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Studies on the Mechanism of the Alkaline Hydrolysis of Thiolsulfinates

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Studies on the Mechanism of the Alkaline Hydrolysis of Thiolsulfinates AN ABSTRACT OF THE THESIS OF WAYNE HARVIE STANLEY for the . M. S. in Chemistry (Name) (Degree) (Major) Date this thesis presented 40 ,sr /7 jc/64. Title STUDIES ON THE MECHANISM OF THE ALKALINE HY- DROLYSIS OF THIOLSULFINATES Redacted for Privacy Abstract approved c (Major professor) í- The alkaline hydrolysis of phenylbenzenethiolsulfinate was studied at various pHs in an aqueous solution of 25% dioxane. A pH stat was constructed to follow the rate of disappearance of hydroxide ion under pseudo- first -order conditions. Comparative studies were made under identical conditions by following the disappearance of the thiolsulfin- ate in a buffered solution in the ultraviolet at 296 m,t(. A product study was made which indicates that the reaction fol- lows the course indicated in Equation 1. 3(pSóS() + 20H 2COSS1) + 20S02 + H2O (Eq. 1) The kinetic studies indicate that the reaction does not follow simple first -order kinetics but is quite complex. The first -order plots exhibit a marked curvature, being fast initially and slowing to a final lesser first -order rate. Possible schemes are discussed which can explain this curvature but no mechanistic conclusions are dr awn. The extreme complexity of the data suggests that the glass elec- trode response is altered by the presence of the dioxane to such a degree as to render it unreliable as a mechanistic tool. For this reason, it is suggested that further studies on the mechanism of the reaction be carried out in purely aqueous media. To this end the synthesis of a sufficiently water - soluble thiolsulfinate was attempted. The results of this work indicate that the alkaline hydrolysis of thiolsulfinates is a complex and very facile reaction, requiring study in several systems to fully elucidate its mechanism. STUDIES ON THE MECHANISM OF THE ALKALINE HYDROLYSIS OF THIOLSULFINATES by WAYNE HARVIE STANLEY A THESIS submitted to OREGON STATE UNIVERSITY in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE June 1967 APPROVED: Redacted for Privacy Professor of Chemistry in Ch(rge of Major Redacted for Privacy Chairman of Department of Chemistry Redacted for Privacy Dean of Graduate School Date thesis is presented 4 <<r < ¡ 7, f c¡ Typed by Janet L. Allen TABLE OF CONTENTS Subject Page INTRODUCTION 1 RESULTS 7 Product Study (I) 7 Kinetic Studies (II) 8 DISCUSSION 14 EXPERIMENTAL 19 pH Stat (I) 19 Preparation of p- Carboxyphenyl Disulfide (II) 24 Attempted Preparation of p- Carboxyphenyl p- Carboxybenzenethiolsulfinate (III) 24 Preparation of Phenylbenzenethiolsulfinate (IV) 25 Preparation of Benzenesulfinyl Chloride (V) 26 Thiophenol (VI) 26 Product Study (VII) 26 Preparation of Buffer Solutions (VIII) 27 Purification of Dioxane (IX) 27 Kinetic Runs in the pH Stat (X) 27 Kinetic Runs Via Ultraviolet Absorption (XI) 29 BIBLIOGRAPHY 30 APPENDIX 34 LIST OF FIGURES Figure Page 1 Pseudo -First -Order Kinetics of the Disappearance of Hydroxide Ion 34 2 Pseudo -First -Order Kinetics of the Disappearance of Hydroxide Ion in the Presence of Salts 35 3 Pseudo- First -Order Kinetics of the Rate of Disap- pearance of Thiolsulfinate. 36 4 The Dependence of Rate on the Apparent pH 37 5 Recorder Pen Assembly for Pipette Control 38 6 Pipette Control Module 39 7 pH Stat Reaction Vessel 40 LIST OF TABLES Table Page 1 Alkaline Hydrolysis of Phenylbenzenethiolsulfinate 7 2 Pseudo -First -Order Hydrolyses of Phenylbenzene- thiolsulfinate at Various Apparent pHs S 3 Alkaline Hydrolysis of Phenylbenzenethiolsulfinate in the Presence of Various Nucleophiles at Various Ionic Strengths 9 4 Kinetic Studies of the Rate of Disappearance of Phenylbenzenethiolsulfinate at Various Apparent pHs in Several Buffer Solutions 11 5 Comparison of pH Stat Data with Cary Model L -15 Absorption Data for the Alkaline Hydrolysis of Phenylbenzenethiolsulfinate 13 STUDIES ON THE MECHANISM OF THE ALKALINE HYDROLYSIS OF THIOLSULFINATES INTRODUCTION Thiolsulfinates, compounds of the formula RS(0)SR, appear in the literature as early as 1912 when they were reported by Zincke and co- workers (29, 30, 31, 32, 33). This group referred to them both as "sulfenic anhydrides" (31), when they were prepared by hydrolysis of an aromatic sulfenyl chloride, and as "sulfur oxides" (29, 30, 32, 33) when prepared by treatment of an aromatic sulfenyl chloride with sodium hydroxide in benzene. Zincke's structural as- signments were made on the basis of elemental composition, the fact that the compounds yielded the starting aromatic sulfenyl chlor- ides when treated with concentrated hydrochloric acid or phosphorus pentachloride in ether , and the fact that they "behaved as a n h y - drides" (33). By this Zincke meant that they dissolved in hot alkali or ammonia yielding strongly -blue solutions, although no salts were isolated. Recently, however, Oae and co- workers have raised doubts about at least two of these compounds (22) . In an attempt to repro- duce Zincke's synthesis of o- and p- nitrophenyl thiolsulfinate, Oae obtained a 1:1 mixture of the corresponding thiolsulfonate and disul- fide. 2 At about the same time as Zincke's work, Fries reported the synthesis of 2- anthraquinonesulfenic anhydride. He had previously prepared the free 1- anthraquinone sulfenic acid and its sodium salt by hydrolysis of the sulfenyl chloride (11), but attempts to make the 2 -acid resulted only in the formation of the anhydride (12). About 25 years later, Small and co- workers showed that the compound obtained from perbenzoic acid oxidation of allyl disulfide was identical to the natural antibacterial isolated from garlic (24). This group then prepared eight thiolsulfinates by peracid oxidation of their corresponding disulfides. All displayed antibacterial and anti - fungal action, which they surmised was due to reaction of the thiol- sulfinate with the -SH groups of the essential cell protein. Jacini and Lauria (15) also prepared several thiolsulfinates by oxidation of some unsymmetric disulfides with perbenzoic acid, which they called disulfide monoxides. In 1950, Burawoy and Turner (8) prepared several aromatic azothiolsulfinates. Then, in 1954, Backer and Kloosterziel noted that two different isomers of a thiol- sulfinate were obtained from the reaction (Equation 1) ArSOCI + Ar'SH Ar (Eq. 1) > it O if the aromatic groups in the starting compounds were reversed (1). In 1957, Vinkler and Klivenyi (25) prepared a series of compounds of the general formula RS(0)SR by the three methods reported in pre- vious literature (Equations 2, 3, 4). 3 ArSH + ArSOC1 --j ArrAr + HC1 (Eq. 2) 2ArSC1 + H20 - ArrAr + 2HC1 (Eq. 3) ArSSAr (0) ArSAr ö (Eq. 4) O A product study of the above reactions showed the compounds ob- tained to be the same in each case. Further evidence from infrared. spectra has borne out these conclusions (18, p. 248; 13, 14). Nearly all the workers that have reported on thiolsulfinates have noted their instability in aqueous media. Two reactions, closely related in that they involve the thiolsulfinate as the only or- ganic entity, have been reported. One is the disproportionation in acid solution (Equation 5). 2RSASR RSO2SR + RSSR (Eq. 5) This reaction has been studied both in this laboratory* and by sev- eral other groups (27) and will not be discussed further here. The other aqueous reaction =_s the alkaline hydrolysis (Equation 6). 2RSSR ----> 2RSO2 + RSSR (Eq. , O Zincke reported this reaction 50 years ago (33). He noted (31) that het alkaline solutions of nitro -substituted aromatic thiolsulfind ates developed intense colors which disappeared to yield the cor- responding disulfides and sulfinic acids, and he used this reaction as a qualitative test for the presence of thiolsulfinates (29, 31, 32, 33,. Cliff Venier; unpublished results. 4 Fries (11) also reported a colored solution occurred when 2- anthra- quinonethiolsulfinate was dissolved in a potassium hydroxide solution, but he did not attempt to isolate the resultant products. Small and co- workers (24) reported their alkyl thiolsulfinates were unstable to- ward alkalies, the products they isolated being the disulfides and sulfur dioxide. Savage and co- workers (23) have prepared and char- acterized the "S- monoxide" of cystine, cystamine and homocystine. They observed that the rate of hydrolysis of these thiolsulfinates in- creased with an increase in pH. Burawoy (8, 9) reported that al- kaline hydrolysis occurred with his aromatic -azo- thiolsulfinates, and he isolated the corresponding disulfide and sulfinic acid as pro- ducts. Burawoy stated that the alkaline hydrolysis of sulfenic acids and sulfenyl halides as well as thiolsulfinates produced essentially the same products in each case (Equation 6) (18, p. 283), which Kharasch postulated was due to the reaction sequence (Equation 7), RSC1. --> RSOH > RSSR 7PRSSR + RSO2 - (Eq. 7) in alkaline media (18, p. 392). Kharasch had previously reported that the brightly- colored solutions obtained in aqueous alkali were due to the presence of the sulfenic acid anion (6, 17), suggesting that the second step in Equation 7 above is reversible. Kharasch (18, p. 392) was led, therefore, to postulate the equilibrium (Equa- tion 8) 5 2RSOH RSSR + H2O RSH + RSO2H (Eq. 8) O as the mechanism for the so- called disproportionation cf sulfenic acids to mercaptans and sulfinic acids. This would imply that all reactions involving sulfenic acids will also involve thiolsulfinates as intermediates at one stage or another. Vinkler and Klivenyi (26, 27) do not agree that the sulfenic acid is in equilibrium with the thiolsulfinate, but they do postulate that the thiolsulfinate is the first hydrolysis product of sulfenic acid hy- drolysis regardless of the structure of the compounds involved. They found the disulfide and the sulfinic acid to be the major products of the reaction in all cases but found some sulfonate to be formed in the phenyl sulfenic acid hydrolysis. This product was believed to be produced via reduction of the thiolsulfinate by the initially- produced sulfinic acid (Equation 9). ArSSAr + ArSO2 - > ArSSAr + ArSO3- (Eq.
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