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Acid-catalysed hydrolysis of N-sulphonyl sulphilimines—II
Authors:I Kapovits  F Ruff  J Gulyás  Á Kucsman
Institution:Institute of Organic Chemistry, L.Eötvös University, Budapest, Hungary
Abstract:The basicity and the acid-catalysed hydrolysis of ph(R)SNTs and o-HC6H4(Me)SNTs sulphilimines have been studied by UV spectrophotometric and kinetic methods, respectively, in aqueous HClO4 (1–10 M) and 1:1 (v/v) EtOH/H2O-HClO4 (0.5–6 M). Depending on the constitution of the substrates, sulphilimine hydrolysis can follow three different courses, according to rate-acidity profiles, Bunnett-Olsen's treatment, activation parameters and product analysis. Most typical for sulphilimines is SN2 hydrolysis with SIV-N bond cleavage. In this case the reaction starts with the nucleophilic addition of water and is promoted by acid-base catalysis. If a relatively stable carbenium ion can be formed from R group, an SN1 reaction with SIVC bond cleavage takes place. Sulphilimine with X = o-CO2H due to neighbouring-group participation hydrolyses very rapidly via acyloxy-sulphurane and acyloxy-sulphonium ion intermediates with five-memembered ring (SNi reaction involving SIVN bond cleavage).
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