OXYGEN Selective oxidation

Iron complexes stabilized in a ZSM-5 zeolite matrix produce a new form of surface oxygen (a-oxygen) upon decomposition of N20[58], a-Oxygen selectively oxidizes methane and benzene ... 

Alcohols are oxidized slowly with PdCh. Oxidation of secondary alcohols to ketones is carried out with a catalytic amount of PdCh under an oxygen atmo-sphere[73.74]. Also, selective oxidation of the allylic alcohol 571 without attacking saturated alcohols is possible with a stoichiometric amount of PdfOAc) in aqueous DMF (1% H OifSll],... 

Sta.rting from Phenol. Phenol can be selectively oxidized into -benzoquinone with oxygen. The reaction is catalyzed by cuprous chloride. At low catalyst concentration, the principal drawback of this method is the high pressure of oxygen that is required, leading to difficult safety procedures. It appears that a high concentration of the catalyst (50% of Cu(I)—phenol) allows the reaction to proceed at atmospheric pressure (58). 

However, the same oxygen also oxidizes ethane and ethylene to CO2 and other oxygenated products. Therefore, selectivity to olefins is a serious consideration. Literature citations (93,94) claim development of low temperature, highly selective oxydehydrogenation catalysts. Although this process has not yet been commercialized, it seems promising. 

When used at room temperature in the presence of an active platinum catalyst in an inert solvent, e.g., acetone or ethyl acetate, oxygen will oxidize nonhindered, saturated hydroxyl groups and exposed allylic alcohols. This reagent has found extensive use in sugar chemistry and is particularly suited for the selective oxidation of either 3a- or 3j -alcohols of steroids. Other hydroxyl groups on the steroid skeleton are much less sensitive to oxidation. As a result, this reaction has been used extensively in research on polyhydroxy cardiac-active principles, e.g., the cardenolides and bufadienolides, where the 3-hydroxyl group is easily oxidized without extensive oxidation or dehydration of other hydroxyl groups. The ordinarily difficult selective oxidation of the... 

The analogous 6-methyl derivative (126) was prepared by the same authors from 6-methyl-3,6-dithioxo derivative (123) as the corresponding monothioxo derivative is not easily available. Even here the substitution with ammonia took place selectively in position 4 (124) and the remaining sulfur atom was replaced with oxygen by oxidation with alkaline potassium permanganate (125). A similar procedure is protected by a patent. ... 

Ethylene is selectively oxidized to ethylene oxide using a silver-based catalyst in a fixed-bed reactor. Ethylene and oxygen are supplied from the gas phase and ethylene oxide is removed by it. The catalyst is stationary. Undesired, kinetically determined by-products include carbon monoxide and water. Ideally, a pure reactant is converted to one product with no by-products. 

From these results, it was believed that the decrease of the V2O5 reoxidation property, caused by the increase of the reducing power, leaded to the deterioration of the activity of V2O5 catalyst in the selective oxidation of H2S under the environment of coal-derived synthesis gas. And the decreased reoxidation property of the V2O5 was enhanced by increasing oxygen and/or water content. 

Under microwave irradiation and applying MCM-41-immobilized nano-iron oxide higher activity is observed [148]. In this case also, primary aliphatic alcohols could be oxidized. The TON for the selective oxidation of 1-octanol to 1-octanal reached to 46 with 99% selectivity. Hou and coworkers reported in 2006 an iron coordination polymer [Fe(fcz)2Cl2]-2CH30H with fez = l-(2,4-difluorophenyl)-l,l-bis[(l//-l,2,4-triazol-l-yl)methyl]ethanol which catalyzed the oxidation of benzyl alcohol to benzaldehyde with hydrogen peroxide as oxidant in 87% yield and up to 100% selectivity [149]. An alternative approach is based on the use of heteropoly acids, whereby the incorporation of vanadium and iron into a molybdo-phosphoric acid catalyst led to high yields for the oxidation of various alcohols (up to 94%) with molecular oxygen [150]. 

Selective oxidation and ammoxldatlon of propylene over bismuth molybdate catalysts occur by a redox mechanism whereby lattice oxygen (or Isoelectronlc NH) Is Inserted Into an allyllc Intermediate, formed via or-H abstraction from the olefin. The resulting anion vacancies are eventually filled by lattice oxygen which originates from gaseous oxygen dlssoclatlvely chemisorbed at surface sites which are spatially and structurally distinct from the sites of olefin oxidation. Mechanistic details about the... 

In the present study, we report the synthesis, characterisation and catalytic properties (in selective oxidation reactions) of copper acetate, copper tetradecachlorophthalocyanine and copper tetranitrophthalocyanine encapsulated in molecular sieves Na-X, Na-Y, MCM-22 and VPI-5. Both molecular oxygen and aqueous HjOj have been used as the oxidants. The... 

Transition metal oxides represent a prominent class of partial oxidation catalysts [1-3]. Nevertheless, materials belonging to this class are also active in catalytic combustion. Total oxidation processes for environmental protection are mostly carried out industriaUy on the much more expensive noble metal-based catalysts [4]. Total oxidation is directly related to partial oxidation, athough opposes to it. Thus, investigations on the mechanism of catalytic combustion by transition metal oxides can be useful both to avoid it in partial oxidation and to develop new cheaper materials for catalytic combustion processes. However, although some aspects of the selective oxidation mechanisms appear to be rather established, like the involvement of lattice catalyst oxygen (nucleophilic oxygen) in Mars-van Krevelen type redox cycles [5], others are still uncompletely clarified. Even less is known on the mechanism of total oxidation over transition metal oxides [1-4,6]. 

In the cases of the selective oxidation reactions over metal oxide catalysts the so-called Mars-van Krevelen or redox mechanism [4], involving nucleophilic oxide ions 0 is widely accepted. A possible role of adsorbed electrophilic oxygen (molecularly adsorbed O2 and / or partially reduced oxygen species like C , or 0 ) in complete oxidation has been proposed by Haber (2]. However, Satterfield [1] queried whether surface chemisorbed oxygen plays any role in catalytic oxidation. 

TS-1 is a material that perfectly fits the definition of single-site catalyst discussed in the previous Section. It is an active and selective catalyst in a number of low-temperature oxidation reactions with aqueous H2O2 as the oxidant. Such reactions include phenol hydroxylation [9,17], olefin epoxida-tion [9,10,14,17,40], alkane oxidation [11,17,20], oxidation of ammonia to hydroxylamine [14,17,18], cyclohexanone ammoximation [8,17,18,41], conversion of secondary amines to dialkylhydroxylamines [8,17], and conversion of secondary alcohols to ketones [9,17], (see Fig. 1). Few oxidation reactions with ozone and oxygen as oxidants have been investigated. 

Lenoir, D. (2006) Selective Oxidation of Organic Compounds - Sustainable Catalytic Reactions with Oxygen and without Transition Metals Angewandte Chemie International Edition, 45, 3206-3210. 

The resulting microgel-stabilized metal nanoclusters are easily isolated, stored and further manipulated. Their remarkable catal5dic activity in technologically relevant reactions, such as C-C couplings [13a- ] and selective oxidations with molecular oxygen [13e] has been demonstrated. Extension of the applications of these nanoparticles to other areas of catalysis and materials science is currently underway. 

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