A series of esters of phosphorous-phosphoric anhydride containing cyclic ester groups at one or both phosphorus atoms were prepared. The typical biphilic character of these compounds has been found. Unexpectedly observed lack of reactivity of anhydrides containing cyclic ester groups at trivalent phosphorus atom with respect to diethylphosphoric and acetic acids is the starting point for discussion on the mechanism of acidolysis. Unusual inertness of PIII cyclic esters of phosphorous-phosphoric anhydride towards protic acids is discussed in terms of Hudson’s concept of steric retardation on quaternisation.
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