Hydroperoxides degradation

Cumene hydroperoxide degradation. The degradation of the cumene hydroperoxide proceeds via a carbocation mechanism. In the first step, a pair of electrons on the oxygen of the hydroperoxide s hydroxyl group is attracted to a proton of the H30+ molecule, forming an oxonium ion. 

H. S. Isbell and H. L. Frush, Mechanisms for hydroperoxide degradation of disaccharides and related compounds, Carbohydr. Res., 161 (1987) 181-193 and references cited therein. 

Substituted thietanes 102 and 132-134 are inhibitors of the cumene oxidation to cumyl hydroperoxide. These properties result from the termination of the radical oxidation chain process as well as from the catalysis of the hydroperoxide degradation <2001RJAC114>. 

Lipid hydroperoxides are fairly stable molecules under physiological conditions, but their decomposition is catalysed by transition metals and metal complexes (O Brien, 1969). Both iron(II) and iron(III) are effective catalysts for hydroperoxide degradation, but the former is more so (Halliwell and Gutteridge, 1984). These include complexes of iron salts with low molecular weight chelates, non-haem iron proteins, free haem, haemoglobin, myoglobin. 

Peroxide value (PV, also referred to as initial peroxide) The presence of fatty acid hydroperoxides, formed by the oxidative degradation of fatty acids, is a measure of oxidative abuse and degradation of the lipid. Products generated by hydroperoxide degradation will confer a rancid note in edible applications. 

Peroxide Value, The method for determination of peroxide concentration is based on the reduction of the hydroperoxide group with HI or Fe +. The result of the iodometric titration is expressed as the peroxide value. The Fe " method is more suitable for detemuning a low hydroperoxide concentration since the amount of the resultant Fe +, in the form of the ferrithiocyanate (rhodanide) complex, is determined photometrically with high sensitivity (Fe-test in Table 14.27). The peroxide concentration reveals the extent of oxidative deterioration of the fat, nevertheless, no relationship exists between the peroxide value and aroma defects, e. g. rancidity (already existing or anticipated). This is because hydroperoxide degradation into odorants is influenced by so many factors (cf. 3.7.2.1.9) which mdkc its retention by fat or oil or its further conversion into volatiles unpredictable. 

Furthermore, these hydroperoxides ean start a radical chain reaction, leading to additional aroma-active fat degradation products and enhanced autooxidation. The hydroperoxide degradation can happen spontaneously and may also be catalyzed by enzymes. Finally it should be emphasized that XO contributes to lipid oxidation in milk fat only if an appropriate substrate is present. 

The fimction of an antioxidant is to divert the peroxy radicals and thus prevent a chain process. Other antioxidants fimction by reacting with potential initiators and thus retard oxidative degradation by preventing the initiation of autoxidation chains. The hydroperoxides generated by autoxidation are themselves potential chain initiators, and autoxidations therefore have the potential of being autocatalytic. Certain antioxidants fimction by reducing such hydroperoxides and thereby preventing their accumulation. 

Another method for slowing oxidation of rubber adhesives is to add a compound which destroys the hydroperoxides formed in step 3, before they can decompose into radicals and start the degradation of new polymer chains. These materials are called hydroperoxide decomposers, preventive antioxidants or secondary antioxidants. Phosphites (phosphite esters, organophosphite chelators, dibasic lead phosphite) and sulphides (i.e. thiopropionate esters, metal dithiolates) are typical secondary antioxidants. Phosphite esters decompose hydroperoxides to yield phosphates and alcohols. Sulphur compounds, however, decompose hydroperoxides catalytically. 

A recent communication described the cleavage of 17a-hydroperoxy-20-keto steroids with base to give 17-ketoandrostanes in good yield. Since such hydroperoxides are now accessible from 20-ketopregnanes in one step vide infra), this constitutes a convenient two-step degradation process. In practice, the intermediate hydroperoxide need not be isolated. Other enolizable... 

Many impurities are present in commercial caprolactam which pass into the liquid wastes from PCA manufacture from which caprolactam monomer may be recovered. Also, the products of die thermal degradation of PCA, dyes, lubricants, and other PCA fillers may be contained in the regenerated CL. Identification of die contaminants by IR spectroscopy has led to the detection of lower carboxylic acids, secondary amines, ketones, and esters. Aldehydes and hydroperoxides have been identified by polarography and thin-layer chromatography. 

Increase the oxidation rate of polymers, e.g. metal ions which increase the hydroperoxide decomposition rate. Photodegradation and thermal degradation are enhanced by transition metal ion containing pro-oxidants, such as iron dithiocarbamate (as opposed to nickel dithiocarba-mate, which acts as a photo-antioxidant). 

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