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C-Aihrlsulfonylacetic ACIDS a 1ID THEIR

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C-Aihrlsulfonylacetic ACIDS a 1ID THEIR A KINETIC STUDST OP THE DECOMPOSITION OF SOME «C-AiHrLSULFONYLACETIC ACIDS A1 ID THEIR SALTS HI VARIOUS SOLVENTS DISSERTATION sented in Partial Pulfillxncnt of the Requirement for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Donald Joseph CJ’Connor, B.S. The Ohio State University 1952 Approved by: i J d b l Advioer ACKNOWLEDGEMENT The author would Ilka to aeknowladgs his indebtedness to Dr. Frank Varhoek for hid halpful eounsal during the eouraa of this work. -1 S 0 9 4 GO TABLE OF CONTENTS INTRODUCTION 1 EXPERIMENTAL Preparation of Solvents 3 Preparation of p-Toluenemercaptoacetic Acid 3 Preparation of p-ToluenesulfonylacetIc Acid k Preparation of Sodium p-Toluenesulfonylacetate 5 Apparatus 5 Procedure 6 RESULTS The Reaction 8 Order of the Reaction 8 Dissociation Constant of p-Toluenesulfonyl- acetic Acid 9 Reaction Rate Constants 10 Effect of Solvent 1^ Effect of Concentration 23 Effect of Added Ease 23 Energy of Activation 24- Entropy Factor 26 Decomposition of the Free Acid 23 DISCUSSION Effect of Solvent on the Activation Energy 30 Sffect of Solvent on the Sntrooy Factor 3Jl Effect of Ion Association 1u2 SUMMARY h 5 SUGGESTIONS FOR FURTHER WORK I4.6 EXPGRIHGNTAL DATA REFERENCES 61 AUTOBIOGRAPHY -ii- A KINETIC STUDY OP THE DECOMPOSITION OP SOME og-ARYLSULPONYLACETIC ACIDS AND THEIR SALTS IN VARIOUS SOLVENTS INTRODUCTION 1 2 Recent review articles * have highlighted the great Interest in decarboxylation reactions of many types of organ­ ic acids. In this paper, the major concern is for that tyne of reaction which involves first order decomposition of the anion of the acid as examplified by trinitrobenzoic acid,^*^ trihaloacetic acids^'^*?»8 and X-nitroa].Vcylcarboxylic^' ^ ! r-/ acids. Verhoek ^ * has suggested that the mechanism of this reaction involves only a unimolecular decom oosition of the acid anion to form a carbanion and carbon dioxide with a sub­ sequent rapid reaction of the carbanion with a nroton from the solvent. Eyring^ has suggested a bimolocular reaction between the acid anion and a solvent molecule to give direct­ ly the product and carbon dioxide. On the basis of available evidence no clear cut flee is ion between these hypotheses could be reached. It was hoped, how ever, that study of another system of acids of a similar re­ action type would help in the resolution of this problem. Professor G.L. Wilson suggested that af-arylsulfonylfat by acids might be of interest. In the early literature phenyl- sulfonylacetIc acid and the toluene analogue wero reoorted 1 ° to yield the methylarylsulfones and carbon dioxide when heat­ ed at 170° In strong alkali. Substituted of-nltroarylsulfonyl - 2 - fatty acids have been transformed * i f likewise into «i-nitro- arylalkylsulfones by heating the alkali metal salts of the acids in aqueous feebly acid solutions. In no case, however, were any quantitative kinetic investigations carried out. Therefore, it x*as decided to investigate the decomposi­ tion of p-toluenesulfonylacetic acid and some of its salts In water and water-glycol, water-dioxane mixtures under vari­ ous conditions of temperature, concentrations and added sub­ stances. The results of this investigation Trill be found in the pages following. 0 - 3 - SXPSilU'EJIiTAL Preparation of Solvents. Ethylene glycol, obtained from the Carbide and Carbon Chemical Corporation, was dried over drierite for three days and distilled at 1,7 nun. of mercury through a 1|.0 cm. column packed with monel metal scroening. The middle half was col­ lected and stored in a glass stopnered bottle under nitrogon. Analysis with Fischer Beagent showed loss than 0.05 percent wator. Dioxanc, obtained from the Carbide .and Carbon Chemical Corporation, was purified by the mobhod of 'less and Prohm 15 as described by Fieser. ^ The distillation was carried out through a 90 cm column packed with glass helices under nitro­ gen. The middle three fifths (101.1-101.2°) was collected and stored under nitrogen in a glass stoppered bottle. The mixed solvents wore prepared by transferring r. weighed quantity of the particular solvent to a glass stop­ pered bottle previously flushed with nitrogen. To mis uas then added a weighed quantity of double distilled wa.,er mb'- ficient to yield the solvent mixture desired. All weighin. -j were made to the nearest centigram. Preparation of p-toluenemercaptoacetlc acid. Cd-j-<j>-3 ClL: Lh i p-Toluenenercaptoacetic acid was prowared accoi’diug ; It) a modified procedure of Anwers and Thies. In 5^0 ml. c " water 100 g. (0.8 moles) of p-thlocrosol (Eastman Kodak C.., - k - white label) was neutralized with. 32 g. (0.8 moles) of sodium hydroxide. The resulting salt solution was poured rawidly with stirring into ij.00 ml. of a water solution entaining 76 g. (0.8 moles) of monochloroacetic acid (Ilallinkrodt A.R. grade) neutralized with sodium hydroxide. In a few minutes, sodium p-toluenemercaetoacetate precipitated forming a white pasty mass. The precipitate was allowed to stand in contact with the supernatant liquid 3 to Ij. hours before filtration. The salt was washed on the filter nanor with one 100 ml. wortion of cold water, then resuspended in fj'OO ml. of water. The free acid was formed fro i the salt by the add. it ion of 1^0 ml. of concentrated hydrochloric acid. After filtration, the acid was recrystallized once from -water, from, which It separates as an oily liquid before solidifying, and twice from benzene forming beautiful white flakes. (n.p. 93* 0° G ) The yield was 90 percent of the theoretical. Preparation of p-toluenesulfonylacetic acid. CH^-^^SQo-CrigCQQH The purified mercaptoacetic acid was oxidized in glacial acetic acid by 30 percent hydrogen peroxide by a modification of the method of Siebert and Fromm.^ In 200 ml. of rc -,1c acid was dissolved lj.3 g« (0 .21|. moles) of the acid. Over a one hour period ml. of 30 percent hydrogen peroxide . • ■: .w ’ slowly while the temperature was maintained bo two on 1':° el 20°. After standing 2l\. hours, the solvent was distilled almost to dryness under the vacuum of a water as virator. The rosl e as - 5 - then poured into a small amount of water and recrjstallized rapidly. Two recrystallizations from benzene gave white crystals of p-toluenesulfonylacetic acid (m.p. 117• 0°-117»5>° ) • The melting point was taken as an indication of purity. The neutral equivalent was determined to bo 211|.*1 compared to a theoretical value of 2H4..2. Preparation of sodium p-toluonosulfonylacotate. — TO^e^-'Stfo-gBp-doofa ------------------ ------------ The sodium salt of this acid was prepared by mixing equi­ valent amounts of alcohol solutions of sodium hydroxide and the acid. The salt precipitated im odiatcly and w:i3 recrystal­ lized from alcohol. The salt was then dried and stored over Drierite. Apparatus. The thermostatically controlled baths wore those described 18 by Trivich. Mineral oil was used as heat transfer medium. Temperature control, using a mercury in gloss regulator to control the grid of a FG5>7 thyratron tube, was maintained at iO.Of?° in all three baths, 7^«0°» 8£.0° and 95»0°* In addi­ tion to the intermittent heater a permanent 2^0-watt heater controlled to about 1S>° below the bath temperature by moans of a powerstat was used. The sample tubes used on most runs were those described l8 by Trivich consisting of a tube of about ij.0 ml. capacity fitted with a standard taper, 19/.3 J3 * ground glass cover, end - 6 - around this another large cover, standard taper, 3h A !-£, which prevented seepage of oil into the sample tube. Procedure. The reaction samples were prepared by dissolving a weighed sample of the appropriate salt or acid in 2%0 ml. of the ap­ propriate solvent. Ten milliliter sai^mles were pipetted into the reaction flasks which were then closed. All of the re­ action flasks, suspended from bars, wore immersed in the baths at the same time. This nroceduro is justified by the similar­ ity in construction of all the tube3. After one half hour had elapsed to insure that the temperature of the bath had been attainod, the first sample was withdrawal and olun.god into an ice bath to halt the reaction. After cooling and opening the reaction flask, 10 ml. of standard hydrochloric acid was added to the flask to mako the solution acid. ITitrogon was then bubbled through the solution for 10 minutes to remove the carbon dioxide formed during trie reaction. Jhe excess hydrochloric acid was titrated to a phonolphthaloin end point with standard sodium hydroxide solution from a 10 ml. nicro- burette. All analytical solutions used were obtained from the Ohio State University Control and deagent Laboratory. When the reacting solutions contained only acid rather than salt, the procedure was altered slightly. After samples were removed from the bath and cooled, nitrogen was nassed - 7 - bhrou^h the solution Tor 10 minutes cl remove carbon dioxido, and the acid v;as then titrated directly with the standard sodium hydroxide solution. RESULTS The Reaction To verify that the reaction proceeds as reported by O t t o , ^ viz. , ° 0 - <j> H CH3 - Q y 0H2°*0 “* CH3-0"?-°-U + 'IC03 0 , 6 ^ 7 1 g» of sodium p-toluenesulfonylacetate wus dis­ solved in a 0.06 N sodium hydroxide solution and refluxed for six days, sufficient for 96-99 percent of reaction to occur. From, the cooled alkaline solution 0 .iiJpG3 g. of methyl-p-tol- uenesulfone corresponding to 97 percent reaction was recovered by means of an ether extraction followed by evaporation of the solvent on a steam bath. The molting oolnt of the sulfone was 8£*5>°“6£>.20 compared to a literature"^ value of u6o-07°.
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