Disulfides sulfonic acid chloride

Sulfonic acid chloride Thioacyl disulfides from dithiocarboxylic acids... 

Sulfonic acid chlorides from disulfides via sulfinic acids s. 18, 561 SOgH SO2GI... 

Sym. disulfides from sulfonic acid chlorides 2 RSO2CI RSSR... 

General Reaction Chemistry of Sulfonic Acids. Sulfonic acids may be used to produce sulfonic acid esters, which are derived from epoxides, olefins, alkynes, aHenes, and ketenes, as shown in Figure 1 (10). Sulfonic acids may be converted to sulfonamides via reaction with an amine in the presence of phosphoms oxychloride [10025-87-3] POCl (H)- Because sulfonic acids are generally not converted directiy to sulfonamides, the reaction most likely involves a sulfonyl chloride intermediate. Phosphoms pentachlotide [10026-13-8] and phosphoms pentabromide [7789-69-7] can be used to convert sulfonic acids to the corresponding sulfonyl haUdes (12,13). The conversion may also be accompHshed by continuous electrolysis of thiols or disulfides in the presence of aqueous HCl [7647-01-0] (14) or by direct sulfonation with chlorosulfuric acid. Sulfonyl fluorides are typically prepared by direct sulfonation with fluorosulfutic acid [7789-21-17, or by reaction of the sulfonic acid or sulfonate with fluorosulfutic acid. Halogenation of sulfonic acids, which avoids production of a sulfonyl haUde, can be achieved under oxidative halogenation conditions (15). 

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

Sulfonic acids are conveniently made by oxidation of the corresponding thiones or disulfides. Direct sulfonation is best effected with chlorosulfonic acid. Direct thiation can be achieved with sulfenyl chlotides to give 5-thiopyrimi-dines in excellent yields. For example, the reaction of 6-hydroxy-4(l//)-pytimidinone [4,6(1//,5//)-pyrimidinedione] 72 with benzylsulfenyl chloride or 2-methoxyphenylsulfenyl chloride gave the respective 5-thio derivatives 73 in 96% and 97% yields <1993SC2363, 2001JME3355>. 

Thiols can be prepared by the reduction of sulfonyl halides652 with LiAIH4. Usually, the reaction is carried out on aromatic sulfonyl chlorides. Zinc and acetic acid, and HI. also give the reduction. Sulfonic acids have been reduced to thiols with a mixture of triphenyl-phosphine and either Ii or a diaryl disulfide.633 Disulfides RSSR can also be produced.634 For the reduction of sulfonyl chlorides to sulfinic acids, see 0-118. 

LACTAMS Di-n-butyltin oxide. Ily-droxylamine-O-sulfonic acid. Iodine azide. Sodium eyanoborohydride. (3-LAC TAMS Cyanuric chloride. Grignard reagents. Ion-exchange resins. Lithium phenylethynolate. Sodium dicarbonyl-cyclopentadienylferrate. Titanium(lll) chloride. Titanium(IV) chloride. Tri-phenylphosphino-Carbon tetrachloride. Triphenylphosphine-Die thyl azodicar-boxylate. Triphenylphosphine-2,2 -Dipyridyl disulfide. 

The at complex from DIB AH and butyllithium is a selective reducing agent.16 It is used tor the 1,2-reduction of acyclic and cyclic enones. Esters and lactones are reduced at room temperature to alcohols, and at -78 C to alcohols and aldehydes. Acid chlorides are rapidly reduced with excess reagent at -78 C to alcohols, but a mixture of alcohols, aldehydes, and acid chlorides results from use of an equimolar amount of reagent at -78 C. Acid anhydrides are reduced at -78 C to alcohols and carboxylic acids. Carboxylic acids and both primary and secondary amides are inert at room temperature, whereas tertiary amides (as in the present case) are reduced between 0 C and room temperature to aldehydes. The at complex rapidly reduces primary alkyl, benzylic, and allylic bromides, while tertiary alkyl and aryl halides are inert. Epoxides are reduced exclusively to the more highly substituted alcohols. Disulfides lead to thiols, but both sulfoxides and sulfones are inert. Moreover, this at complex from DIBAH and butyllithium is able to reduce ketones selectively in the presence of esters. 

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,... 

Orthanilic acid was first made by the reduction of nitro-benzenesulfonic acid by ammonium sulfide.2 This reduction has also been carried out electrolyticallv, and by the use of iron or zinc.3 The acid has also been made by the rearrangement of phenylsulfamic acid,4 by the action of sodium hypobromite upon potassium o-carbaminebenzenesulfonate,5 by the reduction of the mixed nitrobenzenesulfonic acids followed by separation of the isomers,6 by the action of methyl alcohol upon o-nitro-phenylsulfurchloride,7 by the action of acid upon diacetyl diphenylsulfamide,8 by the debromination of />-bromoaniline-e-sulfonic acid,9 by the reduction of 1,2,6-aminothiophenolsulfonic acid,10 and by the hydrolysis and reduction of e-nitrobenzene-sulfonyl chloride, which was obtained from di-o-nitrophenyl-disulfide.11... 

The present procedure is that of Adams and Ferretti. Another method is the reduction of 1,2-benzenedisulfonyl chloride with zinc powder. In a third method a 2-aminomercaptobenzene is diazotized and converted to an intermediate xanthate and then to the corresponding mercaptosulfonic acid. The latter can be converted to the dimercaptan either by (1) oxidation to a di-sulfonic acid, conversion to the disulfonyl chloride, and reduction to the dimercaptan, or (2) mild oxidation to the corresponding disulfide, conversion to the sulfonyl chloride disulfide, and reduction to the dimercaptan. 

Oxidation of disulfides with halogens may lead to sulfonyl chlorides or the much less stable bromides which afford sulfonamides. However, replacement of the sulfur function by halogen or complete desulfurization may also occur. Treatment of the sulfonyl chloride does not yield the expected esters but is the best way to prepare the sulfonic acids. Electrolytic oxidation of thiones affords a mixture of sulfonic acids and desulfurized compounds. The action of ozone on disulfides is a feasible but not very convenient reaction leading to sulfonic acids. Scheme 54 summarizes some of these relationships and the unusual nitration of the sulfonamide (147) (62BEp619423) for convenience the generalized triazole Tr is shown in... 

Imidazole- and benzimidazole-2-thiols usually exist largely as the thione tautomers. The thiol (thione) group is susceptible to alkylation (especially in alkaline media), and can be oxidized to sulfide, disulfide and sulfonic acid. This oxidation can often be carried out quite selectively by careful choice of oxidizing agent. The sulfur function can be removed with nitric acid, iron(III) chloride, hydrogen peroxide or, most commonly, Raney nickel. Alkyl- and arylthio groups can be oxidized to sulfoxide or sulfone. 

In acetic acid solution 30% hydrogen peroxide converts 2-imidazolyl methyl sulfides into sulfones" " and sometimes sulfoxides. In tri-fluoracetic acid the sulfoxides are formed preferentially periodate, too, can give the sulfoxides. Oxidation of 4-mercaptoimidazoles under mild conditions gives bis(4-imidazolyl) disulfides which can be cleaved by hydrogen sulfide. With 15% alkaline hydrogen peroxide at 90°C the sulfonic acid is the major product. Imidazole-5-sulfonyl chlorides give sulfonamides... 

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