REACTIONS OF О2•– CONTAINING SUPRAMOLECULAR COMPLEXES WITH ORGANIC SUBSTRATES

Abstract

Solving the problem of biooxidation without considering the role of superoxide anion-containing supramolecules as a mediator of radical chain oxidation cannot be possible. The lack of data of this kind in the literature makes it relevant to study the effect of superoxide anion in the processes of free radical oxidation. The reactions of О2•– with alkyl halides are also of important biological importance, as one of the main ways of formation of highly reactive intermediates – tetraoxides, peroxides, singlet oxygen, peroxyl radicals. A joint solution of these issues will allow us to clarify the mechanisms of action of active oxygen in relation to biological substrates and antioxidants of various types – to generalize scattered experimental data in this important for theory and practice area. We have studied the process of chemiluminescence – HL, which accompanies the interaction of О2• – with alkyl halides. Chemiluminescence was detected in the following systems: KO2 – crown – solvent, KO2 – crown – solvent – propyl bromide; KO2 – crown – solvent – benzoyl chloride, KO2 – crown – solvent – allyl chloride; and also in the KO2 system – crown – solvent – cumene. Kinetic data were obtained, the applicability of schemes involving ROO peroxyradicals was analyzed, and kinetic parameters of CL intensity were calculated. The mechanism of chemiluminescence is proposed. The physicochemical regularities of the oxidation of various organic substrates in the presence of superoxide anion-containing supramolecules as well as reactions of O2• – with alkyl halides were established. It was proved that during the chemiluminescent oxidation of cumene in the presence of KO2•18Cr6 in dimethylsulfoxide, a direct dependence of the induction period on the concentration of the supramolecular complex is observed. For the first time, the possibility of using active oxygen as a mediator of radical chain oxidation is shown.