Oxidation promoters

Several types of Pd-catalyzed or -promoted reactions of conjugated dienes via TT-allylpalladium complexes are known. The Pd(II)-promoted oxidative difunctionalization reactions of conjugated dienes with various nucleophiles is treated in Chapter 3, Section 4, and Pd(0)-catalyzed addition reactions of conjugated dienes to aryl and alkenyl halides in this chapter. Section 1.1.1. Other Pd(0)-catalyzed reactions of conjugated dienes are treated in this section. 

Air-Atmosphere Furnaces. These furnaces are appHed to processes where the workload can tolerate the oxidation that occurs at elevated temperatures in air. In some special appHcations, the oxidation is not only tolerable but is desired. Some furnaces heat the work solely to promote oxidation. Furnaces designed for air operation are not completely gas-tight which results in somewhat lower constmction costs. There are no particular problems encountered in selecting the insulation systems because almost all refractory insulations are made up of oxides. Heating element materials are readily available for the common temperature ranges used with air atmospheres. 

Catalytic oxidizer Used to promote oxidization of a combustible pollutant. 

Anti-oxidants are the most extensively used additives and will be found in oils and greases which are expected to operate for considerable periods or under conditions that would promote oxidation. Typical examples are crankcase oils and bearing greases. 

As previously noted, determination of the promotion index PI0s- of the promoting oxide ions O6 requires knowledge of the coverage of O6 on the... 

The wear and subsequent failure of a cutting tool is a complex mechanism that usually involves a number of physical and chemical phenomena. Temperatures at the tool/workpiece interface (cutting edge) may reach up to 1200°C in a very short period of time. This creates a pronounced thermal shock and promotes oxidation of the tool surface and the diffusion of metallic constituents of the tool into the chip with a resulting loss of tool strength. 

The role of the base seems merely to be to inhibit acid-promoted oxidations. The base does not appear to play any part in the mechanism Taylor, J.E. Green, R. Can. J. Chem., 1985, 63, Till. 

Winyard, P.G., Blake, D.R., Chirco, S., Gutteridge, J.M.C. and Lunec, J. (1987a). Mechanism of exacerbation of rheumatoid synovitis by total-dose iron-dextran infusion in vivo demonstration of iron-promoted oxidant stress. Lancet i, 69-72. 

A carbon treatment also removes residual color. THF proved to be the best solvent for this operation. One antioxidant often used to stabilize commercial TH F is BHT 53 (butylated hydroxy toluene). The carbon promotes oxidation of the BHT to give a yellow dimer 54 (Scheme 3.20). After sufficient washing of the carbon with THF, the dimer is no longer formed. Although the dimer is removed in crystallization of the product, it is best to wash the carbon prior to use. 

The ceric ammonium nitrate (CAN) promoted oxidation of oxazoles with various substitution patterns was investigated and yielded the corresponding imides 108 in good yields, tolerating a wide variety of functional groups and substituents on the oxazole moiety <06OL5669>. 

These instruments employ a continuous flow of persulfate solution to promote oxidation prior to ultraviolet irradiation, and have a low system blank and low detection limit. Since all reactions take place in the liquid phase, problems suffered by combustion techniques, such as catalyst poisoning, reactor corrosion, and high-temperature element burnouts, are obviated. However, the ultraviolet-promoted chemical oxidation technique is not designed to handle particulate-containing samples, and tends to give incomplete oxidation for certain types of compounds such as cyanuric acid. 

Van Hall et al. [100] inject a 20 litre sample into a high-temperature furnace at 950 °C containing catalyst to promote oxidation of carbon compounds to carbon dioxide, which is then passed into a non-dispersive infrared analyser. The carbonate interference can be determined by passing an acidified portion of the sample through a low-temperature furnace [101-103]. 

The propensity of organotin hydrides for SET reactions has been utilized to initiate radical chain reactions. Anodically promoted oxidation of Ph3SnH to [Ph3Sn] at 0.80 V (vs SCE) initiates the cyclization of several haloalkyne and haloalkene ethers as well as of some fi-lactam derivatives. The catalytic cycle shown in Scheme 1 is based on... 

Chan has discovered a completely atropdiasteroselective synthesis of a biaryl diphosphine by asymmetric intramolecular Ullmann coupling or Fe(m)-promoted oxidative coupling. A chiral atropisomeric biaryl bisphosphine ligand 2 was synthesized through this central-to-axial chirality transfer.38 Recently, a xylyl-biaryl bisphosphine ligand, Xyl-TetraPHEMP, was introduced by Moran, and is found to be effective for the Ru-catalyzed hydrogenation of aryl ketone.39... 

The oxidative coupling/cyclization process occurs via stoichiometric carbo-palladation using a Pd(II) species, typically Pd(OAc)2. In an early example, submission of diphenylamines 3 to the palladium(II)-promoted oxidative intramolecular cyclization conditions yielded carbazoles 4 [15-... 

Diketones. Some years ago Heiba and Dessau reported that Mn(OAc), promotes oxidative addition of isopropenyl acetate to ketones to give 1,4-diketones in 20-35% yield (6, 356). Use of CAN as the oxidant results in higher yields (65-80%) and a regioselective reaction at the more substituted a-position of the ketone.1 Use of vinyl acetate results in the dimethyl acetal of 4-oxo aldehydes. 

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