Peroxide intermediates of oxidation processes: Organic trioxides

Abstract

The review discusses the results of studies on the chemistry of organic trioxides ROOOR (R = H or an organic radical) carried out in the past years. The spectral identification, structure, thermal stability and chemical properties of HOOOH, HOOO ⋅ , hydrotrioxides, open‐chain and cyclic trioxides (including fullerene ozonides) are described. The significance of trioxides for biochemistry, environmental chemistry, and organic synthesis is much higher than it was believed previously. The chemical reactions that these compounds undergo resemble those of peroxides. However, the temperature range in which trioxide reactions occur is shifted considerably towards low temperatures. Homolytic decomposition at one of the OO bonds is the most typical reaction of trioxides. Trioxides are liable to induced and catalytic decomposition. Hydrotrioxides demonstrate high oxidative activity. Decomposition of some trioxides is accompanied by efficient generation of singlet oxygen.

Facile Ozonation of Light Alkanes to Oxygenates with High Atom Economy in Tunable Condensed Phase at Ambient Temperature

“…In separate experiments at ambient pressure and −20 to −10 °C, we confirmed that at the ozone/dioxygen fractions used in our work, either a neat substrate (2-butanol or butanone) or a mixture of these substrates in CCl 4 can be oxidized; 2-butanol to butanone; and butanone to acids, 3-hydroxybutanone, and 2,3-butanedione. Given that high concentrations of both tert -butyl hydroperoxide and ozone mutually promote their decomposition possibly by forming excess free radicals, ,− we infer that hydroperoxide may not form in significant amounts at the conditions used in our work where high ozone utilization is observed. As for 3-hydroxybutanone and 2,3-butanedione as oxidation products from butanone, they form in significant amounts only at relatively high concentrations of either 2-butanol or butanone.…”

“…Further, peroxides cannot possibly activate butanols − and butanes without a catalyst at ambient temperature. Therefore, trioxides are more likely involved, although, at ambient temperature, they are probably too unstable , to observe by 1 H NMR spectroscopy …”

“…Further, peroxides cannot possibly activate butanols 66−68 and butanes without a catalyst at ambient temperature. Therefore, trioxides are more likely involved, although, at ambient temperature, they are probably too unstable 62,65 to observe by 1 H NMR spectroscopy. 69 Due to the reactivity gap between n-butane and the products, including 2-butanol and butanone, the foregoing over-oxidation is likely more competitive at consuming ozone compared to the alkane activation.…”

Comprehensive Study of the Mechanism of the “Aromatic Nitroso Oxide–Olefin” Interaction as a Function of the Reagents’ Structure

“…A ZW intermediate has a chain of three covalently bound electronegative atoms, being a far-off analog of trioxides ROOOR . These compounds are easily decomposed along the peroxide bond, and ZW may undergo a similar transformation.…”

“…A ZW intermediate has a chain of three covalently bound electronegative atoms, being a far-off analog of trioxides ROOOR. 46 These compounds are easily decomposed along the peroxide bond, and ZW may undergo a similar transformation. The activation energies of this TS11 process are rather small (Table 4); moreover, TS11 energy is decreased in the solvent.…”