Autoxydation von Kohlenwasserstoffen, VII. Mitteil.: über Peroxyde einfacher Benzolkohlenwasserstoffe

Oxidation of Aromatic Hydrocarbons with HBr/H2O Promoters

“…PhCH,00* + HBr -> PhCH2OOH + Br* (4) benzyl hydroperoxide Dissociation of the hydroperoxide to benzaldehyde, which can be oxidized to benzoic acid, is (Hock and Lang, 1943) by PhCH2OOH -> H20 + PhChO B PhCOOH (5) Degradation products probably follow the decomposition of the peroxide radical to phenyl or phenoxy radicals (Conant and Pratt, 1926; Minkoff and Tipper, 1962, p. 125;Tomura, 1949).…”

Oxidation of Alkylaromatics

“…Hartmann and later Hock and Susemihl 8 succeeded independently in the isolation of crystalline peroxide in the oxidation of tetralin at 70-80°C and identified it as -hydroperoxy tetralin. Hock and Lang showed that in the oxidation of indane 9 and from simple alkylaromatics like p-xylene 10 , ethylbenzene 10 and cumene 11 , the corresponding hydroperoxides as primary products could be isolated in which the -OOH group is present at the carbon atom at -position to the aromatic ring. IG-Farben processed a method for the oxidation of ethylbenzene 12 .…”

Sequence studies in liquid-phase hydrocarbon oxidation. I. Alcohol-ketone transition in the oxidation of ethylbenzene

“…Emanuel and coworkers assumed23•24 that reaction 2 could also proceed with the participation of peroxy radicals ROr + ROOH -> ROOH + R'COR" + OH (5) Reaction 5 is likely to occur in two steps (c) Based on the works of Cullis, Fish, and co-workers29-31 as well as Knox,32 it has been recently assumed that in the gas-phase oxidation of hydrocarbons isomerization and subsequent decomposition of peroxy radicals play an important role in the formation of the products. A similar, though less important, role is attributed to peroxy radicals in liquid-phase oxidations by Zaikov, This would mean that peroxy radicals produce directly ketone (or aldehyde) molecules and a new radical.…”