Decyl hydroperoxide, decomposition

In real systems (hydrocarbon-02-catalyst), various oxidation products, such as alcohols, aldehydes, ketones, bifunctional compounds, are formed in the course of oxidation. Many of them readily react with ion-oxidants in oxidative reactions. Therefore, radicals are generated via several routes in the developed oxidative process, and the ratio of rates of these processes changes with the development of the process [5], The products of hydrocarbon oxidation interact with the catalyst and change the ligand sphere around the transition metal ion. This phenomenon was studied for the decomposition of sec-decyl hydroperoxide to free radicals catalyzed by cupric stearate in the presence of alcohol, ketone, and carbon acid [70-74], The addition of all these compounds was found to lower the effective rate constant of catalytic hydroperoxide decomposition. The experimental data are in agreement with the following scheme of the parallel equilibrium reactions with the formation of Cu-hydroperoxide complexes with a lower activity. 

As mentioned above, autoxidation studies124 indicate that reaction (104) is much faster than reaction (105) in hydrocarbon media. The kinetics of the reaction between manganous stearate and n-decyl hydroperoxide have been studied, and both metal-induced and radical-induced decomposition of hydroperoxide were observed. 

The decomposition of -decyl hydroperoxide in the presence of cobalt complexes has been studied in detail by Bulgakova, Skibida and Maizus [363,364] and found to proceed via a radical pathway at 50 °C. The reaction mechanism depended on the nature of the anionic ligand in this case. Thus, when cobalt(II) acetylacetonate was used as the catalyst a linear dependence on [Co(acac)2] concentration was observed. This and other evidence suggested to these authors [364] that decomposition of -decyl hydroperoxide in the presence of [Co(acac)2] proceeds via monomolecular decomposition of a mononuclear complex [Co(acac)2(ROOH)], equations (216) and (217). Inhibition studies indicated that while decomposition of n-decyl hydroperoxides gave radicals, a chain mechanism was not involved. 

In the decomposition of w-decyl hydroperoxide catalyzed by copper(II) stearate, the formation of radicals was preceded by the formation of the complex [CuSt2(ROOH)2] [365]. 

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See also in sourсe #XX -- [ ]

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