Kinetics of ozonation. 5. Reactions of ozone with carbon-hydrogen bonds

Metal-Free Functionalization of the Unactivated Carbon-Hydrogen Bond: the Oxidation of Cycloalkanes to Cycloalkanones with Ozone

“…Hydride transfer from the alkane [9] forms a hydrotrioxide (8). This mechanistic detail has been suggested [10] to account for the oxygenation of some ethers and is in agreement with the fact that oxygen is inserted into the methylene group adjacent to the heteroatom both in the oxygenation of ethers to esters [8] and in the oxygenation of amines to amides [10].…”

Biomarkers of oxidative stress study V: Ozone exposure of rats and its effect on lipids, proteins, and DNA in plasma and urine

“…It is well known that most markers of oxidative stress are assumed to be a consequence of free radical attack on macromolecules resulting in lipid-, protein-, and DNA oxidation [1, 36]. However, in the case of ozone literature data indicate that some of the fastest reactions are for direct reaction with Cys residues (and GSH), with k ∼ 10 7 M -1 s -1 , with the rate constants for reaction with other aminoacid side chains being considerably slower [37]. In contrast, reaction with mono- and polyunsaturated fatty acids and their esters (oleic and linoleic) and α-tocopherol have been reported as being 1 × 10 6 M -1 s -1 [37].…”

Kinetics and Mechanism of the Ozone Reaction with Alcohols, Ketones, Ethers and Hydroxybenzenes

“…This mechanism was also supported by the data of Erickson and Bailey [2,67,69], Murray and coworkers [70], who measured the activation parameters of the decomposition of a series of HTO, obtained by the ozonolysis of some ethers. Giamalva and co-workers [71] summarized the possible mechanisms known today, i.e. interaction with the ether oxygen atom, 1,3-dipolar insertion of ozone into the α-C-H bonds, homolytic abstraction of the α-H atom and heterolytic abstraction with carboanion and carbocation formation.…”

“…The mechanism B with linear complex LC-II in the transition state was put forward and discussed by Bailey [2]. The interaction of ozone with C-H bonds with the formation of trioxide [71,73] as a possible parallel reaction is indicated in mechanism C. The acetylated forms of dihydroxybenzenes can react only via attack on the benzene ring according to the mechanism D or C. Formally, the mechanism D can be regarded as an extended version of mechanism B, involving the formation of TS similar to π-or σ-complexes. We propose a new mechanism, an extended version of the Razumovskii mechanism, whereby the transition state is linear with LC-I structure.…”