Hydrolysis of p-Phenylenediamine Antioxidants: The Reaction Mechanism, Prediction Model, and Potential Impact on Aquatic Toxicity

While p-phenylenediamine antioxidants (PPDs) pose potential risks to aquatic ecosystems, their environmental persistence and transformation remain ambiguous due to the undefined nature of PPD C-N bond hydrolysis. Here, we investigated the hydrolysis patterns of PPDs by analyzing their hydrolysis half-lives, hydrolysis products around neutral pH (pH 6.0-7.7), and the role of atoms within the C-N bonds in PPDs. Hydrolysis preferentially targets the aromatic secondary amine N with the strongest proton affinity and the C atom of C-N with the highest nucleophilic-attack reactivity. The hydrolysis half-life (t_1/2) shortens when the maximum proton affinity of N increases. These results are supported by theoretical calculations, demonstrating a hydrolysis reaction propelled by proton transfer from water to N and complemented by aromatic nucleophilic substitution of N in C-N by water hydroxyl. With the experimental results and the atom reactivity-based predictive model, the t_1/2 around neutral pH for 60 PPDs (monitored in environment, commercially available, or under investigation) is determined, showing variations ranging from 2.2 h to 47 days. The model prediction of primary C-N hydrolysis is confirmed through typical PPDs. With the elucidated mechanism and developed model, this research provides new insights into PPD hydrolysis, underscoring its significance in delineating environmental impacts.