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

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 Bronsted 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.

Automated summary

This study investigates the alkaline hydrolysis of organophosphates and evaluates the impact of leaving and non-leaving groups. A linear correlation model is successfully established to predict optimal neutralization processes. The study finds that the contribution of non-leaving groups is as important as leaving groups, and the presence of heteroatoms affects the contribution of these groups.