Copper catalytic effect

When the operating temperature exceeds ca 93°C, the catalytic effects of metals become an important factor in promoting oil oxidation. Inhibitors that reduce this catalytic effect usually react with the surfaces of the metals to form protective coatings (see Metal surface treatments). Typical metal deactivators are the zinc dithiophosphates which also decompose hydroperoxides at temperatures above 93°C. Other metal deactivators include triazole and thiodiazole derivatives. Some copper salts intentionally put into lubricants counteract or reduce the catalytic effect of metals. 

House investigated the role of cuprous ions in the conjugate addition of organometallic reagents. He found that the catalytic effect can be explained by the intervention of a methyl copper derivative, which reacts rapidly with the carbon-carbon double bonds of the conjugated system. 

Hayama et al.132 discussed the catalytic effects of silver ion-polyacrylic add systems toward the hydrolyses of 2,4-dinitrophenylvinylacetate 84 (DNPVA) by using the weak nudeophilicity of carboxylic groups and the change-transfer interactions between olefinie esters and silver ions133Metal complexes of basic polyelectrolytes are also stimulating as esterase models. Hatano etal. 34, 13S) reported that some copper(II)-poly-L-lysine complexes were active for the hydrolyses of amino acid esters, such as D- and L-phenylalanine methyl ester 85 (PAM). They... 

The major problem of these diazotizations is oxidation of the initial aminophenols by nitrous acid to the corresponding quinones. Easily oxidized amines, in particular aminonaphthols, are therefore commonly diazotized in a weakly acidic medium (pH 3, so-called neutral diazotization) or in the presence of zinc or copper salts. This process, which is due to Sandmeyer, is important in the manufacture of diazo components for metal complex dyes, in particular those derived from l-amino-2-naphthol-4-sulfonic acid. Kozlov and Volodarskii (1969) measured the rates of diazotization of l-amino-2-naphthol-4-sulfonic acid in the presence of one equivalent of 13 different sulfates, chlorides, and nitrates of di- and trivalent metal ions (Cu2+, Sn2+, Zn2+, Mg2+, Fe2 +, Fe3+, Al3+, etc.). The rates are first-order with respect to the added salts. The highest rate is that in the presence of Cu2+. The anions also have a catalytic effect (CuCl2 > Cu(N03)2 > CuS04). The mechanistic basis of this metal ion catalysis is not yet clear. 

The effects of aluminium, zinc, iron, nickel and copper powders on the thermal degradation of waste PS were studied. The results showed that the catalytic effects of metal powders were related to their activities. The catalytic effects increased with increasing activities of metals. It was suggested that PS degraded through a transient intermediate in the presence of metal powders and that the degradation of the transient intermediate was the rate-determining step. 10 refs. 

Many of the early workers who studied the thermal decomposition reactions of diazocarbonyl compounds found that the addition of copper metal or copper salts allowed the reaction to be achieved at a lower temperature,<63AG(E)565, 64CB2628, 73JOU431> although no detailed study of this catalytic effect was undertaken. Alonso and Jano studied the copper-salt reaction of ethyl diazopyruvate 26 with acetonitrile and benzonitrile. The... 

Z>) Addition of iron(in) ions results in the increase of Fj to infinity. Copper(fl) ions have a similar catalytic effect but, their activity does not depend on the acid concentration of the solution. 

The presence of transition metal ions has a catalytic effect on reduction of halides and tosylates by LiAlH4.166 Various copper hydride reducing agents are effective for removal of halide and tosylate groups.167 The primary synthetic value of these reductions is for the removal of a hydroxy function after conversion to a halide or tosylate. 

A substance which results in the chemical inactivation of a metal. The catalytic effect of heavy metals, mainly copper and manganese, on the oxidation of unsaturated compounds such as rubber, results in very rapid deterioration. Chelating agents convert the metal into a chelate co-ordination compound and thus render the metal inactive. The term sequestering agents has been applied to chelating agents but this infers that the metal has been removed and not merely inactivated. 

The above transformation takes place via the catalytic effect of copper (I), which generated the corresponding carbenoid from a-diazo-p-keto esters. These Cu-carbenoides react with the thiocarbonyl group of thioamides, after cyclocondensation to afford 2-aryl-l,3-thiazole-5-carboxylates (Scheme 18).40... 

Other studies in this specific area are also based on the catalytic effect of a variety of metal ions such as copper (II), cobalt (II), nickel (II), iron (III), and manganese (II) on the luminol-hydrogen peroxide reaction providing a rapid and efficient detection mode for these five ions, when an online CL detector is used before separation by CE [88], This contribution combines capillary ion analysis (CIA) and CL detection by means of a postcapillary reactor similar to the one originally developed by Rose and Jorgenson [80] and finally modified by Wu... 

Interestingly, the catalytic effects of the two metal ions were not additive the copper(II) catalyzed reaction became significantly slower on the addition of Fe(III) to the reaction mixture. This observation was interpreted in terms of the model proposed by Zwart and co-workers (64) by assuming that one of the two copper centers is replaced by Fe in the catalytically active dimer (67). 

Nucleophilic displacement of halogen by amines is an important method of introducing amino groups into the anthraquinone ring system. In the Ullmann reaction the displacement is catalysed by metallic copper or by copper ions so that relatively mild conditions can be used. Mechanistic studies suggest that copper(I) ions exert a catalytic effect via complex formation. Derivatives of 1,4-diaminoanthraquinone are of considerable industrial significance. Many compounds are prepared from the reduced form of quinizarin (6.6). 

The synthetic application of organocopper compounds received a major impetus from the study of the catalytic effect of copper salts on reactions of Grignard reagents with y.,(i-unsaturated ketones.1 Whereas Grignard reagents normally add to conjugated enones to give the 1,2-addition product, the presence of catalytic amounts of Cu(I) results in... 

It was demonstrated that the growth of Cu nuclei goes on with time, while the OCP values of Fig. 13 reach a plateau after a long time. This effect was attributed to a weaker catalytic effect of the large copper clusters that balance the continuing increase in the size of the clusters. 

Dr. Anbar First, concerning hydride transfer, our information shows that with longer chained diamines, say 1,3-propylenediamine and certainly, 1,4-butyl-enediamine, the catalytic. effect of copper disappears. With a longer chain the coordination is essential for the reaction. Then, an internal hydride transfer has to be assumed, that is an intramolecular and not extramolecular process. 

Experimental observations indicate that the oxidation of cobalt (II) to cobalt (III) and the formation of ethylenediamine from N-hydroxyethylethylene-diamine occur simultaneously. This is quite the opposite to what is usually assumed in other instances of transition metal catalysis of organic reactions—for example, the catalytic effect of manganese in the oxidation of oxalic acid (7, 8), of iron in the oxidation of cysteine to cystine (22) and of thioglycolic acid to dithioglycolic acid (5, 23), of copper in the oxidation of pyrocatechol to quinone and in the oxidation of ascorbic acid (29, 30), and of cobalt in the oxidation of aldehydes and unsaturated hydrocarbons (4). In all these reactions the oxidation of the organic molecule occurs by the abstraction of an electron by the oxidized form of the metal ion. 

Substituted l,2,4-thiadiazol-5-yl diazonium tetrafluoroborates (314) react with potassium halides in acetonitrile in the absence of catalysts to afford the corresponding 5-halogeno compounds (315) in excellent yields.169 The isomeric 5-phenyl-l,2,4-thiadiazol-3-yl diazonium salts, however, resist substitution by this procedure, except with iodide ions by taking advantage of the catalytic effect of copper... 

A systematic attempt to correlate the catalytic effect of different surfaces with their adsorptive capacity was made by Taylor and his collaborators. Taylor and Burns, for example, investigated the adsorption of hydrogen, carbon dioxide, and ethylene by the six metals nickel, cobalt, palladium, platinum, iron, and copper. All these metals are able to catalyse the hydrogenation of ethylene to ethane, while nickel, cobalt, and palladium also catalyse the reduction of carbon monoxide and of carbon dioxide to methane. 

In contrast to the reactivity of the nitroethylenes, acrylonitrile generally reacts with indoles to form the l-(2-cyanoethyl) derivatives (B-70MI30500,79MI30501), whereas Michael addition at the 3-position requires the catalytic effect of copper(II) salts. The addition-elimination reaction of pyrroles and indoles with l,l-dicyano-2-ethoxyethylene proceeds in low yield (<30%) to give the dicyanovinyl derivatives, which can be converted by standard procedures into the formyl compounds (81H(16)1499). Tetracyanoethylene forms charge transfer complexes with indoles, which collapse to the Michael adduct anions and subsequently eliminate a cyanide ion with the formation of the tricyanovinylindole (B-70MI30500). 

Metal-catalyzed lipid oxidative reactions were recognized in dairy products as early as 1905 (Parks 1974). Investigations throughout the years have shown that copper and iron are the important metal catalysts in the development of oxidized flavors. Of these two metals, copper exerts the greater catalytic effect, while ferrous ion is more influential than feric ion. 

Arsenious oxide in the solid state is not affected by oxygen under ordinary conditions,4 but if subjected at high temperature to oxygen under pressure oxidation to the pentoxide results. Thus, if heated at 400° to 480° C. with oxygen at pressures of 130 to 180 atm., oxidation occurs, but is incomplete the amount oxidised increases with the temperature.3 According to Razuvaev and Malinovskil,6 at 200° to 300° C. the optimum pressure for oxidation by air is 60 to 80 atm., and under these conditions the reaction is complete in about 20 minutes finely divided iron has a wreak and copper a strong catalytic effect. In the presence of potassium iodide or activated carbon, a suspension of the oxide in water is oxidised by air or oxygen at 130° to 140° C. and 4 to 5 atm. pressure.7 The usually accepted reaction is... 

---