On the selectivity of the biomimetic oxidation of the saturated hydrocarbon 1,3-dimethyladamantane in a Gif-type system containing a Fe²⁺ salt, picolinic acid, and pyridine

Author： Vasil’eva V. Nekhaev A. Shchapin I. Bagrii E.

Publisher： MAIK Nauka/Interperiodica

ISSN： 0023-1584

Source： Kinetics and Catalysis, Vol.47, Iss.4, 2006-07, pp. : 610-623

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Abstract

The effects of the composition of a heterogeneous catalytic system based on Fe₂SO₄ · 7H₂O, picolinic acid (pyridine-2-carboxylic acid), and pyridine and system preparation procedures on the selectivity of oxidation of 1,3-dimethyladamantane (1,3-DMA) with an aqueous 30% hydrogen peroxide solution in an aqueous acetonitrile solvent at room temperature and ambient pressure were studied. The yields of 1,3-DMA oxidation products were increased from fractions of a percent in initial experiments to the tens of percent under new catalytic conditions of final experiments. It was found that three different mechanisms can occur in the test system under various conditions; conceivably, these are radical, ion-molecule, and radical-cation mechanisms. In the first case, a statistical mixture of the products of 1,3-DMA oxidation at tertiary and secondary C-H bonds was formed. In the second and third cases, oxidation occurred only at secondary and tertiary C-H bonds, respectively. Unlike the first two cases, the selectivity of 1,3-DMA oxidation to a tertiary alcohol under conditions of the Gif-type test system corresponds to the selectivity of biological oxidation and, to the best of our knowledge, is the first example of this kind.