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I a Study of the Basicities of Some Aryl Methyl Sulfoxides Ii a Study of the Hydrolysis of Arenesulfinamides in Basic Aqueous Ethanol

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I a Study of the Basicities of Some Aryl Methyl Sulfoxides Ii a Study of the Hydrolysis of Arenesulfinamides in Basic Aqueous Ethanol University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Spring 1968 I A STUDY OF THE BASICITIES OF SOME ARYL METHYL SULFOXIDES II A STUDY OF THE HYDROLYSIS OF ARENESULFINAMIDES IN BASIC AQUEOUS ETHANOL JOSEPH BRIAN BIASOTTI Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation BIASOTTI, JOSEPH BRIAN, "I A STUDY OF THE BASICITIES OF SOME ARYL METHYL SULFOXIDES II A STUDY OF THE HYDROLYSIS OF ARENESULFINAMIDES IN BASIC AQUEOUS ETHANOL" (1968). Doctoral Dissertations. 871. https://scholars.unh.edu/dissertation/871 This Dissertation is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. This dissertation has been microfilmed exactly as received ^ ^ BIASOTTI, Joseph Brian, 1942- I. A STUDY OF THE BASICITIES OF SOME ARYL METHYL SULFOXIDES H. A STUDY OF THE HYDROLYSIS OF ARENESULFINAMIDES IN BASIC AQUEOUS ETHANOL. University of New Hampshire, Ph.D., 1968 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan I. A STUDY OF THE BASICITIES OF SOME ARYL METHYL SULFOXIDES . A STUDY OF THE HYDROLYSIS OF ARENESULFINAMIDES IN BASIC AQUEOUS ETHANOL j T b r i a n b i a s o t t i B. S., Boston College, 1964 A THESIS Submitted to the University of New Hampshire In Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Graduate School Department of Chemistry June, 1968 ABSTRACT I. A STUDY OF THE BASICITIES OF SOME ARYL METHYL SULFOXIDES II. A STUDY OF THE HYDROLYSIS OF ARENESULFINAMIDES IN BASIC AQUEOUS ETHANOL by J. BRIAN BIASOTTI I. There exists a minimum of quantitative data con­ cerning the basicities of sulfoxides. In this work ten meta- and para-substituted phenyl methyl sulfoxides were titrated potentiometrically using perchloric acid as the titrant and acetic anhydride as the solvent. Their apparent pKa values were determined by placing the values for the half-neutralization potentials on a straight line determined by plotting the pKa values vs. the half-neutralization potential for some amines whose pKa values were known. £- Anisyl methyl sulfoxide was found to be the strongest base (pKa = +0.55) and £-nitrophenyl methyl sulfoxide the weakest base (pKa = -3.51). A good Hammett plot correlation was obtained with p = 3.79, a correlation coefficient of 0.993, and a standard deviation of 0.169. Utilizing Taft's method for determining specific resonance effects, a resonance value of -0.26 was obtained for £-anisyl methyl sulfoxide indicating that electron donation by the substituent is greater in the protonated than in the unprotonated state. Such electron accepting type conjugation necessitates sulfur to expand its octet to ten electrons, causing (p->d)TT bonding between sulfur and carbon. The large rho value ob­ tained from the Taft treatment indicates that a large change in charge at sulfur is occurring between the protonated and unprotonated states, reflecting the double bond character of the sulfur oxygen bond. pKa values were also determined for dimethyl sulfoxide, diphenyl sulfoxide, cis-4-(4- chlorophenyl)-thiane-l-oxide, trans-4-(4-chlorophenyl)- thiane-1-oxide, S ,S-diphenyl-N-benzenesulfonylsulfilimine, and the S,S-dimethyl-, S,S-diphenyl-, and S-phenyl-S-methyl- N-£-toluenesulfonylsulfilimines. A plot of the pKa values for the S,S-diphenyl, S,S-dimethyl, and S-phenyl-S-methyl-N- jD-toluenesulfonylsulfilimines vs. the pKa values for the corresponding diphenyl, dimethyl, and phenyl methyl sulfoxides did not yield a straight line. II. In considering nucleophilic substitution reac­ tions at tricoordinate sulfur, little is known about the influence of the sulfur compound's structure on reactivity. Also the question of the existence of an intermediate of higher coordination number than that of the substrate has never been unequivocally answered. It was the purpose of this investigation to explore these two aspects. A series of nine meta- and para-substituted N-mesityl benzenesulfin- amides were prepared and the kinetics of their reaction with hydroxide ion in aqueous ethanol studied. Second order rate constants were obtained. The reaction was shown to be first order in base and first order in sulfinamide. Activation parameters were determined with AH ^ = +20.0 kcal/mole and AS = -8.9 eu. The rate constants gave a good correlation with Hammett’s cr constants (p = +1.3) indicating that the transition state is being stabilized by electron withdrawing substituents. The procedure of Taft for determining specific resonance effects was applied to the sulfinamides. A resonance value of (-0.08) was obtained for N-mesityl £- methoxybenzenesulfinamide indicating that the resonance contribution to the resonance hybrid is greater in the ground state than in the transition state. No significant resonance value (+0.03) was observed for the ]D-nitro substituent. The resonance contribution to the resonance hybrid for N-mesityl £-nitrobenzenesulfinimide is of the same magnitude for both the ground state and the transition state. The lack of a significant resonance value for the £-nitro substituent argues against the formation of an unstable addition inter­ mediate. Mass spectra were measured for the nine substituted N-mesityl benzenesulfinamides. The base peak at 134 m/e was assigned to (CH3 )3NH+ . A plot of log ([XC^H^S0+ ]/ [C6 H2 (CH3 )3NH+ ]) for X = £-N02 , R-CH3, £-CH30, m-CF3 , £-Cl, and H versus the Hammett substituent constants gave a straight line with p of -1 .1 . This thesis has been examined and approved. iIlItMMX aA m . JyfHtsii AI (vweU>7H/M (Li/rrJy? /)<!/} / / '' Ay .^yrurrrl^c^ A ljU^uux C f lUJL 17 i 1^6 if ACKNOWLEDGEMENT The author wishes to extend his sincere gratitude to Dr. Kenneth K. Andersen, whose guidance and encouragement aided greatly in the completion of this work. The author would like to thank Dr. J. J. Uebel for making many helpful suggestions in the writing of this thesis and to Anne Kohl for her excellent typing. Thanks are also due to the entire organic staff for their coopera­ tion and assistance and in particular Dr. J. John Uebel. Financial support from the National Science Foundation is gratefully acknowledged. The author wishes to dedicate this thesis to his wife, Phyllis, as an expression of gratitude for her en­ couragement and confidence. TABLE OF CONTENTS Page List of Tables............................................ vi List of Figures.......................................... vii PART I INTRODUCTION............................................... 1 RESULTS AND DISCUSSION..................................... 4 Determination of pKa values for sulfoxides and sulfilimines.......................................... 4 Effects of structure on basicity........................... 9 Taft’s method for determining specific resonance effects..11 Application of Taft’s method to sulfoxides................12 EXPERIMENTAL.............................................. 20 Materials................................................. 20 Titration procedure....................................... 21 Titration data............................................ 22 BIBLIOGRAPHY.............................................. 55 PART II INTRODUCTION.............................................. 58 RESULTS AND DISCUSSION.................................... 64 Effects of structure on reactivity........................ 64 Kinetic order of the reaction............................. 64 Activation parameters for the reaction.................... 66 Taft’s method for determining specific resonance effects..69 Application of Taft's method to sulfinamides..............69 Possibility of an unstable addition intermediate..........75 iv Page Mass spectra.............................. 78 Ultraviolet spectra....................................... 96 EXPERIMENTAL............................................. 104 Materials................................................ 105 Kinetic procedure........................................ 121 Kinetic data............................................. 123 BIBLIOGRAPHY............................................. 140 SUMMARY.................................................. 144 S V LIST OF TABLES PART I Page Table 1 - pKa Values for sulfoxides and sulfilimines..... 5 Table 2 - Specific resonance effects..................... 14 Table 3 - Sulfoxides titrated............................ 22 Table 4 - Standards and sulfilimines titrated............24 Table 5 - Accuracy for sulfoxide titrations............. 46 Table 6 - Accuracy for standards and sulfilimines titrates........................................ 48 Table 7 - Half-neutralization-potentials of sulfoxides.... 51 Table 8 - Half-neutralization-potentials of standards and sulfilimine................................. 53 PART II Table 1 - Rate constants for the hydrolysis of sulfina- mides........................................... 65 Table 2 - Dependence of rate constants for the base hydrolysis of N-mesityl £-chlorobenzene- sulfinamide on hydroxide ion concentration..... 6 6 Table 3 - Rate constants and activation parameters for the hydrolysis of N-mesityl £-chlorobenzene- sulf inamide..................................... 67 Table 4 - Specific resonance effects..................... 72 Table 5 - Major fragments in the mass spectra of aryl sulf
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