Oxidative cleavage, degradation with hydrogen peroxide

While die above reactions will provide carboxylic acid products, each has problems associated with it. The cleavage of olefins to carboxylic acids [reaction (7.1)] can be carried out using potassium permanganate or by ozonolysis at low temperature followed by oxidative workup with hydrogen peroxide. Neither of diese mediods is very useful since only symmetric olefins provide a single carboxylic acid product. Unsymmetrical olefins give a mixture of two acids which must be separated. Furthermore the most useful synthetic processes are those which build up structures, whereas these reactions are degradative in nature. 

Degradation of aldehydes is accomplished via their silyl enol ethers by oxidative cleavage with hydrogen peroxide in a two-phase system with added PTC. ... 

The Me" transition metal ion can be oxidized further, for example, Fe(II), Cu(I), or Ti(III), and can activate oxidative cleavage of hydrogen peroxide, as in the Fenton mechanism. It was suggested that the hydroperoxyl radical, HOO, is the species that attacks the membrane. As will be clearly seen below, some of the transition metal ions may react directly with the sulfonic groups of the membrane, thus providing an additional degradation pathway. 

Oxidative degradation in polyolefins with a minimum level of unsaturated contents (< 0.1 wt.%) at temperatures below 150 °C generally causes chain cleavage. Table 5.41. Autoxidation is promoted by the decomposition of hydrogen peroxides which can, as previously mentioned, be catalyzed by transition metals or residual acids. At low temperatures, the content of unsaturated and tertiary hydrogen atoms (chain branching, comonomer content or density) plays a subordinate role. 

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