Reactivity and selectivity of homolytic substitution reactions on the peroxyacid group

Thermolysis of organic peroxides in solution

“…The kinetic regularities of the thermolysis of peroxy acids depend on the reaction conditions. According to the published data, 122,123…”

Mechanisms of peroxide decomposition. An EPR investigation of the reactions between some transition metal ions (Ti III , Fe II , Cu I ) and monoperoxyphthalic acid and its anion

“…The reaction between Ti"' (as [Ti1"SO4+]; 1.7 x Cu' + MeC(0)OOBu'-MeC0,-+ Cu" + 'OBu' (6) t Concentrations given in the text are those uffer mixing, unless stated otherwise. mixing and observation.…”

“…The former mode of decomposition is believed to occur in the reduction of a number of peracids by Ti"' (these have been studied using an EPR flow technique4), and CO",~ and also in the reduction of some peracids by nucleophilic radicals [see reaction (5)J6 In contrast, the reaction of 4-nitroperbenzoic acid with the hydrated electron is reported to give the hydroxyl r a d i ~a l , ~ in a reaction which appears to be parallel to that invoked to account for the well-known Kharasch reaction between Cu' and peresters * [see e.g. reaction (6)].…”

Derivatization Technique To Identify Specifically Carbonyl Groups by Infrared Spectroscopy: Characterization of Photooxidative Aging Products in Terpenes and Terpeneous Resins

“…The bond dissociation energy of the O−O bond is significantly higher for peroxy acid than for other peroxides. 30,31 Thus, aliphatic peroxy acids have no characteristic UV absorption >300 nm 32 and can therefore be regarded as much more stable than other peroxides under the light conditions tested. These, nevertheless, do decay slowly to primary carboxylic acids (IR band at ≈1840 cm −1 ), which then represent the stable end products.…”