlnatlon of both Isomers to the same l-chloro-4-dichloromethylenecyclooctane, which, through ozonation was converted to 4-ehlorocyclooctanone. The addition of trichlororaethanesulfonyl chloride gives substantial amounts of l-ehloro-2-i-trichloromethyl- cyclooctane in addition to the transannular products. Addition of bromotrichloromethane.gives.principally l-bromo-2-i-trichloromethylcyclooctane with minor amounts of the 1,4 isomers.. Chlorinations of cyclooctene and cyclodecene give the 1,2-dlchlorocycloalkanes as the only addition products under both ionic and free radical conditions. The competition between vicinal and transannular addition is discussed in terms of the kinetic and energy requirements for the two processes. vii CHAPTER I INTRODUCTION Medium ring compounds (those of ring size eight to twelve carbon atoms) exhibit certain chemical and physical properties which set them apart from other ring sizes.^ Thermochemical measurements indicate that these rings are 2 3 unusually strained and X-ray dataJ show considerable devi­ ation from the tetrahedral valence angle. A major source of this strain Is the end-on interaction of the hydrogens 14 on opposite sides of the ring (transannular strain). Cope suggests the use of the term "proximity effect" to include other non-viclnal interactions in which an atom or group is fixed in the proximity of another group by steric require­ ments of the molecule. Because of this closeness (or proximity), it is possible for usually inert groups to par­ ticipate In a reaction occurring three or more carbon atoms away. If this participation involves migration of an atom or group, it may be classified as a transannular rearrangement. For medium rings, the migration of a hydride ion to a transannular carbonium ion site has been most extensively 1 4 studied. * The first observations of transannular hydride migrations were reported almost simultaneously by Cope"^ and Prelog^ In the peroxyformic acid oxidations of cyclooctene 1 2 and cyclodecene. Medium ring olefins give little or none of the expected 1,2-dlols; the l,4-t 1,5-* and 1,6-diols are obtained from cyclooctene, cyclononene, and cyclodecene, respectively.1 Since these Initial investigations, numerous examples of transannular hydride migrations have been reported. In contrast, few data have been reported concerning the analogous hydrogen atom migration to a transannular free radical site. This present work is concerned with this question. Among several possible methods of generating a free radical on a medium ring, addition to an olefin seemed the most promising for this type of study. The free radical addition of an addend A-B to an olefin has been shown to 7 occur in several steps: heat (1) initiation: A-B — *-► A* + B* light heat or: Ing — ► 2In* Wherd In2 represents an "initiator" such as benzoyl peroxide. In* + A-B ► In—B + A* (2) addition: A* + )t>0^ — ► A-(J-(J * (3) chain transfer: A-^-^« + B-A — ► A-^-^-B + A* In principle, introduction of a single free radical in the initiation step (1) may cause hundreds or even thousands 3 of molecules to react since the radical A* is reformed In the chain transfer step. Actually this simple scheme Is always complicated by the competing reactions listed below: (4) dlmerizatlon: R« + R'* — ► R-R' (5) polymerization: (6) allylic substitution: R* + -CHg-O RH + (7) dlsproportlonatlon: 2A- By proper choice of experimental conditions the addition reaction can usually be made to predominate over polymerization and allylie substitution. Addition of an addend to an olefin under free radical conditions is usually accompanied by the several reactions typical of a free radical: dlmerizatlon, abstraction and dlsproportlonatlon. Therefore, one can assume that a free radical intermediate is formed in the addition reaction and that its rearrangement may be studied by examination of the products formed from such an addition. The related problem of a transannular free radical ring closure (involving the transannular migration of an unpaired electron) has been studied by several workers. Dowbenko reports that free radical additions to 1,5-cyclo-
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  • Secondary Organic Aerosol Formation from Cyclohexene Ozonolysis: Effect of OH Scavenger and the Role of Radical Chemistryseconda

    Secondary Organic Aerosol Formation from Cyclohexene Ozonolysis: Effect of OH Scavenger and the Role of Radical Chemistryseconda

    Environ. Sci. Technol. 2004, 38, 3343-3350 in the cyclodecene-ozone system, in the presence of propanol Secondary Organic Aerosol scavenger, Ziemann (5) observed the formation of cyclic Formation from Cyclohexene peroxyhemiacetals, and while these products were not shown explicitly to result in an increase in aerosol yield we may Ozonolysis: Effect of OH Scavenger suppose that these large cyclic peroxyhemiacetals partition to the aerosol phase. In contrast to this, Docherty and and the Role of Radical Chemistry Ziemann (1) observed a reduction in SOA yield for the â-pinene ozonolysis when propanol scavenger was used, M. D. KEYWOOD, J. H. KROLL, compared with cyclohexane as a scavenger. V. VARUTBANGKUL, R. BAHREINI, The reaction between cyclohexene and ozone is initiated R. C. FLAGAN, AND J. H. SEINFELD* by the addition of ozone to the double bond to form a primary Departments of Environmental Science and Engineering and ozonide which stabilizes or decomposes to an excited Chemical Engineering, California Institute of Technology, bifunctional Criegee intermediate that has two isomers (5) Pasadena, California 91125 (Figure 1). How this intermediate then goes on to form SOA has been discussed extensively (5, 7-9). The predominant low molecular weight SOA products identified in the cyclo- hexene-ozone system are dicarboxylic acids and hydroxylated To isolate secondary organic aerosol (SOA) formation in dicarboxylic acids (8). Hydroxyl radicals can be produced ozone-alkene systems from the additional influence of hydroxyl from various reactions in the alkene ozonolysis mechanism. (OH) radicals formed in the gas-phase ozone-alkene The dominant pathway of OH formation is understood to be reaction, OH scavengers are employed.