Structure-Reactivity Insights on the Alkaline Hydrolysis of Organophosphates: Non-Leaving and Leaving Group Effects in a Bilinear Brønsted-Like Relationship.

ABSTRACT

The high toxicity of organophosphates, along with its wide use as agrochemicals and chemical warfare, urges efficient degradation methods. Alkaline hydrolysis stands out, which is strongly structure-dependent. The alkaline hydrolysis of various organophosphates is described using a bilinear variation of the Brønsted equation, which evaluates concomitantly the effect of the leaving and non-leaving groups. Over 50 reactions were successfully correlated linearly and the contribution of the usually underestimated non-leaving group seems to be as important as the leaving group. The hetero atom effect (P=O and P=S) seems to vary the contribution of these groups. This concise understanding of the structure-reactivity relationship allows to predict optimal neutralization processes and is key for chemical security, saving time, resources and avoiding unnecessary manipulation of toxic chemicals.