Browsing by Author "Cubillos, M"

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    Mechanism of the alkaline hydrolysis of O-ethyl S-(2,4,6-trinitrophenyl) thio- and dithiocarbonates
    (ROYAL SOC CHEMISTRY, 1999) Castro, EA; Cubillos, M; Santos, JG; Bujan, EI; Remedi, MV; Fernandez, MA; de Rossi, RH
    The alkaline hydrolysis of O-ethyl S-(2,4,6-trinitrophenyl) thio- and dithiocarbonates, 1 and 2, respectively, were studied kinetically in 5% dioxane in water, at 25.0 degrees C, and ionic strength 0.2 mol dm(-3) (KCl). Two kinetic processes, well separated in time, were detected. The fast process involves the formation of a sigma-complex by addition of HO- to one of the unsubstituted positions of the aromatic ring, followed by fast ionisation of this complex. The slow process leads to the formation of a mixture of 2,4,6-trinitrophenoxide and 2,4,6-trinitrobenzenethiolate ions in a 10 : 1 ratio, respectively, in the reaction of 2, and to a mixture in a 2. 1 ratio in the reaction of 1, independent of KOH concentration. Although the substrates show different kinetic behaviour with KOH concentration, the results can be discussed on the basis of a common reaction mechanism.