Sulfinic from hydrocarbons

Because of its relevance in environmental chemistry the reaction of photochemically excited sulfur dioxide with hydrocarbons in the gas phase has received considerable attention in recent years. In this reaction the principal path for formation of sulfinic acids is believed (Sherwell and Tedder, 1978) to be that shown in Scheme 2. Sherwell and Tedder do not think that abstraction of a hydrogen atom from RH by RS02-, i.e., RS02 + RH - RS02H + R-, occurs to any significant extent in such systems, although a summary of earlier studies of this reaction (Horowitz and Rajbenbach, 1975) shows that such a reaction has been proposed on occasion in the past. 

The production of industrially important perfluoroalkane sulfonic acids is generally accomplished by electrochemical fluorination. This method of preparation remains expensive and proceeds in good yields only for short hydrocarbon chains.30 Recently however, Wakselman and Tordeux have described a chemical method for the preparation of trifluoromethane sulfonic acid.31 The procedure involves reaction of a metal selected from zinc, cadmium, manganese, and aluminum with sulfur dioxide in DMF, followed by the introduction of trifluoromethyl bromide under slight pressure. The intermediate sulfinate is subsequently oxidized by hydrogen peroxide, and then hydrolyzed which leads to formation of the trifluoromethane sulfonic acid. Successful extension of the sulfination process to the modification of PCTFE should result in the formation of a sulfinated polymer which can ultimately be oxidized to give a sulfonic-acid modified polymer. 

Thiazolyl sulfamic acids, rearrangement of sulfonic acid, 70 rearrangement to sulfonic acid, 75 by sulfonation, 75 2-Thiazolyl sulfenyl chloride, transformation to, thiazolyl disulfides. 412 2-Thiazolyl sulfide, in hydrocarbon synthesis, 406 oxidation of, with m-chloroperbenzoic acid, 415 with CrOj, 415 with Hj02,405,415 with KMn04,415 physical properties, infrared, 405 NMR, 404 pKa, 404 ultraviolet, 404 preparation of, from 2-halothiazoles and 5-Thiazolyl sulfides, bis-5-thiazolyl sulfide, oxidation of, 415 general, 418 5-(2-hydroxythiazolyl)phenyl sulfide case, 418 physical properties, 418 preparation of, 417-418 table of compounds, 493-496 uses of. 442 2-Thiazolyl sulfinic acid, decomposition of, 413 preparation of, from 2-acetamidothiazole sulfonyl chloride, 413 from A-4-thiazoline-2-thione and H, 0, 393,413 table of compounds, 472-473 5-Thiazolyl sulfinic add, preparation of,... 

Sulfinic acids and hydrocarbons from sulfones SO2R -> SOgH + HR... 

In contrast to the sulfinic and carboxylic acids, the sulfonic acids are very highly ionized. As might be expected from their structure, they are fairly soluble in water and the lower members are therefore isolated usually in the form of salts. Many sulfonic acids may be hydrolyzed by heating with 25 per cent to 50 per cent sulfuric acid to yield the corresponding hydrocarbons or derivatives. The ease of hydrolysis differs with different members, and it appears that those compounds which are sulfonated most readily yield sulfonic acids which hydrolyze the most easily. Benzene sulfonic acid does not yield benzene except under special... 

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