Acquiring full knowledge of the reactivity of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) is crucial for the better understanding of the transformation and degradation of TCDD-like dioxins in the environment. To clarify the reactivity of the organic hydroperoxides toward TCDD, in this study, the reactions between the neutral/anion of the hydrogen peroxide (H₂O₂) and TCDD have been systematically investigated theoretically. It was found that the neutral H₂O₂ is relatively difficult to react with TCDD compared with its anion, exhibiting the pH dependence of the title reaction. As for the anion of H₂O₂, it reacts with TCDD through two reaction mechanisms, i.e., nucleophilic substitution and nucleophilic addition. For the former, the terminal O atom of HO₂- nucleophilically attacks the C atom of the C-Cl bond in TCDD to form an intermediate containing an O-O bond, accompanying the dissociation of the chlorine atom. For the latter, the terminal O atom of HO₂- can be easily attached to the C atom of the C-O bond in TCDD, resulting in the decomposition of C-O bond and the formation of an intermediate containing an O-O bond. For these formed intermediates in both reaction mechanisms, their O-O bonds can be homolytically cleaved to produce different radicals. In addition, the selected substitution effects including F-, Br-, and CH₃- substituents on the above reactions have also been studied. Hopefully, the present results can provide new insights into the reactivity of the organic hydroperoxides toward TCDD-like environmental pollutants.
Keywords: 2,3,7,8-tetrachlorodibenzo-p-dioxin; hydrogen peroxide; reaction mechanisms; theoretical calculations.