Arylsulfonyl chloride, nucleophilic reactions

The mechanism of the reaction of arylsulfonyl halides with nucleophilic reagents has been widely studied and reviewed. " The majority of kinetic and other evidence indicates that the reactions of an arylsulfonyl chloride 1 with a nucleophile (Nu") generally follow the concerted bimolecular SN2-type mechanism as depicted in Equation 7 with a linear bipyramidal transition state which is similar to the Sn2 (acyl) pathway established for acyl halides. ... 

Theoretical studies of the gas-phase hydrolysis or methanolysis of methylsul-fonyl chloride indicated a concerted Sn2 process involving a four-membered cyclic transition state. The tertiary amine-catalysed hydrolysis of benzenesul-fonyl chloride was shown to be inhibited by chloride ion and a nucleophilic mechanism of catalysis was favoured. Kinetic studies" of the solvolysis of p-substituted benzenesulfonyl chlorides in aqueous binary mixtures with acetone, methanol, ethanol, acetonitrile and dioxime showed that the reactions were third order processes, with first order rate constants determined mainly by the molar concentrations of the protic solvent, so that the reaction rates appear to be dominated by solvent stoichiometry. The solvolyses in methanol and ethanol yield both an alcoholysis (ap) and a hydrolysis product (hp). Solvolyses of electron-rich arylsulfonyl chlorides, under neutral or acidic conditions, exhibited surprising maxima in solvent-dependent S values as defined by Equation 15. 

Imlnium ions. N-Arylsulfonyliminium ions are generated from N-arylsulfonyl-a-amino acid chlorides on treatment with AgSOjCFj. These iminium ions are very reactive and readily undergo nucleophilic addition or intramolecular Friedel-Crafts reactions. ... 

Under the usual conditions one equivalent of the diazoalkane is consumed by the liberated acid but this can be avoided by use of an added base such as triethylamine/ Cyclic a-diazoketones, which are not available from acid chloride, can be prepared by reaction of a nucleophilic derivative such as the a-hydroxymethylene enolate with arylsulfonyl azides. Several combinations of carbon nucleophile and sulfonyl... 

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