The Sulfonation of Isobutylene. 11. Methyl-2-propene-1-sulfonic Acid

Recently it was reported3 that the action of ex- cess dioxane sulfotrioxide upon isobutylene gives methylpropene- 1 ,3-disulfonic acid in considerable...
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Vol. 03


The Sulfonation of Isobutylene. 11. Methyl-2-propene-1-sulfonic Acid' and Related Compounds BY C. M. SUTER, J. D. MALKEMUS~ AND S. ARCHER Recently it was reported3 that the action of excess dioxane sulfotrioxide upon isobutylene gives methylpropene- 1,3-disulfonic acid in considerable amounts. The monosulfonation products of this olefin have now been studied. The disulfonation of isobutylene proceeds a t a moderate rate a t about 0' in the presence of dioxane3 without serious interference from polymer formation. It seemed possible that in the absence of the dioxane sulfonation might occur at a much lower temperature where polymerization would be unimportant. However, the addition of chlorosulfonic acid to a large excess of isobutylene at -70' resulted in the formation of a mixture of polymers and no definite sulfonation product was isolated. The addition of dioxane sulfotrioxide or chlorosulfonate to isobutylene dissolved in ethylene chloride a t 0' also caused appreciable polymerization unless the reaction time was brief. In one experiment where dioxane chlorosulfonate was used there was isolated, in addition to t-butyl chloride and diisobutylene, a considerable quantity of a sodium octylenesulfonate; this gave a benzylthiuronium salt with a sharp melting point but has not been studied further. The crude sodium isobutylenesulfonate obtained by the rapid sulfonation of isobutylene with dioxane sulfotrioxide contained an appreciable quantity of a hydroxysulfonate, probably (CH& C(OH)CHZS03Na. This was indicated by analysis and by the evolution of hydrogen chloride upon treatment with phosphorus pentachloride or oxychloride. The hydroxysulfonate prepared from isobutylene oxide and sodium bisulfite gave a sulfonyl chloride identical with that obtained from the sulfonation product. This sulfonyl chloride was also identical with that obtained

of physical properties and conversion of the chloride into the benzylanilide. However, this evidence was believed to be inconclusive in distinguishing between I and I1 as structures for tlic

(1) Much of the material in this paper was presented before the Organic Division of the American Chemical Society at St. Louis, .4pril 9, 1941. (2) Present address, the Colgate-Palmolive Peet Company, Jersey City. New Jersey. (3) Suter and Malkemiis, THISJOORNAL, 6% 978 (1941).

(4) Linstead and Noble, J . Chem. Soc., 615 (1934); Kon, Linsteird and Wright, ibid., 599 (1934). ( 5 ) We are grateful to the Shell Development Company for a sample of isocrotyl chloride. (8) Hunter and Sorenson, THIS J O U R ~ A L . 64, ,1384 (19:32) (7) Mereshkowsky A n n , 431, 113 (19.23)








isobutylene sulfonation product since there was the possibility of the olefinic linkage shifting during formation of the sulfonyl chloride. Furthermore, the hydroxysulfonate might be expected to give the sulfonyl chloride of I1 rather than of I. It was then found that a pure benzylthiuronium sulfonate readily obtained from the isobutylene sulfonation product was identical with the corresponding derivative of the sulfonic acid prepared Erom methallyl chloride. Inasmuch as @-unsaturated carboxylic acids readily rearrange to the aisomers in alkaline solution4 there still remained the possibility that in the action of methallyl chloride upon sodium sulfite the product formed was I1 rather than 1. An attempt to prepare I1 by the action of isocrotyl chloride5 upon aqueous sodium sulfite a t a high temperature was unsuccessful. It was then found that the isobutylene sulfonation product reacted with a mixture of phosphorus pentabromide and tribromide t o give 1,2,3-tribromo-2-methylpropane.The loss of the sulfonate group from I would be expected since it is known6 that sodium w-toluenesulfonate undergoes cleavage in this manner forming benzyl bromide. If the compound I1 reacted with loss of the sulfonate group, only 1,1,2-tribromo-2methylpropane could result. The structure of the 1,2,3-tribromo-2-methylpropane was established by comparing it with a sample obtained by bromination of isobutylene? and by conversion into 1(CH&C(OH)CH2S03Na + 2PC15 + CaH,SO&l + 2HC1 + NaCl + 2 P O c l ~ bromo-3-acetoxy-3-methyl-l-propene through the action of potassium acetate. This reagent profrom the sodium methylpropenesulfonate syntheduces l,l-dibromo-2-methyl-l-propene from 1,1,2sized from methallyl chloride and sodium sulfite. These identities were established by comparison tribromomethylpropane.'


June, 1041

Reduction of the methylpropenesulfonyl chloride with zinc and 15% sulfuric acid gave almost entirely gaseous products including hydrogen sulfide. No thiol was isolated. Hydrolysis of the sulfonyl chloride gave the original sodium sulfonate and refluxing of this with aqueous alkali caused no detectable isomerizaiion. The evidence is, therefore, conclusive that in the monosulfonation of isobutylene, methylpropene-2-sulfonic acid is an important producl; this is accompanied by 2-hydroxy-2-methylpropane-l-sulfonic acid or an intermediate which yields this on hydrolysis. This suggests immediately that both of these compounds arise from the same intermediate, a primary addition product of the carbyl sulfate type, (CH,)?C--CH2

>so, so2-0


+ (CHs)2-C