Abstract
Abstract Organic monopyrophosphates, structural analogues of biologically important diphosphates, undergo spontaneous thiolo-thiono isomerization (1). On the basis of the detailed kinetic mechanistic studies of the isomerization of bis(5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinane) 1 in 1-methylnaphtalene (MN), beiizoiiitryle or propylerie carbonate solutions the dissociative mechanism has been proposed (2): To support this mechanism we hove studied the kinetics of isomerization of 1 labelled with 35S in pyridine (Py) solutions. As To support this mechanism we hove studied the kinetics of isomerization of 1 labelled with 35S in pyridine (Py) solutions. As expected the reaction is very fast. The first-order reaction rate constant in Py at 25°C is about 107 times greater then the value obtained by extrapolation of the kinetic data for the reaction in MN. The reaction rate constant in Py solutions is almost not sensitive to triethylanunonium salt of the acid AH. This demonstrates that the dissociative step (k1...
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