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The Mechanisms of Some Reactions of Thiolsulfinates (Sulfenic Anhydrides)

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The Mechanisms of Some Reactions of Thiolsulfinates (Sulfenic Anhydrides) AN ABSTRACT OF THE THESIS OF CLIFFORD GEORGE VENIER for the Ph. D. in Chemistry (Organic) (Name) (Degree) (Major) .tt. .r_,,,/ Date thesis is presented L /j, Title THE MECHANISMS OF SOME REACTIONS OF THIOLSULFINATES (SULFENIC ANHYDRIDES) Abstract approved Redacted for Privacy , " (Major p ofessor) Thiolsulfinates ( sulfenic anhydrides) have been found to react readily with sulfinic acids (equation 1) in acetic acid solvent. Kinetic O AASAr + 2 Ar'SO2H -> 2 Ar'SO2SAr + H20 (1) studies show that the reaction is first -order in thiolsulfinate and first -order in sulfinic acid. The dependence of the rate on acidity and a solvent isotope effect of kH /kD = 1. 27 suggest that the reac- tion is general acid -catalyzed. The results seem best accommo- dated by the mechanism shown in equation 2. OH G 6® bO OH + Ì ACD+ HO2SAr'+ --H (2) b® L I I O+ Ar' Ar J HA + Ar'SO2SAr + ArSOH %- ArSOH + Ar'SO2H > Ar'SO2SAr + H20 Both the sulfinic acid- thiolsulfinate reaction and the dispro- portionation of thiolsulfinates, equation 3, can be markedly accelerated by the addition of small amounts of organic sulfides. Both sulfide- catalyzed reactions have the same formal rate laws, O 2 ArSSAr > ArSO2SAr + ArSSAr (3) being first -order in catalyzing sulfide, first -order in thiolsulfinate and respond to acidity according to the Hammett acidity function, Ho. They show, however, a rather different dependence of rate on sulfide k /k = 27, 000 for catalyzed reaction 1, but structure, Et2S Ph2S only 47 for the catalyzed disproportionation. A plot of the loga- rithm of the rate constant for catalyzed reaction 1 versus o* gives p = -2. 0, indicating a substantial decrease in electron density on the sulfide sulfur in the transition state. This and correlation of rates with the rates of peroxide oxidation of sulfides, show that the sulfide acts as a nucleophile. Chart 1 is suggested as a general mechanism for the sulfide - catalyzed processes. Lack of dependence of the rate of catalyzed reaction 1 on sulfinic acid concentration suggests that this reagent acts simply to trap the thiosulfonium ion and sulfenic acid formed in the k2 step, i. e. , k4(Ar `SO2H) > k With no trapping agent, r however, k > k3. CHART 1 O K OH ArgSAr + HO - ArS-SAr ® OH k2 ® i ArS-SAr i R2S - _.- R2SSAr + ArSOH ® k-2 e k3 R2SSAr + ArSOH i "oxidized and reduced intermediates" O k4 (ArSO2H) k5(ArSSAr) Ar'SO2SAr + H20 (R2S) ArSSAr + ArSO2SAr Support for this mechanism has been gained through studies of the sulfide- catalyzed loss of optical activity of optically active phenyl benzenethiolsulfinate, equation 4. O k 9 (+) - PhSSPh a > (t) - PhSSPh + PhSSPh + PhSO2Ph (4) As predicted by the mechanism proposed in Chart 1, the rate of sul- fide- catalyzed loss of optical activity in the absence of sulfinic acid parallels the rate of sulfide- catalyzed reaction 1, rather than the rate of the catalyzed disproportionation. The nature of the k3 step has not been determined. However, several possibilities are sug- gested and discussed. The kinetics of the uncatalyzed disproportionation of thiolsul- finates (equation 3) are complex. Mechanistic possibilities are pre- sented and discussed. APPROVED: Redacted for Privacy Pr fessor of Ch mistry . - Charge of Major Redacted for Privacy Chairman Department of Chemistry Redacted for Privacy Deán of Graduate School v Date thesis is presented ._.. , "ík.-;- Typed by Opal Grossnicklaus 'l'o my parents, Clifford L. and Augusta Venier, and to my wife, Lynn. ACKNOWLEDGEMENT I would like to thank Dr. John L. Kice for his continual interest, discussions, and encouragement. His help has not only been invaluable, but is sincerely appreciated. I wish also to thank the Air Force Office of Scientific Research and the National Science Founda- tion for financial support during the course of this work. TABLE OF CONTENTS INTRODUCTION 1 RESULTS .. ... 12 Disproportionation of Thiolsulfinates 12 Stoichiometry 13 Kinetics of the Disproportionation 15 Sulfide - Catalyzed Disproportionation of Thiolsulfinates . , 19 Stoichiometry 21 Kinetics of the Sulfide- Catalyzed Disproportionation . 21 Kinetic Order with Respect to the Catalyzing Sulfide 21 Dependence of Rate on Sulfide Structure 22 Order with Respect to Thiolsulfinate 26 Dependence of Rate on Strong Acid Concentration . 26 Activation Energy 29 Deuterium Isotope Effect 29 Chloride Ion Catalysis 30 Sulfinic Acid - Thiolsulfinate Reaction 30 Stoichiometry 32 Kinetics of the Sulfinic Acid - Thiolsulfinate Reaction. 33 Kinetic Order with Respect to Sulfinic Acid 34 Effect of Changing Sulfinic Acid Structure 36 Order with Respect to Thiolsulfinate 39 Effect of Thiolsulfinate Structure on Rate 39 Dependence of Rate on Sulfuric Acid Concentration . 40 Deuterium Isotope Effect 41 Activation Energy 45 Sulfide - Catalyzed Sulfinic Acid - Thiolsulfinate Reaction 45 Stoichiometry .. 45 Kinetics of the Sulfide -Catalyzed Sulfinic Acid -Thiolsulfinate Reaction 48 Order with Respect to Sulfide 48 Dependence of Rate on Sulfide Structure 48 Order with Respect to Thiolsulfinate 51 Dependence of Rate on Su lfinic Acid Concentration. 54 Dependence of Rate on Sulfinic Acid Structure 54 Dependence of Rate on Acidity .. , . 56 Deuterium Isotope Effect 57 Activation Energy 59 Chloride Ion Catalysis 59 Kinetics of Chloride Ion Catalysis ........ 59 TABLE OF CONTENTS (CONTINUED) Thiol - Thiolsulfinate Reaction 60 Stoichiometry 60 Kinetics of the Thiol - Thiolsulfinate Reaction 61 Sulfide - Catalyzed Thiol - Thiolsulfinate Reaction 65 DISCUSSION 68 Sulfide - Catalyzed Processes 68 Acidity Dependence 71 Mechanism of the Sulfide - Catalyzed Sulfinic Acid - Thiolsulfinate Reaction 73 Mechanism of the Sulfide -Catalyzed Disproportionation. 79 Mechanism of the Sulfide- Catalyzed Loss of Optical Activity 88 Mechanism of the Sulfinic Acid - Thiolsulfinate Reaction . 92 Mechanism of the Thiolsulfinate Disproportionation 98 Mechanism of the Thiol - Thiolsulfinate Reaction 102 EXPERIMENTAL 104 Preparation of Materials 104 Sodium p- Toluenesulfinate 104 Sodium p- Bromobenzenesulfinate 104 Sodium p- Nitrobenzenesulfinate 104 p- Toluenesulfinic Acid 104 p- Bromobenzenesulfinic Acid 105 p- Nitrobenzenesulfinic Acid 105 Benzenesulfinic Acid 105 p- Toluenesulfinyl Chloride 106 Benzenesulfinyl Chloride 106 Thi oph enol 106 p- Toluenethiol 107 Di(p- tolyl) Sulfide 107 Phenyl Benzenethiolsulfinate 107 Phenyl p- Toluenethiolsulfinate 107 p -Tolyl Benzenethiolsulfinate 108 p -Tolyl p- Toluenethiolsulfinate 108 t -Butyl Benzenethiolsulfinate 108 p -Tolyl p- Toluenethiolsulfonate 108 Phenyl Benzenethiolsulfonate 109 Diphenyl Sulfoxide 109 Dibenzyl Sulfide 109 TABLE OF CONTENTS (CONTINUED) Diphenyl Sulfide 109 Di(n- butyl) Sulfide 110 Diethyl Sulfide 110 Tetrahydrothiophene 110 Benzyl Phenyl Sulfide, Thiodiglycolic Acid, and Thiodipropionic Acid 110 Acetic Acid 110 Acetic Acid -d 111 Stock Solutions 111 Procedure for Kinetic Runs 112 Dilution Method 112 Direct Method 114 Procedure for Product Studies 114 CONCLUSION 118 BIBLIOGRAPHY 121 APPENDICES 133 Appendix 1. Data for the Disproportionation of Thiolsulfinates 133 Appendix 2. Data for Sulfide - Catalyzed Dispropor- tionation of Phenyl Benzenethiolsulfinate . 134 Appendix 3. Data for Sulfinic Acid - Thiolsulfinate Reaction 136 Appendix 4. Data for Sulfide - Catalyzed Sulfinic Acid - Thiolsulfinate Reaction 140 Appendix 5. Data for the Benzenethiol- Phenyl Benzenethiolsulfinate Reaction 144 Appendix 6. Data for the Benzyl Sulfide -Catalyzed Benzenethiol- Phenyl Benzenethiolsulfinate Reaction 145 LIST OF TABLES Table Page 1. Variation of observed first -order rate constant with 16 initial phenyl benzenethiolsulfinate concentration. 2. Acidity dependence of disproportionation of phenyl 17 benzenethiolsulfinate in acetic acid at 60 ° C. 3. Independence of second -order rate constant, kd, of 25 catalyzing sulfide concentration. 4. Dependence of kd on acidity. 29 5. Stoichiometry calculations based on equation 14. 34 6. Independence of second -order rate constant, k2, of 36 sulfinic acid concentration. 7. Effect of para substituent on the rate of the p -X benzene- 37 sulfinic acid -phenyl benzenethiolsulfinate reaction. 8. Independence of second -order rate constant, k2, of 39 phenyl benzenethiolsulfinate concentration. 9. Dependence of rate on thiolsulfinate structure. 40 10. Dependence of k2 on sulfuric acid concentration. 44 11. Effect of water concentration on k2. 44 12. Products of benzyl sulfide catalyzed p- toluenesulfinic 47 acid -p -tolyl p- toluenethiolsulfinate reaction. 13. Independence of second -order rate constant, k , of 49 sulfide concentration. c 14. Independence of second -order rate constant, k , of 55 sulfinic acid concentration. c 15. Dependence of k for phenyl benzyl sulfide on sulfinic 55 acid. c LIST OF TABLES (CONTINUED) Table Page 16. Dependence of k on acidity. 58 c 1 7. Rate constant summary for changing thiophenol 64 concentration. 18. Rate constant summary for changing phenyl 64 benzenethiolsulfinate concentration. 19. Comparison of rate constants for sulfide- catalysis 70 of various thiolsulfinate reactions. 20. Comparison of sulfides as catalysts in sulfinyl 77 sulfone solvolysis and sulfinic acid -thiolsulfinate reaction. 21. Variance of stoichiometry with initial sulfinic acid 98 concentration. LIST OF FIGURES Figure Page 1. Ultraviolet Absorbtion Spectra of Phenyl Benzene- 14 thiolsulfinate (Curve A), Phenyl Benzenethiolsul - fonate (Curve B), and Phenyl Disulfide (Curve C). 2. Acidity Dependence of Phenyl Benzenethiolsulfinate 18 Disproportionation at 60 ° C. 3. Disproportionation of
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