1 -arenesulfonyl-2-

The reactions of N-arenesulfonylcarbodiimides with oxalyl chloride afford five membered ring 1 -arenesulfonyl-2,2-dichloro-3-alkylimidazolidine-4,5-diones 377... 

Amino-5-nitrothiazole, on treatment with arenesulfonyl halides and dimethylformamide at 140 C, gives (5-nitro-2-thiazolyl)amidme (274) (Scheme 168) (507, 508). The condensation products of the reaction of 2-aminothiazole derivatives with various aldehydes are grouped in Tables... 

Commercially important arenesulfonyl isocyanates are not directly accessible from the corresponding sulfonamides via phosgenation due to lack of reactivity or by-product formation at elevated temperatures. A convenient method for their preparation consists of the reaction of alkyl isocyanates with sulfonamides to produce mixed ureas which, upon phosgenation, yield a mixture of alkyl and arenesulfonyl isocyanates. The desired product can be obtained by simple distillation (16). Optionally, the oxalyl chloride route has been employed for the synthesis of arenesulfonyl isocyanate (87). 

Organoperoxysulfonic acids and their salts have been prepared by the reaction of arenesulfonyl chlorides with calcium, silver, or sodium peroxide treatment of metal salts of organosulfonic acids with hydrogen peroxide hydrolysis of di(organosulfonyl) peroxides, RS(0)2—OO—S(02)R, with hydrogen peroxide and sulfoxidation of saturated, non aromatic hydrocarbons, eg, cyclohexane (44,181). 

Di(arenesulfonyl) peroxides (24, = ryl) react with aromatic solvents to form aryl arenesulfonates (33) ... 

In addition to (461), Dorn has described the imine (463) isolated from 5-amino-l-methylpyrazole and arenesulfonyl chloride (80CHE1). Upon heating, or in the presence of triethylamine, it undergoes rearrangement to the more stable 5-bis(arylsul-fonamido)pyrazoles (464). 5-Iminopyrazolines (461) react with acyl chlorides at the exocyclic nitrogen atom to afford amidopyrazolium salts (B-76MI40402). 

Pyridinium imine, N-arenesulfonyl-synthesis, 2, 345 Pyridinium imines, 2, 344 1-Pyridinium imines ring expansion, 7, 42... 

Strong acids or superacid systems generate stable fluorinated carbocations [40, 42] Treatment of tetrafluorobenzbarrelene with arenesulfonyl chlorides in nitro-methane-lithium perchlorate yields a crystalline salt with a rearranged benzo barrelene skeleton [43] Ionization of polycyclic adducts of difluorocarbene and derivatives of bornadiene with antimony pentafluonde in fluorosulfonyl chloride yields stable cations [44, 45]... 

The ring contraction of 3//-azepines is also promoted by acylating agents,54 35 and by arenesulfonyl halides.34 For example, in refluxing acetic anhydride A,-phenyl-3//-azepin-2-amine yields 2-acetamidodiphenylamine (22% mp 121-122°C),34 whereas A,A,-diethyl-3/7-azepin-2-amine (30) with 4-nitrobenzoyl chloride in pyridine yields the benzanilide 31.35... 

When /V-arenesulfonyl-a-amino acid derived boranes 13 and 14 are used in substoichiometric amounts in order to mediate enantioselective aldol additions of a,a-dimethyl substituted ketcnc acetal 15, /J-hydroxycarboxylic esters 16 are obtained in enantiomeric excess of 84 to > 99 %3fi. 

Sulfur dioxide and carbon monoxide react with aryl radicals. The adducts formed are converted to the final products, arenecarboxylic halides and arenesulfonyl halides, by ligand transfer with the corresponding cupric halides (Schemes 10-36 and 10-37). 

In the same manner as described before, arenesulfonyl thiocyanates are able to show self-addition to conjugated systems yielding sulfones243,244. More important, however, is that reactions of selenosulfonates with unsaturated systems as well as with nucleophilic carbon have been proved. 

Benson17 has tried to collect some thermodynamic data based on a number of empirical rules for this class of radicals. He estimated heats of formation for HS02, MeSO 2) PhSO 2 and HOSO 2 as —42, —55, —37 and — 98kcalmor respectively. He also estimated a stabilization energy for the benzenesulfonyl radical of 14 kcal mol"1, which is very similar to that of the benzyl radical. However, recent kinetic studies18 (vide infra) have shown that arenesulfonyls are not appreciably stabilized relative to alkanesulfonyl radicals, in accord with the ESR studies. 

Sulfones are thermally very stable compounds, diaryl derivatives being more stable than alkyl aryl sulfones which, in turn, are more stable than dialkyl sulfones allyl and benzyl substituents facilitate the homolysis by lowering the C—S bond dissociation energy17. Arylazo aryl sulfones, on heating in neutral or weakly basic media at 100°C, yield an aryl and arenesulfonyl radical pair via a reversible one-bond fission followed by dediazoni-ation of the aryldiazenyl radical (see Scheme 2 below)20. However, photolysis provides a relatively easy method for generating sulfonyl radicals from compounds containing the S02 moiety. 

This is one of the steps in the copper-catalyzed redox-transfer chain addition of arenesulfonyl chlorides to styrenes (vide infra). The p-value of + 0.56 indicates the involvement of a simple atom transfer as well as a polar contribution to the transition state. 

FIGURE 1. Proposed mechanism for the disproportionation reaction of the arenesulfonyl radicals. 

The H and 13C CIDNP studies have shown that not only the sulfone 14, but also the sulfmic ester 15, is generated as cage products from the phenyl/p-toluenesulfonyl radical pair during the thermal decomposition of phenylazo aryl sulfone (13)54 (Scheme 2). The cross-termination of arenesulfonyl and triethylgermyl radicals was found to occur exclusively via the formation of germyl sulfinate, ArS(0)0GeEt333. 

The copper-catalyzed additions of sulfonyl chlorides to conjugated dienes and trienes73 as well as to aryl-substituted cyclic olefins74 and substituted styrenes have been described75 for example, arenesulfonyl chlorides add to vinylarenes providing good to excellent yields75 of /J-chlorosulfones ... 

Arenesulfonyl chlorides77 as well as alkenesulfonyl chlorides78 react with vinylarenes in the presence of RuCl2(PPh3)3 and 1 molar equiv. of Et3N to form a,/ -unsaturated sulfones in 70-90% yields. The reaction mechanism for the ruthenium(II) catalyzed reaction involves a free-radical redox-transfer chain process as outlined below77 ... 

The three steps 32-34 have been suggested77 to be equilibria, and the overall equilibrium must lie far to the left because no adduct 23 is found in the reaction mixture when the reaction of sulfonyl chloride with olefin is carried out in the absence of a tertiary amine. A second possible mechanism involving oxidative addition of the arenesulfonyl halide to form a ruthenium(IV) complex and subsequent reductive elimination of the ruthenium complex hydrochloride, [HRulvCl], was considered to be much less likely. 

When arenesulfonyl radicals are generated in benzene the only reported products are those of disproportionation50,95 (vide supra). However, Camaggi and coworkers95 have found that arenesulfonyl radicals in halobenzene replace the halogen atom at 150-190 °C, the relative reactivities being for Cl Br I, 1 5.9 18.6. These authors95 proposed that the reaction proceeds via a reversible ip.vo-substitution,... 

The synthesis of sulfones included electrophilic substitution, specifically, Frie-del-Crafts catalysis by A1C13, FeCl3, SbCl5, AlBr3 and BF3, and so on, which are efficient catalysts for the sulfonylation by arenesulfonyl halides.1 22... 

Ardel D-100 bisphenol-A polyarylate, 48 Arenesulfonyl chlorides, 329 Aromatic-aliphatic alternating... 

Note When attached to an atom other than carbon, alkyl- or arylsulfonyl groups are usually known as alkane- or arenesulfonyl groups (lUPAC Rule C 21)1076 considerd as acyl-type derivatives rather than sulfones. 

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