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A Study of the Free Radical Addition of Thiophenol to Substituted A-Methylstyrenes and Vinylarenes

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A Study of the Free Radical Addition of Thiophenol to Substituted A-Methylstyrenes and Vinylarenes AN ABSTRACT OF THE THESIS OF Daniel Frank Churchfor the degree of Doctor of Philosophy in CHEMISTRY (Organic)presented on I a_ --)s- Title: A STUDY OF THE FREE RADICAL ADDITION OF THIOPHENOL TO SUBSTITUTED a-METHYLSTYRENES AND VINY LARENES Redacted for Privacy Abstract approved: Drj. Gerald Ay Gleicher The relative rates of addition of thiophenol to substituted a-methylstyrenes in benzene at 70°C have been determined.These relative rates correlated with the Okamoto-Brown sigma-plus sub- stituent parameters.The rho value thus obtained was -0. 38±0. 02 (correlation coefficient = -0. 984).The relative rates of addition of substituted thiophenols to E-chloro-a-methylstyrene in benzene at 70°C also correlated with the sigma-plus parameters to give a rho value of -0. 27±0. 03 (correlation coefficient = -0. 975).These results indicate that the transition states of both the addition and the chain transfer steps for the addition of thiophenol to a-methyl- styrene involve substantial contributions from charge-separated forms. CH3 CH3 PhCCH : SPh PhS H : CPhI 2 + I CHSPH 2 Addition Chain Transfer A study was also made of the addition of thiophenol to vinyl- arenes in benzene at 70°C.The relative reactivities determined for this series of compounds were then correlated with various quantities calculated by a semi-empirical SCF-MO method.These calculations utilized a variable bond length approach.The best correlation was between the relative reactivities and the total energy difference between the starting olefin and the intermediate radical. This correlation was better than that obtained using the pi energies alone.Likewise, use of the Heckel method to derive the energy difference or of the free valence led to less satisfactory relation- ships.These results were taken as evidence that the transition state of the addition step has considerable radical character. Several attempts were also made to find a radical reaction in which the azarene analog of a benzyl-type free radical was generated. The hope was to correlate the relative reactivities for a series of azarene compounds with energy differencescalculated similarly to above.However, the nucleophilicity of the nitrogen atom in these systems caused these attempts to be unsuccessful. A Study of the Free Radical Addition of Thiophenol to Substituted a-Methylstyrenes and Vinylarenes by Daniel Frank Church A THESIS submitted to Oregon State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy June 1976 APPROVED: Redacted for Privacy Associate Professor-f1ChemistrY\ in charge of major Redacted for Privacy Head of Department of Chemistry Redacted for Privacy Dean ofGraduate School Date thesis is presented Typed by Opal Grossnicklaus for Daniel Frank Church To my parents ACKNOWLEDGEMENTS I wish to express my many thanks to Dr. Gerald Jay Gleicher for suggesting this problem, for his guidance and for his many enlightening discussions of the results, and for providing the com- puter programs and several of the compounds and intermediates used in these experiments.Thanks are also due to OSU Computer Center for providing the computer time for these studies.I would like to express my appreciation to Dr. J.H. Kreuger, Dr. D. D. Newkirk, and Mr. J.C. Arnold for helpful discussions relating to this work. A special thanks are due Miss Suae-chen Chang for helping in the preparation of the manuscript of this thesis. TABLE OF CONTENTS Page INTRODUCTION Free Radical Thiol Additions 1 Linear Free Energy Relationships 6 Molecular Orbital Calculations 12 DISCUSSION OF THE PROBLEM 17 RESULTS 23 Synthesis of Substituted a-Methylstyrenes 23 Synthesis of Isopropenylarenes 24 Synthesis of Vinylarenes 25 Reaction of Thiophenol and a-Methylstyrene 26 Reaction of Thiophenol and E-Methoxy-a-methylstyrene 26 Reaction of Thiophenol and p.-Nitro-a-methylstyrene 26 Overall Reversibility of Addition of Thiophenol to a-Methylstyrene 27 Reaction of Thiophenol and 1-Vinylnaphthalene 27 Catlaysis of the Reaction between Thiophenol and R-Methoxy-a-methylstyrene 28 Reaction of Pyridine and Bromotrichloromethane 28 Reaction of Pyridine and N-Bromosuccinimide 28 Relative Reactivities of Substituted a- Methyl styrenes towards Thiophenol 29 Relative Reactivities of Substituted Thiophenols towards E-Chloro-a-methylstyrene 29 Relative Reactivities of Isopropenylarenes towards Thiophenol 35 Relative Reactivities of Vinylarenes towards Thiophenol 35 DISCUSSION OF THE RESULTS 40 Substituent Effects in the Addition of Thiophenol to a-Methylstyrenes 40 Correlations with Calculated Parameters 47 EXPERIMENTAL 55 Purification of Reagents 55 Benzene 56 o-Dichlorobenzene 56 Chlorobenzene 56 Cyclohexane 56 Benzoyl Peroxide 56 Thiophenol 56 a-Methylstyrene 56 9 -Vinyla.nthracene 56 a-Chlorothiophenol 56 p_-Methoxythiophenol 57 p- Methylthiophenol 57 Preparation of Compounds 57 Preparation of Substituted a- Methyl styrenes 57 General procedure for a-methoxy-, a-methyl-, m-methyl-, m-rn.ethoxy-, a-chloro-, m-chloro-, and m-trifluoromethyl-a-methylstyrene 58 Procedure for a-nitro-a-methylstyrene 59 Preparation of a-Nitrothiophenol 59 Preparation of Isopropenylarenes 62 General procedure for 1- and 2-isopropenyl- naphthalene and 9-isopropenylanthracene 62 Procedure for 9-isopropenylphenanthrene 63 Preparation of Vinylarenes 64 Procedure for styrene and 1- and 2-vinyl- naphthalene 64 Procedure for 1-vinylanthracene 65 Procedure for 2-vinylanthracene 67 Procedure for 9-vinylphenanthrene 67 Procedure for 1-vinylpyrene 67 Procedure for 6-vinylchrysene 68 Procedure for the Analysis of the Reaction between a-Methylstyrene and Thiophenol 70 Procedure for the Analysis of the Reaction between a-Methoxy-a-methylstyrene and Thiophenol 70 Procedure for the Analysis of the Reaction between p_-Nitro-a-methylstyrene and Thiophenol 71 Procedure for the Analysis of the Reaction between 1-Vinylnaph.thalene and Thiophenol 72 Procedure for Studying the Overall Reversibility of the Addition of Thiophenol to a-Methylstyrene 72 Procedure to Determine the Extent to which Pyridine Catalyzes a Reaction between a-Methoxy- a-methylstyrene and Thiophenol 73 Procedure for Determining the Relative Reactivities of Substituted a-Methylstyrenes towards Thiophenol 73 Procedure for Determining the Relative Reactivities of Substituted Thiophenols towards a-Chloro- a-Methylstyrene 76 Procedure for Determining the Relative Reactivities of Isopropenylarenes towards Thiophenol 77 Procedure for Determining the Relative Reactivities of Vinylarenes towards Thiophenol 77 BIBLIOGRAPHY 79 APPENDIX 86 LIST OF ILLUSTRATIONS Figure Page 1. Correlation of log ky./kw ando-+for the reaction of substituted a-met SylAtyrenes andthiophenol. Direct method of analysis. 31 2. Correlation of log k /kH ando-+ for the reaction of substituted a-met ylstyrenes andthiophenol. Indirect method of analysis. 32 3. Correlation of log k/kT4 ando-+for the reaction of substituted thiophenoIsX and E-chloro-a- methylstyrene. 34 4. Structures of polycyclic arenes. 36 5. Correlation of log kX*Std and "ETotal for the reaction of vinylarenes with thiophenol. 39 6. Plot of free energy vs. reaction coordinatefor the addition of thiophenol to styrene. 41 LIST OF TABLES Table Page 1. Relative reactivities of substituteda-methylstyrenes towards thiophenol at 70. 0°C 30 2. Reaction constants for the addition ofthiophenol to substituted a-methylstyrenes 30 3. Relative reactivities of substituted thiophenols towards P-thiophenoxy-R-chlorocumyl radicals at 70. 0°C 33 4. Reaction constants for the addition ofsubstituted thiophenols to R-chloro-a-methylstyrene 33 5. Relative reactivities of isopropenylarenestowards thiophenol at 70. 0°C 35 6. Relative reactivities of vinylarenes towards thiophenol at 70. 0°C 38 7. Correlations between the reactivities of vinylarenes and calculated parameters 38 8. Summary of the physical properties and overall yields for the substituted a-methylstyrenes 60 9. Summary of nmr data for substituted a-methyl- styrenes in carbon tetrachloride 61 10. Summary of physical properties and overall yields of the isopropenylarenes 63 11. Summary of nmr data for the isopropenylarenes in carbon tetrachloride 64 12. Summary of physical properties and overallyields of vinylarenes 68 13. Summary of nmr data for the vinylarenes in deutero- chloroform 69 Table Page 14. Relative rate of disappearance of E-methoxy-a- methylstyrene to 2.-chloro-a-methylstyrene 86 15. Relative rate of disappearance of p, a-dimethyl- styrene to R-chloro-a-methylstyrene 87 16. Relative rate of disappearance of m a-dimethyl- styrene to E-chloro-a-methylstyrene 88 17. Relative rate of disappearance of R-chloro- a-meth.ylstyrene to a- methylstyrene 89 18. Relative rate of disappearance of m-methoxy- a-methylstyrene to R-chloro-a-methylstyrene 90 19. Relative rate of disappearance of m-trifluoro- methyl-a-methylstyrene to p.-chloro-a-methyl- styrene 91 20. Relative rate of disappearance of m-trifluoro- methyl-a-methylstyrene to m-chloro-a- methylstyrene 92 21. Relative rate of disappearance of E-nitro-a- methylstyrene to a-chloro-a-methylstyrene 93 22. Relative rate of disappearance of 2_-methoxy- thiophenol to thiophenol 94 23. Relative rate of disappearance of p-methyl- thiophenol to thiophenol 95 24. Relative rate of disappearance of p- chloro- thiophenol to thiophenol 96 25. Relative rate of disappearance of R-nitrothio- phenol to thiophenol 97 26. Relative rate of disappearance of 2-isopropenyl- naphthalene to p.-chloro-a-meth.ylstyrene 98 27. Relative rate of disappearance of 1-isopropenyl- naphthalene
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