Hydroperoxides peroxidation chain mechanism

Oxidation to CO of biodiesel results in the formation of hydroperoxides. The formation of a hydroperoxide follows a well-known peroxidation chain mechanism. Oxidative lipid modifications occur through lipid peroxidation mechanisms in which free radicals and reactive oxygen species abstract a methylene hydrogen atom from polyunsaturated fatty acids, producing a carbon-centered lipid radical. Spontaneous rearrangement of the 1,4-pentadiene yields a conjugated diene, which reacts with molecular oxygen to form a lipid peroxyl radical. 

Organic peroxides and hydroperoxides decompose in part by a self-induced radical chain mechanism whereby radicals released in spontaneous decomposition attack other molecules of the peroxide.The attacking radical combines with one part of the peroxide molecule and simultaneously releases another radical. The net result is the wastage of a molecule of peroxide since the number of primary radicals available for initiation is unchanged. The velocity constant ka we require refers to the spontaneous decomposition only and not to the total decomposition rate which includes the contribution of the chain, or induced, decomposition. Induced decomposition usually is indicated by deviation of the decomposition process from first-order kinetics and by a dependence of the rate on the solvent, especially when it consists of a polymerizable monomer. The constant kd may be separately evaluated through kinetic measurements carried out in the presence of inhibitors which destroy the radical chain carriers. The aliphatic azo-bis-nitriles offer a real advantage over benzoyl peroxide in that they are not susceptible to induced decomposition. 

Vanoppen et al. [88] have reported the gas-phase oxidation of zeolite-ad-sorbed cyclohexane to form cyclohexanone. The reaction rate was observed to increase in the order NaY < BaY < SrY < CaY. This was attributed to a Frei-type thermal oxidation process. The possibility that a free-radical chain process initiated by the intrazeolite formation of a peroxy radical, however, could not be completely excluded. On the other hand, liquid-phase auto-oxidation of cyclohexane, although still exhibiting the same rate effect (i.e., NaY < BaY < SrY < CaY), has been attributed to a homolytic peroxide decomposition mechanism [89]. Evidence for the homolytic peroxide decomposition mechanism was provided in part by the observation that the addition of cyclohexyl hydroperoxide dramatically enhanced the intrazeolite oxidation. In addition, decomposition of cyclohexyl hydroperoxide followed the same reactivity pattern (i.e., NaY < BaY... 

Hydrogen atoms in allylic position are favorite sites for hydroperoxidation of chains. So, this mechanism proceeds in the formation of lateral hydroperoxides, and not like for other polymers, in intramolecular peroxides. Rearrangement of chemical structures coming from ozonides are rapidly observed (Scheme 33). 

The reduction reactions of hydroperoxides are subject to the same types of chain mechanism as the reduction of hydrogen peroxide, and in addition the radical RO can undergo various rearrangement reactions. 

In conclusion, the salient features of the light-induced oxidation of polymers are the formation of hydroperoxide, peroxide, and carbonyl groups, the latter in the form of both aldehyde and keto groups. Moreover, certain reactions, such as reaction (d) in Scheme 7.20 and reaction (b) in Scheme 7.21, result in main-chain cleavage as far as the oxidation of linear macromolecules is concerned. Main-chain cleavage leads to a deterioration in certain important mechanical properties. Therefore, the photo-oxidation of polymers is deleterious and should be avoided in commercial polymers. Appropriate stabilization measures are discussed in Section 9.3. 

Also potentially hazardous are compounds that undergo autooxidation to form organic hydroperoxides and/or peroxides when exposed to the oxygen in air (see Table 3.12). Especially dangerous are ether bottles that have evaporated to dryness. A peroxide present as a contaminant in a reagent or solvent can be very hazardous and change the course of a planned reaction. Autoxidation of organic materials (solvents and otho" liquids are most frequently of primary concern) proceeds by a free-radical chain mechanism. For the substrate R—H, the chain is initiated by ultraviolet... 

Preventative or secondary antioxidants act at the initiation stage of the radical chain mechanism to prevent the formation of radical products. Their mechanism involves the decomposition of hydroperoxides to form stable nonradical products. In the absence of peroxide scavengers, hydroperoxides thermally or photolyti-cally decompose to radical products and accelerate decomposition. The most common secondary antioxidants are sulfur-based thiosynergist or phosphorus-based phosphites. ... 

Isotactic polypropylene, just like other polyolefins, is oxidized according to a radical chain mechanism with degenerate branches. Evidence of this is the presence of a well-defined induction period and autoacceleration of the reaction, which occurs according to the law w = Ae i . Hydroperoxides are the branching products [47]. The introduction of peroxide into the polymer reduces the induction period in proportion to JPer, which gives evidence of the presence of quadratic chain termination. 

The term antioxidant is used to describe the inhibition of polymer peroxidation in both abiotic and biotic systems [6,8,11]. It embraces more specific technological terms such as antidegradants (thermoantioxidants), antifatigue agents (mechanooxidation inhibitors) and light stabilisers (photoantioxidants). It was seen above that peroxidation of carbon-chain polymers occurs by a free radical chain mechanism (reactions 1 and 2) and that the hydroperoxide products that are the intrinsic initiators for peroxidation dissociate to oxyl radicals under the influence of heat and light. Both hydroperoxide formation and hydroperoxide decompostion are thus catalysed by transition metal ions. 

During the following half-century, polymer chemists learned that curing or drying oleoresinous paints in the presence of heavy metal salts ( driers ) and air involved forming hydroperoxides on the carbon atoms adjacent to the ethylenic bonds in the unsaturated oils. In the accepted mechanism, the carbon-carbon double bond shifts to a conjugated configuration, and the peroxide is transferred to another monoallylic carbon atom. Polymerization proceeds via a radical chain mechanism to produce a crosslinked insoluble film. 

Materials that promote the decomposition of organic hydroperoxide to form stable products rather than chain-initiating free radicals are known as peroxide decomposers. Amongst the materials that function in this way may be included a number of mercaptans, sulphonic acids, zinc dialkylthiophosphate and zinc dimethyldithiocarbamate. There is also evidence that some of the phenol and aryl amine chain-breaking antioxidants may function in addition by this mechanism. In saturated hydrocarbon polymers diauryl thiodipropionate has achieved a preeminent position as a peroxide decomposer. 

The early work of Kennerly and Patterson [16] on catalytic decomposition of hydroperoxides by sulphur-containing compounds formed the basis of the preventive (P) mechanism that complements the chain breaking (CB) process. Preventive antioxidants (sometimes referred to as secondary antioxidants), however, interrupt the second oxidative cycle by preventing or inhibiting the generation of free radicals [17]. The most important preventive mechanism is the nonradical hydroperoxide decomposition, PD. Phosphite esters and sulphur-containing compounds, e.g., AO 13-18, Table la are the most important classes of peroxide decomposers. 

In the previous section, we have described some of the mechanisms that may lead to the fijrmation of lipid hydroperoxides or peroxyl radicals in lipids. If the peroxyl radical is formed, then this will lead to propagation if no chain-breaking antioxidants are present (Scheme 2.1). However, in many biological situations chain-breaking antioxidants are present, for example, in LDL, and these will terminate the peroxyl radical and are consumed in the process. This will concomitandy increase the size of the peroxide pool in the membrane or lipoprotein. Such peroxides may be metabolized by the glutathione peroxidases in a cellular environment but are probably more stable in the plasma comjxutment. In the next section, the promotion of lipid peroxidation if the lipid peroxides encounter a transition metal will be considered. 

Mechanisms of lipid peroxidation that have been implicated in atherosclerosis may be pertinent to RA. Cellular lipoxygenase enzymes may promote LDL modification by inserting hydroperoxide groups into unsaturated fetty-acid side chains of the LDL complex (Yla-Herttuala etal., 1990). 15-Lipoxygenase has been implicated as an initiator of LDL oxidation (Cathcart etal., 1991) whilst 5-lipoxygenase does not appear to be involved (Jessup et al., 1991). Products of activated lipoxygenase enzymes within inflammatory synovial fluid surest that this pathway could be activated in RA (Costello etal., 1992). 

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