Chlorocyclophosphazenes reactions with amines

New kinetic data on the reactions of chlorocyclophosphazenes with amines have appeared. The reactions of both N3P3CI6 and N3P3Cl5-NMe2 with dimethylamine in THF were shown by conductivity measurements to follow a second-order rate law, which was first order in dimethylamine. The formation of both mono- and bis-dimethylamino-derivatives was visualized as proceeding by the rapid formation of a five-co-ordinated intermediate, followed by a relatively slow entropy-controlled THF-catalysed dehydrochlorination. It was suggested that the entropy of... 

Several mechanistic pathways have been identified in the nucleophilic substitution reactions of chlorocyclophosphazenes [12]. Most of the kinetic experiments have been carried out in the reactions involving chlorocyclophosphazenes with amines. These experiments are suggestive of various... 

Chlorocyclophosphazenes are quite reactive towards nucleophiles such as amines, alcohols or phenols. Complete replacement of chlorines is readily possible with a number of reagents. For example, the reaction of N3P3CI6 or N4P4CI8 with dimethylamine can lead to the formation of N3P3(NMe2)e or N4P4G e2) (see Eqs. 3.12 and 3.13). These reactions also work quite well with primary, secondary and even aromatic amines although individual differences in reactivity are present. 

Many amines react with chlorocyclophosphazenes in a bimolecu-lar process to afford nongeminal products. Almost exclusive non-geminal product formation is observed in N4P4Clg/amine reactions. 

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