The pathway for the aqueous chlorinolysis of a series of β-sulfonyl-sulfides is elucidated and the SN2 cleavage step examined. Steric effects in the cleavage of the α-polychloro-oxochloro-sulfonium chloride intermediates are held to be responsible for the suppression of the established nucleophilic competition between water molecules and chloride ions with the result that all cleavage products arise from nucleophilic attack by chloride ions. This report details the second known example of successful SN2 displacement on a carbon atom α to a sulfonyl group.

, and DEIG-NEVY SANDOVAL. Can. J. Chem. 57, 1206Chem. 57, (1979.A series of y-sulfone sulfonyl chlorides undergo a novel reduction upon reaction with lithium aluminum hydride to furnish the corresponding ethyl sulfones. The reactions appear to proceed in an SN2 fashion with the chlorosulfonyl moiety functioning as the leaving group. In general sulfonyl chlorides furnish mercaptans as-hydride reduction products.A novel two-phase hydrolysis is shown to convert a thiol ester to a symmetric sulfide which involves hydrolysis and an SN2 displacement in the aqueous phase.HARVEY OWEN FONG, WILLIAM RAYNE HARDSTAFF, DENIS GEORGE KAY, RICHARD FRANCIS LANGLER, RICHARD HERMAN MORSE et DEIG-NEVY SANDOVAL. Can. J. Chem. 57,1206Chem. 57, (1979.Une strie de chlorures de y-sulfone-sulfonyles subit une nouvelle rtduction par rtaction avec de l'hydrure de lithium et d'aluminium pour fournir les sulfones ethyltes correspondantes. Les reactions semblent se produire par un mecanisme SN2 dans lequel 1e groupe chlorosulfonyle agit comme nucltofuge. En gtntral, les chlorures de sulfonyles conduisent aux mercaptans si on les soumets a une rtduction par les hydrures.On montre qu'une nouvelle hydrolyse en deux etapes permet de transformer un thioester en sulfure symttrique; la reaction implique une hydrolyse et une substitution SN2 dans la phase aqueuse.[Traduit par le journal]

A reexamination of previous proposais for the prediction of regioselectivity in sulfide chlorinations has found them to be unsatisfactory. A new basis for such predictions is advanced viz. the electronegativity difference (ΔXp) of the substituents attached to the α- and α′-carbon atoms of the sulfide substrate. Upon establishing that the new basis for these predictions is satisfactory, it is successfully applied to the problem of predicting reactivity differences in isomeric sulfide chlorinations. The formation of isomeric sulfonium ions is used to establish the failure of possible isomerization processes to occur under normal reaction conditions.

Die Chlorierung der Sulfide (I) ergibt ausschließlich die chlorierten Produkte (II) und keine Isomere.

Die Chlorosulfonylgruppe der Sulfone (I) hat bei der LiAlH4‐Reduktion abweichend vom üblichen Verhalten die Funktion einer Fluchtgruppe [Bildung der Sulfone (II)].