Other oxidations

In addition to the epoxidation of olefins, zeolitic materials have been studied for other fine chemical transformations. Table 12.21 indexes the zeolites used for oxidative dehydrogenation of propane, direct hydroxylation of benzene to phenol and e-caprolactam synthesis. A recent review summarizes other reactions for which there is not enough space in the table [138, 139]. 

Zeolite S1O2/ AI2O3 ratio Metal (wt%) Feed H2/HC sv Temperature Pressure Yield information Notes Reference 

5 NiO(1.7) M0O3 (6.7) Arabian heavy atmospheric residue Autoclave 410°G 9.8MPa 74.9% liquid product, 52% HDS activity, 26.8% HDN activity Contains mesopores [123] 

Zeolite Si/Ti ratio Feed Oxidant sv Temperature Pressure Conversion Selectivity Notes Reference 

Although more than one century has gone by since its discovery in 1899, the Baeyer Villiger reaction is still far from being fully developed. In particular, there are only a few catalyst systems which afford products from the Baeyer-Villiger oxidation of 3-substituted cyclobutanones in more than 80% ee. The first example of the enantioselective Baeyer-Villiger oxidation of 3-substituted cyclobutanones catalysed by a chiral organocatalyst and 30% 

Shiigi, H. Mori, T. Tanaka, Y. Demizu and O. Onomura, Tetrahedron Lett., 2008, 49, 5247-5251. 

As previously shown, the marriage of green oxidant agents, like H2O2, and well-developed catalysts, such as TS-1, is able to drive strong improvement in industrial chemistry. 

Moreover, we have to cope with one of the biggest dreams/nightmares of industrial chemists the high productivity AND selectivity AND safe oxidation of organic substrates by oxygen/air in the presence of suitable oxidation catalysts. Usually, this approach does not give fully acceptable results either with respect to the intrinsic safety of the process, or to its performances quite often deep oxidation takes place or difficult safety constraints must be considered. 

In the last 20 years, a number of approaches have been investigated. The most promising are  

Often these approaches do not stand alone but are carefully connected optimized catalysts are used in ad hoc technology configurations, by using proper oxidants. 

A few examples follow that focus on the redox or depletive approach, the het-eropolyacids/peroxide systems, and on oxidative desulfurization. 

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Since scanning tunneling microscopy requires flat conducting surfaces, it is not surprising that most of its early application was to study inorganic materials [17, 19, 20, 29-34]. These studies include investigations of catalytic metal surfaces [24, 35-37], silicon and other oxides [21], superconductors [38], gold... 

Fluorine is known to form three other oxides, OjFj, O3F2 and O4F2 but all these decompose below 200 K. 

Acetoxybenzene is prepared by the reaction of benzene with Pd(OAc)2[325,342-345], This reaction is regarded as a potentially useful method for phenol production from benzene, if carried out with only a catalytic amount of Pd(OAc)2. Extensive studies have been carried out on this reaction in order to achieve a high catalytic turnover. In addition to oxygen and Cu(II) salts, other oxidants, such as HNOi, nitrate[346,347], potassium peroxodisulfate[348], and heteropoly acids[349,3S0], are used. HNO is said to... 

Several Pd(0) complexes are effective catalysts of a variety of reactions, and these catalytic reactions are particularly useful because they are catalytic without adding other oxidants and proceed with catalytic amounts of expensive Pd compounds. These reactions are treated in this chapter. Among many substrates used for the catalytic reactions, organic halides and allylic esters are two of the most widely used, and they undergo facile oxidative additions to Pd(0) to form complexes which have o-Pd—C bonds. These intermediate complexes undergo several different transformations. Regeneration of Pd(0) species in the final step makes the reaction catalytic. These reactions of organic halides except allylic halides are treated in Section 1 and the reactions of various allylic compounds are surveyed in Section 2. Catalytic reactions of dienes, alkynes. and alkenes are treated in other sections. These reactions offer unique methods for carbon-carbon bond formation, which are impossible by other means. 

Because of their use in the rubber industry various sulfenamido thiazoles (131) have been prepared. They are obtained in good yields through the oxidation of A-4-thiazoline-2-thiones (130) in aqueous alkaline solution in the presence of an amine or ammonia (Scheme 66) <123, 166, 255, 286, 308, 309). Other oxidizing agents have been proposed (54, 148. 310-313) such as iodine (152), chlorine, or hydrogen peroxide. Disulfides can also be used as starting materials (3141. 

The oxidation of 2- and 5-sulfides is usually performed in acetic acid and 30% hydrogen peroxide (213, 229, 263, 345-350) Or with m-chloroperbenzoic acid (341). Ary] (8, 272. 349, 351-353) and alkyl sulfones (129, 203, 214, 270, 274, 275) are thus obtained in good yields. Other oxidative reagents such as KMn04 (7, 273) or CrO (7) in acetic add have also been used. 

Thiazolecarboxaldehydes are very easily oxidized to carboxylic acids by most oxidizing agents, the most common being KMn04 in cold pyridine or boiling acetone. Thiazolecarboxylic acids are obtained in 50% yield (29). Other oxidizing agents such as Ag 0 in dioxane and water (29, 103), chromic acid, and so forth are also used. 

In view of the widespread use of nitrogen and argon in surface area and porosity studies, data for the construction of the standard a,-curves for these adsorbates on hydroxylated silica, are given in Table 2.14 (p. 93) for nitrogen and in Table 2.15 for argon. From the arguments of Section 2.12, these should be adequate for other oxides such as alumina, if high accuracy is not called for. 

Most metals will precipitate as the hydroxide in the presence of concentrated NaOH. Metals forming amphoteric hydroxides, however, remain soluble in concentrated NaOH due to the formation of higher-order hydroxo-complexes. For example, Zn and AP will not precipitate in concentrated NaOH due to the formation of Zn(OH)3 and Al(OH)4. The solubility of AP in concentrated NaOH is used to isolate aluminum from impure bauxite, an ore of AI2O3. The ore is powdered and placed in a solution of concentrated NaOH where the AI2O3 dissolves to form A1(0H)4T Other oxides that may be present in the ore, such as Fe203 and Si02, remain insoluble. After filtering, the filtrate is acidified to recover the aluminum as a precipitate of Al(OH)3. 

In this manner, a current efficiency of 100% is maintained. Furthermore, since the concentration of Ce + remains at its initial level, the potential of the working electrode remains constant as long as any Fe + is present. This prevents other oxidation reactions, such as that for liiO, from interfering with the analysis. A species, such as Ce +, which is used to maintain 100% current efficiency, is called a mediator. 

Activated carbons contain chemisorbed oxygen in varying amounts unless special cate is taken to eliminate it. Desired adsorption properties often depend upon the amount and type of chemisorbed oxygen species on the surface. Therefore, the adsorption properties of an activated carbon adsorbent depend on its prior temperature and oxygen-exposure history. In contrast, molecular sieve 2eohtes and other oxide adsorbents are not affected by oxidi2ing or reducing conditions. 

The lower molecular weight PCTFE oils, waxes, and greases are used as inert sealants and lubricants for equipment handling oxygen and other oxidative or corrosive media. Other uses include gyroscope flotation fluids and plasticizers for thermoplastics. 

Si02, AI2O2—Si02, and many other oxides. 

The heavy mineral sand concentrates are scmbbed to remove any surface coatings, dried, and separated into magnetic and nonmagnetic fractions (see Separation, magnetic). Each of these fractions is further spHt into conducting and nonconducting fractions in an electrostatic separator to yield individual concentrates of ilmenite, leucoxene, monazite, mtile, xenotime, and zircon. Commercially pure zircon sand typically contains 64% zirconium oxide, 34% siUcon oxide, 1.2% hafnium oxide, and 0.8% other oxides including aluminum, iron, titanium, yttrium, lanthanides, uranium, thorium, phosphoms, scandium, and calcium. 

Chain lengths of some oxidations can be quite long (>100), especially for substrates with easily abstractable hydrogens when they are oxidized under mild conditions at low conversions. Aldehydes are good examples of such substrates (26). Many other oxidations have chain lengths estimated from 3 to 10. At limiting rates, the chain length is near 1 (25). 

The quantitative conversion of thiosulfate to tetrathionate is unique with iodine. Other oxidant agents tend to carry the oxidation further to sulfate ion or to a mixture of tetrathionate and sulfate ions. Thiosulfate titration of iodine is best performed in neutral or slightly acidic solutions. If strongly acidic solutions must be titrated, air oxidation of the excess of iodide must be prevented by blanketing the solution with an inert gas, such as carbon dioxide or... 

Fluxes are usually added in the form of either limestone or dolomite. The fluxes provide the basic constituents (CaO and MgO) needed to balance the acid constituents (Si02 and AI2O2) from the coke and ore. These are the four primary oxides which form the slag, although minor amounts of other oxides such as MnO, Na20, K2O, P2 S Ti02, and sulfur are also present. Proper adjustment of the slag chemistry is necessary to obtain the desired... 

Lignosulfonate Uses. Large-volume uses iaclude productioa of vanillin (qv) and DMSO (76). Commercially, softwood spent sulfite Hquors or lignosulfonates can be oxidized ia alkaline media by oxygea or air to produce vanillin [121 -33-5]. Other oxidizing ageats, such as copper(Il) hydroxide, nitrobenzene, and ozone, can also be used. 

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