Sulfonyl chlorides from hydrocarbons

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,... 

The following products are usually contained in the reaction mixture produced by sulfochlorination 1980 mono-, di-, and poly-sulfonyl chlorides chloro-mono-, -di-, and -poly-sulfonyl chlorides alkyl chloride and unchanged starting material of which the last two are unhydrolysable neutral oils. The individual products obtained on sulfochlorination of aliphatic hydrocarbons of low molecular weight can be separated by distillation, but it has also been found that the mono- can be separated from the poly-sulfonyl portions by treating the mixture with at least a five-fold amount of pentane and cooling to — 30°.206... 

As mentioned above, the chlorosulfonyl group cannot be introduced into aromatic hydrocarbons by Reed s process, but this can be achieved by means of the chlorides from sulfuric acid.213 Preparation of sulfonyl chlorides by means of chlorosulfuric acid depends on using a sufficient excess and on the purity of the acid sulfones may be formed as by-products, and these can be further sulfochlorinated.214 Benzenesulfonyl chloride has been prepared from benzene in 75-77% yield in this way.215... 

Chlorosulfonic acid is widely used in organic qualitative analysis to prepare solid derivatives from liquid or low melting aromatic compounds, e.g. hydrocarbons, halides and ethers." The procedure involves conversion of the aromatic compound into the sulfonyl chloride, which is subsequently reacted with ammonia to yield the solid sulfonamide derivative which is suitable for melting point determination, Chlorosulfonic acid reacts with carboxylic acid anhydrides to give excellent yields of the acid chlorides (Equation 11). 

Poliak et al. claimed that the reaction of biphenyl 32 with excess chlorosulfonic acid (six equivalents) at 18 °C affords dibenzothiophene-5,5-dioxide-3,7-disulfonyl chloride 34, but more recent attempts to reproduce this result were unsuccessful and only the 4,4 -disulfonyl chloride 33 (80%) was isolated. However, the cyclized product 34 was obtained in good yield (72%) when biphenyl 32 was heated with a large excess of chlorosulfonic acid (20 equivalents) at 150 °C (4 hours) (Equation 11). The reaction presumably involves the formation of the intermediate biphenyl-2,4,4 -trisulfonyl chloride, 35 which subsequently cyclizes with loss of hydrogen chloride to give the dibenzothiophene dioxide 34. Further study of the action of chlorosulfonic acid on biphenyl 32 showed that the optimum yield of the 4-sulfonyl chloride (43%) was derived from treatment of 32 with the reagent (1.5 equivalents) in thionyl chloride as solvent at 0 °C (1 week). The best yield (89%) of the 4,4 -disulfonyl chloride 33 was also achieved by treatment of the hydrocarbon 32 with chlorosulfonic acid (three equivalents) in thionyl chloride at room temperature (1 week). 

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