Oxidation of phenolics

Other Methods. A variety of other methods have been studied, including phenol hydroxylation by N2O with HZSM-5 as catalyst (69), selective access to resorcinol from 5-methyloxohexanoate in the presence of Pd/C (70), cyclotrimerization of carbon monoxide and ethylene to form hydroquinone in the presence of rhodium catalysts (71), the electrochemical oxidation of benzene to hydroquinone and -benzoquinone (72), the air oxidation of phenol to catechol in the presence of a stoichiometric CuCl and Cu(0) catalyst (73), and the isomerization of dihydroxybenzenes on HZSM-5 catalysts (74). 

Product identification does not distinguish OH versus hole oxidation, because the products are identical. For example, the products identified in the photo oxidation of phenol (qv) (Fig. 7) may originate either by OH radical attack of the phenol ring, or by direct hole oxidation to give the cation radical which subsequendy undergoes hydration in solvent water. 

Titanium Silicates. A number of titanium siUcate minerals are known (160) examples are Hsted in Table 19. In most cases, it is convenient to classify these on the basis of the connectivity of the SiO building blocks, eg, isolated tetrahedra, chains, and rings, that are typical of siUcates in general. In some cases, the SiO units may be replaced, even if only to a limited extent by TiO. For example, up to 6% of the SiO in the garnet schorlomite can be replaced by TiO. In general, replacement of SiO by TiO bull ding blocks increases the refractive indices of these minerals. Ti has also replaced Si in the framework of various zeofltes. In addition, the catalytic activity of both titanium-substituted ZSM-5 (TS-1) and ZSM-11 (TS-2) has received attention (161), eg, the selective oxidation of phenol, with hydrogen peroxide, to hydroquinone and catechol over TS-1 has been operated at the 10,000 t/yr scale in Italy (162). 

There are numerous stmctures that are similar to 2eofites, such as aluminophosphate molecular sieves, AlPOs, but these have not found catalytic apphcations. Zeofites can be modified by incorporation of cations in the crystalline lattice which are not exchangeable ions, but can play catalytic roles. For example, sificahte, which has the stmcture of ZSM-5 but without Al, incorpora ting Ti in the lattice is a commercial catalyst for oxidation of phenol with H2O2 to give diphenols the catalytic sites may be isolated Ti cations (85). 

Oxidation of phenols or anilines to quinones by means of potassium nitrosodlsuHanate (Fremy s salt). 

Muconic acid has been obtained in a variety of ways. The procedures that seem most important from a preparative point of view are by treatment of ethyl o ,5-dibromoadipate with alcoholic potassium hydroxide, by condensation of glyoxal (as the sodium bisulfite addition product) with malonic acid, by heating ethyl l-acetoxy-l,4-dihydromuconate (obtained by condensing ethyl oxalate and ethyl crotonate, acetylating, and reducing),and by oxidation of phenol with peracetic acid. ... 

When chloroform or methanol is used as the solvent for the oxidation of phenols, other products, originating from coupling of aryloxy radicals, e.g., polyphenylene ethers and/or diphenoquinones, are also formed. ... 

Oxidation of phenols with chlorine dioxide or chlorine produces chlorinated aromatic intermediates before ring rupture. Oxidation of phenols with either chlorine dioxide or ozone produces oxidized aromatic compounds as intermediates which undergo ring rupture upon treatment with more oxidant and/or longer reaction times. In many cases, the same nonchlorinated, ringruptured aliphatic products are produced using ozone or chlorine dioxide. 

Synthesis of p-quinones, derivatives of fused systems including heterocyclic fragments through oxidation of phenol derivatives 98OPP603. 

The main product of the Elbs reaction is the 1,4-dihydroxybenzene (hydro-quinone). If the para position is already occupied by a substituent, the reaction occurs at an ortho position, leading to a catechol derivative although the yields are not as good as for a hydroquinone. Better yields of catechols 7 can be obtained by a copper-catalyzed oxidation of phenols with molecular oxygen ... 

Intramolecular Friedel-Crafts acylation of diaryl ketones Oxidation of phenols or aromatic amines Oxidation of aromatic hydrocarbons... 

PO performs vitally important functions in the plant cell and is mainly associated with the oxidation of phenolic compounds and with the formation and strengthening of the cell wall (Passardi et al., 2004). PO is involved in the oxidative transformation of molecules in growth-regulating or signalling activities and - as a result - can also perform regulatory functions in the cell. Plant POs are represented by genetically different proteins with the same enzymatic activity (Welinder et al., 2002). 

Carulite (Mn02/Cu0 on alumina) has shown exceptional performance for the complete rapid oxidation of phenol and other difficult substrates at temperatures just above T. The first full-scale SCWO plant has been commercialized by Huntsman, and it is expected that the technology will now become more mainstream as the value of different kinds of supercritical fluid technology becomes generally more widely appreciated and cost effective. 

Previous studies by Sorokin with iron phthalocyanine catalysts made use of oxone in the oxidation of 2,3,6-trimethylphenol [134]. Here, 4 equiv. KHSO5 were necessary to achieve full conversion. Otherwise, a hexamethyl-biphenol is observed as minor side-product. Covalently supported iron phthalocyanine complexes also showed activity in the oxidation of phenols bearing functional groups (alcohols, double bonds, benzylic, and allylic positions) [135]. Besides, silica-supported iron phthalocyanine catalysts were reported in the synthesis of menadione [136]. 

The permanganate oxidation of phenols is complicated by the intervention of lower oxidation states of manganese, (c/. the oxidation of toluene, p. 298). For example, the oxidation of 2,6-dinitrophenol in weakly acidic solution displays an induction period, following second-order kinetics thereafter. However, addition of potassium fluoride inhibits reaction almost completely, but manganous ions strongly accelerate it. 

The oxidation of phenol in alcoholic media by a morpholine complex of Cu(II) (as a model for tyrosinase) to give 4,5-dimorpholino-orr/jo-benzoquinone in 64 %... 

Hyman MR, AW Sansome-Smith, JH Shears, PM Wood (1985) A kinetic study of benzene oxidation to phenol by whole cells of Nitrosomonas europaea and evidence for the further oxidation of phenol to hydroqui-none. Arch Microbiol 143 302-306. 

New materials are also finding application in the area of catalysis reiated to the Chemicals industry. For example, microporous [10] materials which have titanium incorporated into the framework structure (e.g. so-calied TS-1) show selective oxidation behaviour with aqueous hydrogen peroxide as oxidizing agent (Figure 5). Two processes based on these new catalytic materials have now been developed and commercialized by ENl. These include the selective oxidation of phenol to catechol and hydroquinone and the ammoxidation of cyclohexanone to e-caproiactam. 

Table 3 Oxidation of phenols (TON ) with Oj over copper acetate-based catalysts at 298 K...

The oxidation of phenol, ortho/meta cresols and tyrosine with Oj over copper acetate-based catalysts at 298 K is shown in Table 3 [7]. In all the cases, the main product was the ortho hydroxylated diphenol product (and the corresponding orthoquinones). Again, the catalytic efficiency (turnover numbers) of the copper atoms are higher in the encapsulated state compared to that in the "neat" copper acetate. From a linear correlation observed [7] between the concentration of the copper acetate dimers in the molecular sieves (from ESR spectroscopic data) and the conversion of various phenols (Fig. 5), we had postulated [8] that dimeric copper atoms are the active sites in the activation of dioxygen in zeolite catalysts containing encapsulated copper acetate complexes. The high substratespecificity (for mono-... 

Table 6 Oxidation of phenol with over phthalocyanines... 

Table Oxidation of phenol over CuClg Pc-Na-Y (0.26) InOuenceof HjOjConcentration...

High potential Oj reduction to H O coupled to oxidation of phenols... 

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