Formation and decomposition 0f ?-hydroxyethyl hydrotrioxide

Organic hydrotrioxides

“…13,14 A peculiarity of the 1 H NMR spectra of hydrotrioxides is the appearance, in some cases, of the splitting of the OOOH proton signal into two signals. 14,16,17,19,20,24 The chemical shifts of these signals also show little change with dilution. Heating of the samples results in broadening and coalescence of the lines.…”

“…5 Hydrotrioxides derived from alcohols, ethers and acetals can form intramolecularly hydrogen-bonded structures only if these molecules adopt the syn conformation. 13,14,16,17,19,20,24 Hence, the enthalpy of formation of a hydrogen bond, DH 8, includes the anti ± syn interconversion energy. 18 Radical decomposition of the cyclic intermediate removes the conformational strain, thus decreasing the activation energy for this process.…”

“…Thermochemistry of the reactions of ozone with the C7H bonds was investigated taking the reaction with ethanol as an example. Detailed kinetic studies 24,100 of the reaction revealed its first order with respect to both reagents, the rate constants were determined over a wide temperature range (see Table 11) and the dependence of the rate constant on the chemical nature of solvent was investigated.…”

“…Let us consider a feasible mechanism for this reaction. a-Hydroxyethyl hydrotrioxide 6b was reliably established 24,100 to be the major product. As mentioned above, the mechanism of 1,3-dipolar insertion (route a), for which logA & 6.5 and E a & 20 ± 26 kcal mol 71 , is inconsistent with the observed Arrhenius parameters (see Table 11).…”