Mechanistic insights into the amidolysis of a phosphate triester: the antagonistic role of water.

ABSTRACT

The breakdown of O,O-diethyl-2,4-dinitrophenyl phosphate in formamide (FMD) solutions is assessed using kinetic studies and 31P nuclear magnetic resonance (NMR) analysis. Regiospecific nucleophilic amidolysis via P-O bond cleavage is observed, leading to non-toxic diester and FMD regeneration. In the systems evaluated, water plays an antagonistic role while it is key for the breakdown of the reaction intermediate, it inhibits the nucleophilic activity of FMD by hydrogen bonding effects.