Hydrogen polyunsaturated compounds

Adsorption of Ag on the surface of PdO is also an interesting option offered by colloidal oxide synthesis. Silver is a well-known promoter for the improvement of catalytic properties, primarily selectivity, in various reactions such as hydrogenation of polyunsaturated compounds." The more stable oxidation state of silver is -F1 Aquo soluble precursors are silver nitrate (halide precursors are aU insoluble), and some organics such as acetate or oxalate with limited solubility may also be used." Ag" " is a d ° ion and can easily form linear AgL2 type complexes according to crystal field theory. Nevertheless, even for a concentrated solution of AgNOs, Ag+ does not form aquo complexes." Although a solvation sphere surrounds the cation, no metal-water chemical bonds have been observed. 

For all catalysts, the hydrogenation mechanism performed under our conditions (liquid phase and low hydrogen pressure) is consistent with an Horiuti-Polanyi mechanism. We found that the phenylacetylene (PhAc) hydrogenation reaction was zero order with respect to hydrocarbon reactants up to 80% of conversion, in agreement with several other studies devoted to the hydrogenation of polyunsaturated compounds." ... 

Indeed, let us consider, for example, olefin self-hydrogenation. This is generally a multistage process beginning with disproportionation of a pair of olefin molecules to the corresponding alkane and a polyunsaturated compound (diene or alkyne), which rapidly polymerizes to form high-molecular-weight products P ... 

Chemoselective Reduction of Polyunsaturated Compounds via Hydrogen Transfer 323... 

Here we summarize some of our results obtained by exploiting the hydrogen transfer ability of heterogeneous copper catalysts and therefore their activity in the reduction of polyunsaturated compounds, racemization and dehydrogenation of unactivated secondary alcohols, and isomerization of allylic alcohols. 

Because of their content of hydrogen atoms, which can be separated by a radical reaction, ethylene-vinyl acetate copolymers have a good basis for grafting. In earlier papers on the radical crosslinking of EVA copolymers with peroxides, we showed that polyunsaturated compounds, such as triallyl cyanurate, can be incorporated completely in the copolymers by graft reactions (2). 

The efficacy of polystyrene-supported rhodium complexes decreases as the following complexes are used for equilibration of polystyrene-phosphine ligand RhCU, RhCla+PPha, RhCls-t-PHPhj, RhCl3+C2H4, RhCl(PPhs)3, RhCl(PHPh2)3 (Capka et al., 1971). It has also been possible to carry out selective partial hydrogenation of polyunsaturated compounds (Bruner and Bailar, 1972). 

Figure 12.11 Phosphoglyceride structure. The members of this group are derivatives of the parent compound, l,2-diacyl-src-glycerol-3-phosphate (phosphatidic acid) in which X is a hydrogen atom. This is replaced by either an amino alcohol or a polyhydroxy residue. In phosphoglycerides derived from animal tissues R1 is usually a saturated acyl chain of between 16 and 20 carbon atoms and R2 is usually unsaturated. Polyunsaturated acyl chains containing 16 or 18 carbon atoms predominate in leaf phosphoglycerides and those of bacterial origin are often more complex.

The addition of hydrogen across multiple bonds is one of the most widely studied of catalytic reactions. Alkenes and alkynes, as well as di- and polyunsaturated systems can all be hydrogenated, provided the suitable experimental conditions are used. Studies on the ways in which these compounds react with hydrogen have revealed very complex reaction patterns. Because of their resonance stabilization, carbocyc-lic aromatic hydrocarbons are more difficult to hydrogenate than are other unsaturated compounds. 

Catalytic hydrogenation of vegetable oils is widely used to form harder fats and to decrease the content of polyunsaturated fatty acyl groups. The products have a greatly increased resistance to rancidity. However, they also contain fats with trans double bonds as well as isomers with double bonds in unusual positions.251 253 Such compounds may interfere with normal fatty acid metabolism and also appear to affect serum lipoprotein levels adversely. Trans fatty acids are present in some foods. One hundred grams of butter contain 4-8 g, but hydrogenated fats often contain much more. It has been estimated that in the United States trans fatty acids account for 6-8% of total dietary fat.253... 

Localization of double bonds in unknown compounds has frequently been determined by ozonolysis. Unsaturated fatty acids of biological membranes are susceptible to ozone attack, but there are some important differences from autoxidation reactions. These include the fact that malonaldehyde is produced from linoleate by ozonolysis (53) but not autoxidation and also that ozonolysis does not cause double bond conjugation as judged by absorption at 233 nm (52). Reactions with the polyunsaturated fatty acids produce several possibilities for toxic reactions direct disruption of membrane integrity and toxic reactions caused by fatty acid hydroperoxides, hydrogen peroxide, and malonaldehyde. 

Fatty acids are carboxylic acids with long hydrocarbon chains. The fatty acids most frequently found in nature are shown in Table 26.1. Because they are synthesized from acetate, a compound with two carbon atoms, most naturally occurring fatty acids contain an even number of carbon atoms and are unbranched. The mechanism for the biosynthesis of fatty acids is discussed in Section 19.21. Fatty acids can be saturated with hydrogen (and therefore have no carbon-carbon double bonds) or unsaturated (have carbon-carbon double bonds). Fatty acids with more than one double bond are called polyunsaturated fatty acids. Double bonds in naturally occurring unsaturated fatty acids are never conjugated—they are always separated by one methylene group. 

Hubaut et has studied the liquid phase hydrogenation of polyunsaturated hydrocarbons and carbonyl compounds over mixed copper-chromium oxides. The selectivity of monohydrogenation was almost 100 % for conjugated dienes but much lower for a,p-unsaturated carbonyls. This was due to the adsorption competition between the unsaturated carbonyls and alcohols as primary products. It was suggested that the hydrogenation site was an octahed-rally coordinated Cu ion with two anionic vacancies, and an attached hydride ion. The Cr ion in the same environment was probably the active site for side reactions (hydrodehydroxylation, nucleophilic substitution, bimolecular elimination). 

Lipid peroxidation is a special form of autoxidation, where the primary target molecules are polyunsaturated fatty acids and their derivatives [15]. These compounds are more susceptible to peroxidation than cholesterol due to the presence of double-allylic hydrogens, which are easily extracted as a result of stabilization of the radical formed. Cholesterol, a major component in cell membranes together with the polyunsaturated membrane lipids, becomes a second target of the radical chain reaction leading to the formation of compounds 1-8 [15]. 

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