Peroxy acids decomposition

The salt may lead to explosive decomposition of the peroxy acid. 

Vacuum evaporation of the product of untreated conversion of the pyridine to its N--oxide with 5% excess of the peroxy acid in chloroform gave a residue which decomposed violently [1], This was attributed to the relative stability of the peroxy acid in the cold pure state, which when concentrated and finally heated with other materials underwent accelerating decomposition [2],... 

Explosive decomposition occurs at 80-100°C [1], but the isomeric 1-peroxy acid may also have been present in the sample [2],... 

Ethyl peracetate was the first ester of a peroxy acid, and was characterized by Baeyer and Villiger in 1901. Kinetic studies of perester decomposition were reported by Blomquist and Ferris in 1951, and in 1958 Bartlett and Hiatt proposed that concerted multiple bond scission of peresters could occur when stabilized radicals were formed (equation 46). As noted below (equation 57), polar effects in perester decomposition are also significant. 

In early attempts to produce an iron-oxo species (20) from typical porphyrins like chloro-a,/3,y,8-tetraphenylporphinatoiron(III) [Fe(III)TPP-Cl] and chloroferriprotoporphyrin(IX)[Fe(III)PPIX-Cl], we examined the reaction of t-butyl hydroperoxide and peroxy-acids with alkanes and olefins in the presence of these catalysts. With peroxyacids, decomposition of the porphyrin ring was observed, while with the f-butyl hydroperoxides, product distributions were indistinguishable from free-radical chain reactions initiated photochem-ically in the absence of any metals. 

Simple alcohols can be obtained from the decomposition of peroxy acids in cyclohexane or benzene at reflux. This chain reaction, which is efficient for adamantane-l-carboxylic acid (equation 40), is unfortunately usually complicated by side reactions involving hydrogen abstraction from the substrate or sol-... 

In the oxidation of hydrocarbons, CO2 is usually a minor product compared to CO even in cool flames. CO2 predominates in explosions only. It is also formed in surface-catalyzed decompositions of acids and peroxy acids. 

See work by M. Szwarc, J. Polymer Sci., 16, 367 (1955), on the decomposition of the acyl peroxides in liquid phase. Surface dehydration will produce H2O and aldehydes from the peroxy acids. 

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