Supersäurekatalysierte Oxygenierungen von Alkanen

Oxyfunctionalization of hydrocarbons. 1. Protolytic cleavage-rearrangement reactions of tertiary alkyl hydroperoxides with magic acid

“…The cleavage product in the acid-catalyzed rearrangement reaction of 18 and acetic acid gives little or no products arising from acetolysis of the oxonium ions. 22 The l3C NMR spectra of the resultant solution when 18 was treated Olah, Parker, Yoneda, Pelizza / Reactions of tert-Alkyl Hydroperoxides with Magic Acid with magic acid in SO2CIF was consistent with formation of the two carboxonium ions 19 and 20 (Scheme IX). We don in these reactions was held at ~-40°.…”

The Oxidative Power of Protonated Hydrogen Peroxide

“…There are several noticeable features of these results: Firstly, n ‐butane and isobutane are known to be oxidized to the corresponding alcohols by hydrogen peroxide in superacid,8 while in the gas phase even ethane and propane react. Secondly, the reaction product collected in superacid is the alcohol, which means that an O atom has been inserted into the C−H bond.…”

Synergistic Effect of Ketone and Hydroperoxide in Brønsted Acid Catalyzed Oxidative Coupling Reactions

“…[13] For further experiments, we chose tert-butylhydroperoxide in decane as an easily available and safe source of a nonaqueous hydroperoxide. In the presence of 2,6-di-tert-butyl-4-methylphenol (BHT) as a radical inhibitor, substitution of the hydroperoxide in 3 by cyclopentanone occurred, but oxidative coupling of xanthene did not.…”

“…While it has been shown that the oxidative power of H 2 O 2 can be enhanced under acidic conditions, the suggested mechanisms were ionic. [13] For further experiments, we chose tert-butylhydroperoxide in decane as an easily available and safe source of a nonaqueous hydroperoxide. Stirring xanthene, cyclopentanone, and two equivalents of tBuOOH under an atmosphere of argon resulted in low conversion of xanthene.…”