153621-93-3Relevant articles and documents
Mechanism of the alkaline hydrolysis of O-ethyl S-(2,4,6-trinitrophenyl) thio-and dithiocarbonates
Castro, Enrique A.,Cubillos, Maria,Santos, Jose G.,Bujan, Elba I.,Remedi, M. Virginia,Fernandez, Mariana A.,De Rossi, Rita H.
, p. 2603 - 2607 (1999)
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°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 σ-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.
