Peroxy esters ketones

The thermal degradation of lubricant base oils is known to occur at high temperature and to result in the formation of several carbonyl and hydroxy species (lactones, peroxy esters, peroxy acids, esters, ketones, etc.), which are formed by a free radical-initiated chain reaction [33]. 

Vanadium special for ketone peroxide, hydroperoxide, and peroxy esters, giving short gel times, and very high cure speed. 

When treated with a peroxy acid, ketones can be converted into esters via the insertion of an oxygen atom ... 

The reaction of ketones with peroxy acids is both novel and synthetically useful An oxygen from the peroxy acid is inserted between the carbonyl group and one of the attached car bons of the ketone to give an ester Reactions of this type were first described by Adolf von Baeyer and Victor Vilhger m 1899 and are known as Baeyer—Villiger oxidations... 

Section 17 16 The oxidation of ketones with peroxy acids is called the Baeyer-Vilhger oxidation and is a useful method for preparing esters... 

Baeyer-Villiger oxidation (Section 17 16) Oxidation of an aldehyde or more commonly a ketone with a peroxy acid The product of Baeyer-Vilhger oxidation of a ketone is an ester... 

Ketone Peroxy acid Ester Carboxylic acid... 

Oxidative hydrolysis transforms the intermediate ozonide into ketone(s) and/or carboxylic acid(s) in good yields. H202 in water, in sodium hydroxide solution, or in formic acid is the best proven oxidant.582,584,592 Peroxy acids and silver oxide are also employed. Rearrangement and overoxidation may be undesirable side-reactions. A simple two-step ozonation in MeOH yields methyl esters without added oxidizing agent.627... 

In general, aldehydes and ketones, which are two different classes of compounds, are subject to both analogous and different oxidation reactions. Oxidation of the carbonyl group to give the peroxy analog of an acetal is the same reaction for both classes. On the other hand, the oxidation of an aldehyde to the corresponding carboxylic acid and oxidation of a ketone to the corresponding ester are two completely different reactions. 

In 1899 Baeyer and Villiger observed that peroxy acids convert ketones to esters.179 The reaction is first-order each in ketone and in peroxy acid, and it is general acid catalyzed. Criegee first suggested the mechanism shown in Equation 6.69. The role of the acid catalyst is to protonate the leaving group, thereby facilitating its departure.180... 

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