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Effects of Metal Ions in Free Radical Reactions Richard Duane Kriens Iowa State University

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Effects of Metal Ions in Free Radical Reactions Richard Duane Kriens Iowa State University Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1963 Effects of metal ions in free radical reactions Richard Duane Kriens Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Kriens, Richard Duane, "Effects of metal ions in free radical reactions " (1963). Retrospective Theses and Dissertations. 2544. https://lib.dr.iastate.edu/rtd/2544 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. This dissertation has been 64—3880 microfilmed exactly as received KRIENS, Richard Duane, 1932- EFFECTS OF METAL IONS IN FREE RADICAL REACTIONS. Iowa State University of Science and Technology Ph.D„ 1963 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan EFFECTS OF METAL IONS IN FREE RADICAL REACTIONS by Richard Duane Kriens A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Major Subject: Organic Chemistry Approved: Signature was redacted for privacy. In Charge of Major Work Signature was redacted for privacy. ead of Major Departmei^ Signature was redacted for privacy. Iowa State University Of Science and Technology Ames, Iowa 1963 11 TABLE OF CONTENTS Page PART I. REACTIONS OF RADICALS WITH METAL SALTS. ... 1 INTRODUCTION 2 REVIEW OF LITERATURE 3 RESULTS AND DISCUSSION 17 EXPERIMENTAL 54 Chemicals 54 Apparatus and Procedure 66 Reactions of compounds with the 2-cyano-2-propyl radical 66 Reactions of compounds with the phenyl radical 67 Procedure for Sandmeyer type reaction. ... 69 Procedure for reactions with dlmethyl-N- (2-cyano-&-propyl)-ketenlmine (Kelm) ... 70 Gas-liquid chromatographic (GLC) analysis. 81 Infrared (IR) analysis 91 Ultraviolet (UV) analysis 92 SUMMARY 93 ' PART II. SOLVENT EFFECTS IN REACTIONS OF t-BUTOXY RADICALS 95 INTRODUCTION 96 REVIEW OF LITERATURE 97 RESULTS AND DISCUSSION 104 EXPERIMENTAL 141 Chemicals ..... 141 Apparatus and Procedure 146 Procedure for reactions involving the t-fcutoxy radical 146 Procedure for the reactions with ferrocene and the phthalocyanines 150 ill Page Procedure for the reactions with cobaltocene 151 Procedure for reactions involving the phenyl radical 153 G-as-liquid chromatographic (G-LC) analysis. 153 SUMMARY 159 REFERENCES CITED 161 ACKNOWLEDGMENTS 168 iv LIST OF TABLES Page Table 1. Comparison of yields of (CH^)gC(CK)X (designated RX in table) from reaction of compounds of type MXn with 2-cyano-2- propyl radicals formed from decomposition of AIBK at 80° in benzene 19 Table 2. Comparison of yields of 2-chloro-2-cyano- propane with the reduction potential snd electronegativity of the metals used. • 24 Table 3. Comparison of yields of 2-chloro-2-cyano- propane from decomposition of AIBK at 80° in benzene containing cupric and ferric chlorides at different halide:AIBK ratios 27 Table 4. Comparison of yields of 2-chloro-2-cya.no- propane from decomposition of AIBK at 80o in several solvents containing CuClg at several different CuClgrAIBN ratios . 32 Table 5. Comparison of yields of 2-chlo ro - 2- cy ano - propane from decomposition of AIBK at 80° in several solvents containing FeClg at several different FeCl.3:AIBK ratios . 32 Table 6. A comparison of the number of radicals accounted for by 2-chloro-cyanopropane and tetramethylsuccinonitrile in selected typical reactions of metal halides with the 2-cyano-2-propyl radical generated by thermolysis of AIBK at 80° 35 Table 7, Yields of CgHgX from reactions of compounds of type MXn with phenyl radicals generated from thermolysis of PAT in acetonitrile at 60° 37 Table 8. The importance of CuX+ in the Sandmeyer reaction; comparison of the yield of RX from reaction of phenyl radical at 60° and 2-cyano-2-propyl radical at 80° with cuprous salt in acetonitrile with and without added peroxide. 51 V Page Table 2. Comparison of molar concentration of Kelm with infrared absorbance at 4.96 when solvent is acetonitrile and isopropanol . 72 Table 10. Kelm formation and subsequent disappear­ ance in the decomposition of AIBK in acetonitrile at 80° 75 Table 11. Data for Job's law plot 78 Table 12. Retention times of selected compounds ... 89 Table 1-3. Correction factors for G-LC 90 Table 14. Products from decomposition of di-t-butyl peroxide in presence of cyclohexane in various solvents at 135° 106 Table 15. Comparison of k]_/k£ values with several functions of the dielectric constant and with Hendry's Rate - Rj_/2 data. 110 Table 16. Products from decomposition of di-t_-butyl peroxide in various solvents at 135° • • • • 117 Table 17. Products from decomposition of di-t-butyl peroxide in various chlorosubstituted solvents with and without cyclohexane present 120 Table 18. Affects of the other products on the acetone formed in the decomposition of di-t-butyl peroxide in tetrachloroethylene containing cyclohexane 130 Table 19. Comparison of yields of acetone and t- but ano 1 from decomposition of di-t.-butyl peroxide at 135° in various solvents with and without cyclohexane and aromatic metal pi-complexes 131 Table 20. Decomposition of 0.234 M di-t-butyl peroxide at 135° in acetonitrile and in acetonitrile containing 0.116 M cobaltocene 135 vi Page Table 21. The effect of ferrocene and cobaltocene upon the value of kn/kci when PAT is decomposed in an equal molar mixture of cyclohexane and carbon tetrachloride. 140 Table 22. Relative retention times of selected compounds ....... 154 Table 23. Physical constants of solvents used .... 156 vil LIST OF FIGURES Page Figure 1. Dependence of yields of 2-chloro-2- cyanopropane on coordinated neutral ligand of cupric chloride; reactions run in benzene at 80° and reaction mixture heterogeneous; 0.0122 moles AIBN in 200 ml benzene used in each case 30 Figure 2. Dependence of yields of 2-chloro-2- cyanopropane on coordinated neutral ligand of ferric chloride; reactions run in benzene at 80° and reaction mixture heterogeneous; 0.0122 moles AIBK in 200 ml benzene used in each case 30 Figure 3. Dependence of yields of 2-chloro-2- cyanopropane on the solvent in reactions run with cupric chloride at 80°; ability to solvate CuClg is in the order isopropanol acetonitrile benzene; 0.0122 moles AIBK per 200 ml. solvent in each case 34 Figure 4. Dependence of yields of 2-chloro-2- cyanopropane on the solvent in reactions run with ferric chloride at 80°; ability to solvate FeCl.3 is. in the order isopro­ panol benzene; 0.0122 mole AIBK per 200 ml solvent in each case 34 Figure 5. Job's Law plot of the reaction of dimethyl-R-(2-cyano-2-propyl)-ketenimine with CuClg in acetonitrile 41 Figure 6. Infrared spectrum of dimethy1-K-(2-cyano- 2-propyl)-ketenimine in acetonitrile solution 48 Figure 7. Infrared spectrum of the reaction mixture of CuClg with dimethyl-K-(2-cyano-2- propyl)-ketenimine in acetonitrile .... 48 Figure 8. Infrared spectrum of 2-chloro-2-methyl-N- (2-cyano-2-propy1)-propionami d e in acetonitrile 48 viii Page Figure 9 Relationship between Kelm concentretion and infrared absorbance st 4.96 when solvent is acetonitrile 74 Figure 10. Relationship between Kelm concentration and infrared absorbance at 4.96 when solvent is isopropanol 74 Figure 11. Kelm formation and subsequent disappear­ ance in the decomposition of AIBN in acetonitrile at 80° 76 Figure 12 • Nuclear magnetic resonance spectrum of 2-chloro-2-methyl-N-(2-cyano-2-propyl)- propionamide 83 Figure 13. Nuclear magnetic resonance spectrum of 2-methyl-N-(2-cyano-2-propyl)- propionamide 85 Figure 14, Infrared spectrum of 2-chloro-2-methyl-N- (2-cyano-2-propyl)-propionamide in chloroform solution 85 Figure 15. Infrared spectrum of 2-methyl-K-(2-cyano- 2-propyl)-propionamide in chloroform solution 85 Figure 16. Decomposition of di-t-butyl peroxide at 135° in various solvents containing cyclohexane; comparison of k^/kg values with the dielectric constant 112 Figure 17, Decomposition of di-t-butyl peroxide at 1350 in various solvents containing cyclohexane; comparison of k]_/kg values with the Kirkwood-Onsager parameter according to Laidler and Eyring. 112 Figure 18 Decomposition of di-t-butyl peroxide at 135° in various solvents containing cyclohexane; comparison of k^/kg values with the Kirkwood-0nsager parameter according to the method of Fowling and Bernstein 114 ix Page Figure 19. Decomposition of di-t-butyl peroxide at 135° in various solvents containing cyclohexane; comparison of k^/kg values with Hendry's values of (Rate - Rl/2) for the oxidation of cyclohexene 114 Figure 20. Nuclear magnetic resonance spectrum of a mixture of els- and trans-1-cyclohexyl- ethylene 124 Figure 21. Infrared spectrum of a mixture of cls- and trans-l-chloro-2-cyclohexylethylene• . 126 Figure 22. Decomposition of di-t-butyl peroxide in acetonitrile at 135° as a function of time 136 1 PART I: REACTIONS OF RADICALS WITH METAL SALTS 2 INTRODUCTION The purpose of this study was to determine the effects of metal salts on free radical reactions. More specifically, it ) was of interest to study the ability of metal salts to act as trapping agents for organic free radicals in solution, i.e., to see if they can remove radicals from solution. The metal +n salts studied were of the type M Xn where M is a metal with more than one common valence state, such as copper and iron, and where X is a group common to organic molecules, such as the halides and the cyano group.
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