Hydrogenation cyclohexanone

Ketones play an important role in the decomposition of peroxides to form radicals in alcohols undergoing oxidation. The formed hydroxyhydroperoxide decomposes to form radicals more rapidly than hydrogen peroxide. With an increase in the ketone concentration, there is an increase in the proportion of peroxide in the form of hydroxyhydroperoxide, with the corresponding increase in the rate of formation of radicals. This was proved by the acceptor radical method in the cyclohexanol-cyclohexanone-hydrogen peroxide system [59], The equilibrium constant was found to be K — 0.10 L mol 1 (373 K), 0.11 L mol 1 (383 K), and 0.12 L mol 1 (393 K). The rate constant of free radical generation results in the formation of cyclohexylhydroxy hydroperoxide decomposition and was found to be ki = 2.2 x 104 exp(—67.8/7 7) s 1 [59]. 

As expected, cyclohexanone hydrogenation performed in an IL has a longer reaction time than in solventless conditions. Where using iridium nanoparticles dispersed in an IL, the biphasic hydrogenation of cyclohexanone could be performed at least 15 times, without any considerable loss in catalytic activity this contrasted with the use of nanoparticles in solventless conditions, when the catalytic activity begins to decHne after the third cycle. The standard experimental conditions established for the hydrogenation of other carbonyl compounds were 75 °C, 4atm of H2 and a molar substrate Ir ratio of 250. 

Table 15.6 Cyclohexanone hydrogenation by iridium nanoparticles in solventless conditions [50].

An interesting series of reactions has been developed based on the reaction between Fe(II) and hydrogen peroxide adducts of ketones. The cyclohexanone-hydrogen peroxide adduct10431 b reacts with ferrous sulfate in acidic solutions to produce the 5-carboxypentyl radical.105 In the absence of reactive substrates, dodecanedioic acid is formed by dimerization of these radicals ... 

The lower selectivity of PtHFAU catalysts is due to the very rapid formation of Ce cyclic hydrocarbons (family 1). The same trend has been found in the case of acetone transformation [3]. This can be explained by the lower activity of the palladium relatively to the platinum to hydrogenate the C=0 bond. This lower activity which has been found in the case of cyclohexanone hydrogenation on platinum group metals was explained by a weaker adsorption of the ketone on Pd in comparison with Pt and Ru [9]. 

On an activated carbon matrix, the electrocatalytic activity for the cyclohexanone hydrogenation decreases in the following order ... 

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