Chlorides arylsulfonyl

Fluorosulfuric acid may be used to prepare diazonium fluorosulfates, ArN SO.F (44), which decompose on heating to give aryl (Ar) fluorosulfates (36,45). Aryl fluorosulfates are also obtained from arylsulfonyl chlorides and fluorosulfuric acid (35). Alkyl and other organofluorosulfates form during electrolysis of fluorosulfuric acid in the presence of organic species (46,47). 

Arylsulfonyl chlorides and enamines reacted to give sulfonated enamines (452,453,474). The latter could be hydrolyzed to the corresponding sulfonyl ketones. 

Acetyl-3-(perhydropyrido[l, 2-u]pyrazin-2-yl)-1 //-indole was deacety-lated in boiling MeOH in the presence of NaOH, and the product, 3-(perhydropyrido[l,2-u]pyrazin-2-yl)-l//-indole was N-acylated with different arylsulfonyl chloride in THF at 0°C in the presence of (Me3Si)2NNa (99MIP12, 01USP6251893)). 

Far superior yields of l-(arylsulfonyl)-l//-azepines 16 are now available by a one-pot synthesis involving the action of sodium azide on an arylsulfonyl chloride under solid-liquid phase-transfer conditions which prevents the formation of acidic sulfonamides and, hence, the ring-contraction process.75 This procedure also has the advantage of avoiding the use of high pressures and the isolation and handling of the potentially explosive sulfonyl azides. 

A mixture of the arylsulfonyl chloride (5 mmol), benzene (2.56 mol), NaN3 (5 mmol), NaHCO, (20 mmol), and methyltrioctylammonium chloride (0.5 mmol), under N2 in an autoclave, was stirred al 40 C for 3 h. The mixture was then heated slowly to 125 C and maintained at this temperature for another 3 h, during which time the pressure in the vessel rose to 31 -54 atm. The mixture was allowed to cool and the autoclave was depressurized. The residual mass was filtered, and the residue washed thoroughly with cold H20. The benzene solution was separated from the aqueous filtrate, dried, and evaporated to give the crude product as a reddish yellow mass which was purified by column chromatography (neutral alumina, hexane/ benzene 3 2). The 1-(arylsulfonyl)-l//-azepines 16 were crystallized from light petroleum ether (bp 60-80 LC). 

Using method a, oligodeoxyribonucleotides were synthesized from di- to deca-deoxyribonucleotides by means of mesitylenesulfonylimidazole and mesitylenesulfonyl-1,2,4-triazole. With triisoproylbenzenesulfonylimidazole die condensation took place more slowly.11121 Compared widi the corresponding arylsulfonyl chlorides, imidazolides induced intemucleotide condensation much more slowly, but caused no darkening of the reaction mixture, did not affect acid-sensitive bonds in trityl protected nucleotides, and did not sulfonate the 3 -hydroxy groups.11111 The reaction conditions were room temperature, 5—6 days, and pyridine as solvent.11111... 

In these cases, arylsulfonyl chloride/azole mixtures were also used as coupling agents.ll471,[1331... 

Parallel array synthesis was used to access the 3-aryl-tetrahydro-l,2-diazepines 90 (and other related compounds) by cyclisation of the chloro ketones 88 on reaction with hydrazine to give 89 followed by sulfonamide formation the Si-TrisAmine was added at the end as a scavenger to remove any unreacted arylsulfonyl chloride remaining <06MCL3777>. 

The synthetic route to the A-arylsulfonylhydroxamic acids 177 is shown in Scheme 78 /para-substituted arylsulfonyl chlorides 176 are coupled with the appropriate 0-alkylhy-... 

Various arylsulfonyl chlorides reacted with to form peroxy intermediates. 

Other pseudohalides such as aryldiazonium ions (Table 2, entry arylsulfonyl chlorides (Table 2, entry 4)," ... 

Efficient homocoupling of the aryl iodonium salt 827 using Zn is catalyzed by Pd(acac)2[708], Homocoupling of the arylsulfonyl chloride 828 as a pseudohalide takes place in the presence of 2 equiv. of Ti tetraisopropoxide[709]. 

Various arylsulfonyl chlorides reacted with 02 to form peroxy intermediates. 2-Nitrobenzenesulfonylperoxy intermediate 51 had shown a larger oxidizing ability towards olefins compared with the 4-nitrobenzenesulfonylperoxy intermediate. When 2-nitrobenzenesulfonyl chloride reacts with 02 at low temperature (—20 to —35 °C) in CH3CN, the corresponding sulfonylperoxy radical 51 or anion 52 is generated. The radical character of the sulfonylperoxy intermediate 51 was further confirmed by the electrophilic oxidizing nature of a 2-nitrobenzenesulfonyl chloride/K02 mixture. 

Reduction, see also Hydrogenation electrolytic, see Electrolysis of anisoin to deoxyanisoin by tin and hydrochloric add, 40, 16 of arylsulfonyl chlorides to aryl disulfides by hydriodic add, 40, 81... 

Amongst oxidizing reagents, arylsulfonyl chlorides in pyridine simultaneously cyclize and acylate amidinothiourea (and its 2V-phenyl and AT -diphenylhomologs), producing moderate yields of sulfonyl derivatives of 3,5-diamino-l,2,4-thiadiazoles in one step.116... 

Arylsulfonyl chlorides, which are known to oxidize a variety of thioamides,127 also cyclize A-(sulfonamidino)thioureas directly to sulfonyl derivatives of amino-1,2,4-thiadiazloes.110... 

Thiophene sulfoxides and thiophene sulfones can be prepared by direct oxidation of the corresponding sulfides (Section 3.15.9.5.1) with hydrogen peroxide. 2-Thiophene sulfones are also prepared by reaction of arylsulfonyl chlorides with thiophene under mild Friedel-Crafts conditions, or by condensation of 2-thiophenesulfonyl chlorides with aromatic compounds (Section 3.14.2.4). 

From a series of studies of the reaction of arylsulfonyl chlorides with aniline in methanol at 25°, substituents in the aryl moiety appear to exert an effect registered best by a+. The plot incorporating results by both... 

Fig. 7. Log rates of aminolysis of arylsulfonyl chlorides with aniline vs. a. ...

The same products were also obtained by treatment of quinuclidin-3-one (2) with hydrazoic acid under Schmidt reaction conditions175 here the process gives mainly the monocyclic amide (147). Reaction of quinuclidin-3-one oxime (103) with arylsulfonyl chlorides in alkali leads to fragmentation and formation of iV-substituted 3-cyano-piperidines.179,177... 

Vinyl Substitutions with Carboxylic Acid Halides, Aryl Sulflnates and Arylsulfonyl Chlorides 856... 

Normally, the most practical vinyl substitutions are achieved by use of the oxidative additions of organic bromides, iodides, diazonium salts or triflates to palladium(0)-phosphine complexes in situ. The organic halide, diazonium salt or triflate, an alkene, a base to neutralize the acid formed and a catalytic amount of a palladium(II) salt, usually in conjunction with a triarylphosphine, are the usual reactants at about 25-100 C. This method is useful for reactions of aryl, heterocyclic and vinyl derviatives. Acid chlorides also react, usually yielding decarbonylated products, although there are a few exceptions. Likewise, arylsulfonyl chlorides lose sulfur dioxide and form arylated alkenes. Aryl chlorides have been reacted successfully in a few instances but only with the most reactive alkenes and usually under more vigorous conditions. Benzyl iodide, bromide and chloride will benzylate alkenes but other alkyl halides generally do not alkylate alkenes by this procedure. 

Arylsulfonyl chlorides react similarly with palladium(0) catalysts, producing sulfur dioxide and arylpaUadium chlorides. In the presence of activated alkenes, the combination forms arylated alkenes in modest yields (equation 49).110... 

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