Peroxyacids ketone reactions with

Peroxyacids are powerful oxidants and so side reactions are to be expected. Ketones are known to undergo Baeyer-Villiger " oxidation to the carboxylic acid ester on treatment with peroxyacids and so these by-products can be observed if oxime hydrolysis occurs during the oxidation. Paquette and co-workers " " observed such a by-product (61) during the oxidation of the dioxime (59) to the dinitro compound (60) with m-CPBA in hot acetonitrile. 

Carboxylic Acids. The peroxyacids formed may be unstable and explosive.13 Ketones. Hazardous reaction with acetone and nitric acid other ketones yield shock-and heat-sensitive explosive peroxides.14... 

Another route to the preparation of a-hydroxy derivatives consists of the transformation of enolates into silyl enolates and their subsequent oxidation. Oxidation of triaLkylsUyl enolates with peroxyacids, most frequently cpba, has been applied for preparation of a-hydroxy- and a-acetoxy aldehydes or ketones. Reactions require mild conditions and generally give good yields of the expected compound . Mechanistic investigations suggest the intermediate formation of epoxides which evolve to the final products via 1,4-sUyl group migration. 

Conjugated dienes can be epoxidized (1,2-addition), although the reaction is slower than for corresponding alkenes, but a,p-unsaturated ketones do not generally give epoxides when treated with peroxyacids.The epoxidation of a,p-unsaturated ketones with hydrogen peroxide under basic conditions is known as the Waits-Schejfer epoxidation, discovered in 1921. This fundamental reaction has been extended to a,()-unsaturated ketones (including quinones), aldehydes, and... 

To answer this question, we must look at the mechanism of the reaction. The ketone and the peroxyacid react to form an unstable tetrahedral intermediate with a very weak... 

The Baeyer-Villiger process for conversion of open-chain ketones to esters, or cyclic ketones to lactones by a peracid involves an intermediate a-hydroxyperester (235) step, as shown in equation 83. Determination of 235 in the reaction mixture involves selective reduction of the peroxyacid with diphenyl sulfide and reduction of 235 with excess iodide, followed by titration of the liberated iodine. The presence of various transition metal ions may affect the determination by accelerating the final step of the synthetic process, thus... 

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