Copper catalysis oxygenation

Copper catalysis presents some definite advantages over nickcl(O) complexes, since it is not verysensitive to the presenceof small amounts of water or oxygen, but the second hydrocyanation step cannot be conveniently performed with these catalysts and, thus, remains an unsolved problem. 

Effects of a series of transition metal stearates, the concentration of the copper stearate, the solvent, various additives, and other factors on the thermal oxidation of polypropylene were studied in trichlorobenzene solution. The mechanism of copper catalysis is discussed. The order of decreasing catalytic activity of the metal stearates was Cu > Mn > Fe > Cr > Al Ni Co control Ti >> Zn >> V. The addition of propionic acid to the solvent accelerated the oxidation of the polymer. The presence of the copper leveled off oxygen uptake of the polymer after a certain time. The amount of oxygen absorbed decreased with increasing concentration of the copper, and at higher concentration (7.9 X 10 3M) the polymer oxidation was inhibited. 

Oxidation catalysts are either metals that chemisorb oxygen readily, such as platinum or silver, or transition metal oxides that are able to give and take oxygen by reason of their having several possible oxidation states. Ethylene oxide is formed with silver, ammonia is oxidized with platinum, and silver or copper in the form of metal screens catalyze the oxidation of methanol to formaldehyde. Cobalt catalysis is used in the following oxidations butane to acetic acid and to butyl-hydroperoxide, cyclohexane to cyclohexylperoxide, acetaldehyde to acetic acid and toluene to benzoic acid. PdCh-CuCb is used for many liquid-phase oxidations and V9O5 combinations for many vapor-phase oxidations. 

Catalysis plays an important part in the hydrazine/oxygen reaction. Copper salts were formerly added for this purpose, but in recent years certain organic substances, e.g. quinhydrone, have been employed and a number of proprietary activated hydrazines have been available. These are useful at low temperatures above 150°C scavenging rates with normal hydrazine are such that no great benefit is achieved by their use. 

Similarly, when catalyzed the reaction rate decreases significantly as a function of pH level. The optimum reaction pH level is approximately 9.5 to 10.5. Iron, and especially copper, in the boiler may act as adventitious catalysts. However, as metal transport polymers are frequently employed, iron, copper, or cobalt may be transported away from contact with sulfite, and thus are not available for catalysis. (This may be a serious problem in high-pressure units employing combinations of organic oxygen scavengers and metal ion catalysts.)... 

In situ dynamic surface structural changes of catalyst particles in response to variations in gas environments were examined by ETEM by Gai et al. (78,97). In studies of copper catalysts on alumina, which are of interest for the water gas shift reaction, bulk diffusion of metal particles through the support in oxygen atmospheres was shown (78). The discovery of this new catalyst diffusion process required a radical revision of the understanding of regeneration processes in catalysis. 

The photoirradiation effect can be replaced by copper salt catalysis. The catalyzed reactions proceed rapidly and result in a high degree of transformation. Interestingly, ESR method reveals no organic paramagnetic particles in the course of the reaction between haloaryls and phenyl thiolates. The addition of oxidants (oxygen and DNB) or radical acceptors (di(tert-butyl)nitroxide) does not inhibit the substitution. These facts are understandable from Scheme 7.68 (Bowman et al. 1984, Liedholm 1984). 

A trihydroxyphenylalanyl residue (symbolized TPQ) that plays an essential cofactor role in catalysis of amine oxidases that use molecular oxygen and copper ions. 

So-called blue multinuclear copper oxidase enzymes, such as laccase and ascorbate oxidase, catalyze the stepwise oxidation of organic substrates (most likely in successive one-electron steps) in tandem with the four-electron reduction of O2 to water, i.e. no oxygen atom(s) from O2 are incorporated into the substrate (Eq. 4) [15]. Catechol oxidase, containing a type 3 center, mediates a two-electron substrate oxidation (o-diphenols to o-chinones), and turnover of two substrate molecules is coupled to the reduction of O2 to water [34,35]. The non-blue copper oxidases, e.g. galactose oxidase and amine oxidases [27,56-59], perform similar oxidation catalysis at a mononuclear type 2 Cu site, but H2O2 is produced from O2 instead of H2O, in a two-electron reduction. 

In a subsequent study of oxygen heterocychzation, Andersson et al. investigated various catalyst reoxidation conditions with the Pd(OAc)2/DMSO catalyst system (Eq. 27, Table 3) [ 150]. Several conditions result in high substrate conversion to the product, including the use of BQ, BQ with methanesulfonic acid, and molecular oxygen, with and without copper(II) salts as a cooxidant. Only the aerobic methods enable formation of the product 37 with high regio-selectivity. The presence of a copper cocatalyst enhances the rate but is not necessary for catalysis. 

In summary, the oxidation of thiols to disulfides is quantitative in aqueous alkaline solution and may best be effected at high oxygen pressures in the presence of a catalyst. The catalyst should dissolve in the alkaline solutions, and of the simple metal salts, the addition of copper, cobalt, and nickel results in the most effective catalysis. 

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