1,2-Cyclic sulfite have been shown to react with sodium acetoacetate either by SN2 attack at carbon to give γ -lactones or by attack at the S=O group to give acetals.
      The specific rates of solvolysis of benzyl p-toluenesulfonate and nine benzylicring- substituted derivatives have been satisfactorily correlated using NT and YOTs scales within the extended Grunwald–Winstein equation.The reactions of Zphenylethyl X-benzenesulfonates with Y-pyridines in acetonitrile at 60° C have been studied at high pressures. The results indicated that the mechanism of the reaction moves from a dissociative SN2 to an early-type concerted SN2 with increasing pressure.
      In strongly alkaline solution, 2,4-dinitrophenyl 4-hydroxy-β-styrenesulfonate hydrolyses via a dissociation (E1cB) mechanism with the probable intervention of an extended ‘sulfoquinone’ intermediate.
      Tris(fluorosulfuroyl)fluoromethane reacted with bis(diethylamido)benzyl phosphite to yield an intermediate which extruded a molecule of SO₂ to give as final product the bis(fluorosulfonyl) compound. The kinetics and mechanism of the reaction of fluorinated tricoordinate phosphorus compounds and aryl 2,2,2-trifluoroethyl sulfenates have been reviewed.
      Ab initio SCRF/MO methods have been applied to the hydrolysis and methanolysis of methanesulfonyl chloride The aminolysis by aromatic amines of sulfonyl and acyl chlorides has been examined in terms of solvent parameters, the former being the more solvent-dependent process. Solvent effects on the reactions of dansyl chloride with substituted pyridines in MeOH–MeCN were studied using two parameters of Taft’s solvatochromatic correlation and four parameters of the Kirkwood–Onsager, Parker, Marcus and Hildebrand equations. MeCN solvent molecules accelerate charge separation of the reactants and stabilize the transition state.
      The activation parameters of the hydrolysis in aqueous dioxane of p-toluenesulfonyl bromide pass through maxima at dioxane mole fractions of 0.01 and 0.12, which correspond to the range of stabilization of the solvent structure. The chiral spiro-λ 4-sulfurane is easily hydrolysed under basic conditions (1 M NaOH) to give optically pure sulfoxide as a single diastereomer. In contrast, hydrolysis of spiro sulfurane under acidic conditions (1 M HCl) gave sulfoxide, also as a single diastereomer but with an opposite absolute configuration at the sulfur atom. The proposed mechanism of these reactions is as follows: hydrolysis under basic conditions may proceed through the attack of hydroxide ion on the central sulfur atom to give an intermediate. Cleavage of the S-O(acyloxy) bond and isomerization around the sulfur centre generates the pentacoordinate intermediate with the hydroxyl group at the apical position. Then, deprotonation and tandem breaking of the S-O(alkoxy) bond takes place to give the highly diastereoselective formation of the sulfoxide with R absolute configuration. Under the acidic conditions, the reaction may proceed through the initial protonation of the spirosulfurane at the oxygen of alkoxy, then attack by H₂O at the sulfur atom takes place and a hexacoordinate sulfur intermediate is formed. Cleavage of the S-O(alkoxy) bond of the intermediate and isomerization around the sulfur centre produce an intermediate with the hydroxyl group at the apical position. Final deprotonation and consecutive breaking of the S-O(acyloxy) bond gave sulfoxide with S absolute configuration at the sulfur atom.