Phosphororganische Antioxidantien. II. Kinetik und Mechanismus der Zersetzung von Alkylhydroperoxiden durch Esteramide der phosphorigen‐ und Phosphorsäure

Organophosphorus Antioxidants. II. Kinetics and Mechanism of the Decomposition of Alkylhydroperoxides by Esteramides of Phosphorous and Phosphoric Acid The reaction mechanism of 2‐amido‐1,3,2‐benzodioxaphospholes (1) with cumyl and t‐butylhydroperoxide has been studied kinetically by means of 31P‐n.m.r. and e.p.r. spectroscopy and high pressure liquid chromatography. 1 reacts with cumyl hydroperoxide to give the corresponding 2‐oxides (2) which with more hydroperoxide and/or water form the phosphate esters 7 and 8. These acidic phosphates decompose cumyl hydroperoxide catalytically giving phenol and acetone. All amides (1) react with t‐butyl hydroperoxide stoichiometrically to give t‐butanol. The ionic mechanism of hydroperoxide decomposition is accompanied in a minor proportion by a homolytical one.