Sulfonic acid halides fluorides

This reaction, parallel with 10-77, is the standard method for the preparation of sulfonyl halides. Also used are PCI3 and SOCI2, and sulfonic acid salts can also serve as substrates. Sulfonyl bromides and iodides have been prepared from sulfonyl hydrazides (ArS02NHNH2, themselves prepared by 10-126) by treatment with bromine or iodine.Sulfonyl fluorides are generally prepared from the chlorides, by halogen exchange. 

General Reaction Chemistry of Sulfonic Acids. Sulfonic acids may be used to produce sulfonic acid esters, which are derived from epoxides, olefins, alkynes, allenes, and ketenes, as shown in Figure 1 (10). Sulfonic acids may be converted to sulfonamides via reaction with an amine in the presence of phosphorus oxychloride [10025-87-3], POCl3 (11). Because sulfonic acids are generally not converted direcdy to sulfonamides, the reaction most likely involves a sulfonyl chloride intermediate. Phosphorus pentachloride [10026-13-8] and phosphorus pentabromide [7789-69-7] can be used to convert sulfonic acids to the corresponding sulfonyl halides (12,13). The conversion may also be accomplished by continuous electrolysis of thiols or disulfides in the presence of aqueous HQ [7647-01-0] (14) or by direct sulfonation with chlorosulfuric acid. Sulfonyl fluorides are typically prepared by direct sulfonation with fluorosulfuric acid [7789-21-1], or by reaction of the sulfonic acid or sulfonate with fluorosulfuric acid. Halogenation of sulfonic acids, which avoids production of a sulfonyl halide, can be achieved under oxidative halogenation conditions (15). 

Fluorinated and Chlorfluorinated Sulfonic Acids. The synthesis of chlorinated and fluorinated sulfonic acids has been extensively reviewed (91,92). The literature discusses the reaction of dialkyl sulfides and disulfides, sulfoxides and sulfones, alkanesulfonyl halides, alkanesulfonic acids and alkanethiols with oxygen, hydrogen chloride, hydrogen fluoride, and oxygen—chloride—hydrogen fluoride mixtures over metal halide catalysts, such as... 

Reaction with Halides and Sulfonates. Reactive halides such as iodides, allylic, and benzylic halides, and chlorides of organic acids (sulflnic, sulfonic, and phosphonic) react with DAST to form the corresponding fluorides. ... 

Percolation of an ether solution of benzoic acid through a column of a macroporous AER in OH" form put the resin in benzoate form. Stirring of the resin with 4 molar equivalents of ethyl bromoacetate at room temperature produced 99% of ethyl benzoyloxyacetate as shown in equation (18). Similar displacement reactions of alkyl halides have been used to form esters from other carboxylate ions, " alkyl fluorides from phenyl sulfones from PhSO N,N ... 

Cationic fluorinated surfactants have been prepared from perfluoroalkyl esters, obtained by converting an acid fluoride into an ester. Reaction of the ester with a diamine and alkylation with a halide or sulfonate gives a cationic surfactant, for example [166] ... 

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