Tetraline hydroperoxide, catalytic

In 1981 we found that Re(o-phen)(COj Cl shows an intense chemiluminescence during the catalytic decomposition of tetralin hydroperoxide (THPO) in boiling tetraline (1 2). 

The mechanism proposed so far takes account of the induction period and initial stages of the reaction only, and it is difficult to see how it can account for the large amount of hydroperoxide decomposed by the sulfur compound. However, Tetralin hydroperoxide is decomposed catalytically by acids (5). Although in the absence of dilauryl thiodipropionate the decomposition of Tetralin hydroperoxide in the presence of acetic acid at 70 °C. was very slow, if the acid species is a much stronger acid than acetic—e.g., a sulfonic acid as seems likely from the nature of the products of the reaction, the rate of acid-induced decomposition may be comparable with the rate of decomposition by the sulfur compound. Some evidence that acid-induced decomposition does occur at some stage in the over-all reaction is found in the presence of an ortho substituted aromatic compound in the solid product of the reaction. The acid catalyzed decomposition of Tetralin hydroperoxide follows the path of Reaction 14 (5) to give y-(o-hydroxyphenyl)butyraldehyde. This forms a brown resin which is mainly the aldol of this aldehyde (cfthe resin obtained in this work). 

Catalytic properties of complexes of multi-valenced metals with poly(ethylene glycol) (PEG) and polyurethane (PU) have been studied during liquid-phase oxidation processes such as the liquid-phase oxidation of hydrocarbons (phenanthrene, tetralin, cyclohexene), decomposition of hydroperoxides, hydrocarbons and decomposition of hydrogen peroxide [101 -106]. The kinetics of these reactions have been studied. The rate and selectivity of a particular reaction process depend not only on the properties... 

The known examples of catalytic oxygenations involve substrates that undergo relatively facile autoxidation to hydroperoxides often even without an added catalyst. For example tetraline is converted to a-tetralone in the presence of ClFeTPP at 25 °C [96]. CoTTP catalyzes the oxidation of 2,5-dihydrofuran to 2-hydrofuran-5-one and 2-hydrofuran-5-ol in ethyl acetate at 30 C [97]. Furan and 2,3-dihydrofuran were also oxidized but the products were not determined. Tetraline and cumene did not react. The kinetics of autoxidation were interpreted in terms of chain initiation by the dioxygen adduct of CoTTP ... 

Alkylaromatic hydrocarbons, such as tetralin, ethylbaizene, and cumene, are oxidized in a solution of acetic acid in the presence of cobalt acetate via somewhat different mechanism. In these systems, after some rather short acceleration period, a constant oxidation rate v [RH] is established it is independent of either the catalytic concentration, or the partial oxygen pressure. The stationary concentration of hydroperoxide [ROOHJst ([RH]/[C< ]) corresponds to the constant oxidation rate. In a nitrogen atmosphere the hydroperoxide decomposes with the rate v = k[ROOH][Co(Ac)2]. These results agree with the following scheme of chain oxidation ... 

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