Reoxidants

HSCH -CHNHj-COjH. Cysteine is a reduction product of cystine. It is the first step in the breakdown of cystine in the body, one molecule of cystine splitting to give two molecules of cysteine. Cysteine is soluble in water but the solution is unstable, and is reoxidized to cystine. 

Vanadium trioxide, V2O3. Black powder (V2OS plus Hj under heat). Readily reoxidized to VjOj. Stable down to VO,.35. 

Wacker process The oxidation of ethene to ethanal by air and a PdClj catalyst in aqueous solution. The Pd is reduced to Pd in the process but is reoxidized to Pd " by oxygen and Cu. ... 

K3Fe(CN)6 as a reoxidant gives higher ee s- eliminates second cycle... 

Palladation of aromatic compounds with Pd(OAc)2 gives the arylpalladium acetate 25 as an unstable intermediate (see Chapter 3, Section 5). A similar complex 26 is formed by the transmetallation of PdX2 with arylmetal compounds of main group metals such as Hg Those intermediates which have the Pd—C cr-bonds react with nucleophiles or undergo alkene insertion to give oxidized products and Pd(0) as shown below. Hence, these reactions proceed by consuming stoichiometric amounts of Pd(II) compounds, which are reduced to the Pd(0) state. Sometimes, but not always, the reduced Pd(0) is reoxidized in situ to the Pd(II) state. In such a case, the whole oxidation process becomes a catalytic cycle with regard to the Pd(II) compounds. This catalytic reaction is different mechanistically, however, from the Pd(0)-catalyzed reactions described in the next section. These stoichiometric and catalytic reactions are treated in Chapter 3. 

The isocoumarin 151 is prepared by the intramolecular reaction of 2-(2-propenyDbenzoic acid (149) with one equivalent of PdCbjMeCN) . However, the (Z)-phthalide 150 is obtained from the same acid with a catalytic amount of PdjOAc) under 1 atm of Oi in DMSO, alone is remarkably efficient in reoxidizing Pd(0) in DMSO. The isocoumarin 151 is obtained by the reaction of 2-(l-propenyl)benzoic acid (152) under the same conditions[4], 2-Vinylbenzoic acid (153) is also converted into the isocoumarin 154, but not to the five-membered lactone) 167,170],... 

The intermediate 190 of the intramolecular aminopalladation of an allenic bond with jV-tosylcarbamate undergoes insertion of allylic chloride. Subsequent elimination of PdCl2 occurs to afford the 1,4-diene system 191. The regeneration of Pd(II) species makes the reaction catalytic without using a reoxidant[190]. 

TT-Aliylpalladium chloride reacts with a soft carbon nucleophile such as mal-onate and acetoacetate in DMSO as a coordinating solvent, and facile carbon-carbon bond formation takes place[l2,265], This reaction constitutes the basis of both stoichiometric and catalytic 7r-allylpalladium chemistry. Depending on the way in which 7r-allylpalladium complexes are prepared, the reaction becomes stoichiometric or catalytic. Preparation of the 7r-allylpalladium complexes 298 by the oxidative addition of Pd(0) to various allylic compounds (esters, carbonates etc.), and their reactions with nucleophiles, are catalytic, because Pd(0) is regenerated after the reaction with the nucleophile, and reacts again with allylic compounds. These catalytic reactions are treated in Chapter 4, Section 2. On the other hand, the preparation of the 7r-allyl complexes 299 from alkenes requires Pd(II) salts. The subsequent reaction with the nucleophile forms Pd(0). The whole process consumes Pd(ll), and ends as a stoichiometric process, because the in situ reoxidation of Pd(0) is hardly attainable. These stoichiometric reactions are treated in this section. 

In order to make these oxidative reactions of 1,3-dienes catalytic, several reoxidants are used. In general, a stoichiometric amount of benzoquinone is used. Furthermore, Fe-phthalocyanine complex or Co-salen complex is used to reoxidize hydroquinone to benzoquinone. Also, it was found that the reaction is faster and stereoselectivity is higher when (phenylsulflnyl)benzoquinone (383) is used owing to coordination of the sulfinyl group to Pd, Thus the reaction can be carried out using catalytic amounts of PdfOAcji and (arylsulfinyl)benzoquinone in the presence of the Fe or Co complex under an oxygen atmosphere[320]. Oxidative dicyanation of butadiene takes place to give l,4-dicyano-2-butene(384) (40%) and l,2-dicyano-3-butene (385)[32l]. 

Benzoic acid and naphthoic acid are formed by the oxidative carbonylation by use of Pd(OAc)2 in AcOH. t-Bu02H and allyl chloride are used as reoxidants. Addition of phenanthroline gives a favorable effect[360], Furan and thiophene are also carbonylated selectively at the 2-position[361,362]. fndole-3-carboxylic acid is prepared by the carboxylation of 1-acetylindole using Pd(OAc)2 and peroxodisulfate (Na2S208)[362aj. Benzoic acid derivatives are obtained by the reaction of benzene derivatives with sodium palladium mal-onate in refluxing AcOH[363]. 

Although turnover of the catalyst is low, even unreactive cyclohexane[526] and its derivatives are oxidatively carbonylated to cyclohexanecarboxylic acid using KiS Og as a reoxidant in 565% yield based on Pd(II)[527]. Similarly, methane and propane are converted into acetic acid in 1520% yield based on Pd(II) and butyric acid in 5500% yield [528],... 

Because Pd(II) salts, like Hgtll) salts, can effect electrophilic metallation of the indole ring at C3, it is also possible to carry out vinylation on indoles without 3-substituents. These reactions usually require the use of an equiv. of the Pd(ll) salt and also a Cu(If) or Ag(I) salt to effect reoxidation of the Pd. As in the standard Heck conditions, an EW substitution on the indole nitrogen is usually necessary. Entry 8 of Table 11.3 is an interesting example. The oxidative vinylation was achieved in 87% yield by using one equiv. of PdfOAcfj and one equiv. of chloranil as a co-oxidant. This example is also noteworthy in that the 4-broino substituent was unreactive under these conditions. Part B of Table 11.3 lists some other representative procedures. 

The metallic palladium is reoxidized to PdCl2 by the CUCI2 and the resultant cuprous chloride is then reoxidized by oxygen or ait as shown. 

During the reaction, the palladium catalyst is reduced. It is reoxidized by a co-catalyst system such as cupric chloride and oxygen. The products are acryhc acid in a carboxyUc acid-anhydride mixture or acryUc esters in an alcohoHc solvent. Reaction products also include significant amounts of 3-acryloxypropionic acid [24615-84-7] and alkyl 3-alkoxypropionates, which can be converted thermally to the corresponding acrylates (23,98). The overall reaction may be represented by ... 

CO, and methanol react in the first step in the presence of cobalt carbonyl catalyst and pyridine [110-86-1] to produce methyl pentenoates. A similar second step, but at lower pressure and higher temperature with rhodium catalyst, produces dimethyl adipate [627-93-0]. This is then hydrolyzed to give adipic acid and methanol (135), which is recovered for recycle. Many variations to this basic process exist. Examples are ARCO s palladium/copper-catalyzed oxycarbonylation process (136—138), and Monsanto s palladium and quinone [106-51-4] process, which uses oxygen to reoxidize the by-product... 

SO2 adsorbed on copper oxide bed forming CuSO. Bed is regenerated with H2 or H2—CO mixture giving concentrated SO2 stream. Bed is reduced to Cu, but reoxidized for SO2 adsorption. 

The process can be operated in two modes co-fed and redox. The co-fed mode employs addition of O2 to the methane/natural gas feed and subsequent conversion over a metal oxide catalyst. The redox mode requires the oxidant to be from the lattice oxygen of a reducible metal oxide in the reactor bed. After methane oxidation has consumed nearly all the lattice oxygen, the reduced metal oxide is reoxidized using an air stream. Both methods have processing advantages and disadvantages. In all cases, however, the process is mn to maximize production of the more desired ethylene product. 

The yield of hydroquinone is 85 to 90% based on aniline. The process is mainly a batch process where significant amounts of soHds must be handled (manganese dioxide as well as metal iron finely divided). However, the principal drawback of this process resides in the massive coproduction of mineral products such as manganese sulfate, ammonium sulfate, or iron oxides which are environmentally not friendly. Even though purified manganese sulfate is used in the agricultural field, few solutions have been developed to dispose of this unsuitable coproduct. Such methods include MnSO reoxidation to MnO (1), or MnSO electrochemical reduction to metal manganese (2). None of these methods has found appHcations on an industrial scale. In addition, since 1980, few innovative studies have been pubUshed on this process (3). 

In handling, shipping, and storing DRI, care should be taken to avoid oxidation. Millions of tons of DRI in pehet and lump form have been shipped by barge, ocean vessel, tmck, and rad. The key to avoiding oxidation is simply to keep the material cool and dry. The chemical reactions involved have been well documented. In general, oxidation of DRI takes place in two forms reoxidation and corrosion (2). 

Reoxidation occurs when the metallic iron in hot DRI reacts with oxygen in the air to form either Ee O or Ee202. The reaction continues as long as the DRI remains hot and sufficient oxygen is avadable. Because reoxidation reactions are exothermic and DRI is a good insulator, it is possible that once reoxidation begins inside a pde, the DRI temperature increases and accelerates the reoxidation rate. Although the inner core of the pde may reach temperatures up to the fusion point of iron, the maximum temperature of the outer parts of the pde will be much lower because of heat dissipation. 

Allowing DRI to become wet does not necessatily cause it to overheat. When large pdes of DRI are wetted with rain, the corrosion reactions are limited to the outer surface area of the pde and the resultant heat from the corrosion reactions is dissipated into the atmosphere. However, if water penetrates into the pde from the bottom, or if wet DRI is covered with dry DRI, the heat from corrosion reactions can budd up inside the pde to the point where rapid reoxidation begins. Corrosion occurs significantly faster with salt water than with fresh water. DRI saturated with water can cause steam explosions if it is batch charged into an electric arc furnace. 

In comparison, HBI is almost twice as dense as DRI, and thus does not absorb as much water and is much more resistant to reoxidation and corrosion. Several methods of passivating DRI to make it more resistant to reoxidation and corrosion have been developed, but none has been as effective as hot briquetting. Guidelines for offshore shipping of peUet/lump DRI and HBI have been prepared by the International Maritime Organization. 

Fresh butane mixed with recycled gas encounters freshly oxidized catalyst at the bottom of the transport-bed reactor and is oxidized to maleic anhydride and CO during its passage up the reactor. Catalyst densities (80 160 kg/m ) in the transport-bed reactor are substantially lower than the catalyst density in a typical fluidized-bed reactor (480 640 kg/m ) (109). The gas flow pattern in the riser is nearly plug flow which avoids the negative effect of backmixing on reaction selectivity. Reduced catalyst is separated from the reaction products by cyclones and is further stripped of products and reactants in a separate stripping vessel. The reduced catalyst is reoxidized in a separate fluidized-bed oxidizer where the exothermic heat of reaction is removed by steam cods. The rate of reoxidation of the VPO catalyst is slower than the rate of oxidation of butane, and consequently residence times are longer in the oxidizer than in the transport-bed reactor. 

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