Phenols catalytic activity

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). 

In the petroleum (qv) industry hydrogen bromide can serve as an alkylation catalyst. It is claimed as a catalyst in the controlled oxidation of aHphatic and ahcycHc hydrocarbons to ketones, acids, and peroxides (7,8). AppHcations of HBr with NH Br (9) or with H2S and HCl (10) as promoters for the dehydrogenation of butene to butadiene have been described, and either HBr or HCl can be used in the vapor-phase ortho methylation of phenol with methanol over alumina (11). Various patents dealing with catalytic activity of HCl also cover the use of HBr. An important reaction of HBr in organic syntheses is the replacement of aHphatic chlorine by bromine in the presence of an aluminum catalyst (12). Small quantities of hydrobromic acid are employed in analytical chemistry. 

Phenol is the starting material for numerous intermediates and finished products. About 90% of the worldwide production of phenol is by Hock process (cumene oxidation process) and the rest by toluene oxidation process. Both the commercial processes for phenol production are multi step processes and thereby inherently unclean [1]. Therefore, there is need for a cleaner production method for phenol, which is economically and environmentally viable. There is great interest amongst researchers to develop a new method for the synthesis of phenol in a one step process [2]. Activated carbon materials, which have large surface areas, have been used as adsorbents, catalysts and catalyst supports [3,4], Activated carbons also have favorable hydrophobicity/ hydrophilicity, which make them suitable for the benzene hydroxylation. Transition metals have been widely used as catalytically active materials for the oxidation/hydroxylation of various aromatic compounds. 

Crystallite dimensions play a role in determining the rates of reactions and their control is of fimdamental importance not only for the catalytic activity, but also for the selectivity, since, with low rates of the desired reaction, the relative importance of secondary reactions may be greater. The effects of crystallite dimensions have been demonstrated for 1-butene epoxidation and for phenol hydroxylation, and they are significant for many reactions carried out with hquid phase reactants [17]. 

Finally, Jessop and coworkers describe an organometalhc approach to prepare in situ rhodium nanoparticles [78]. The stabilizing agent is the surfactant tetrabutylammonium hydrogen sulfate. The hydrogenation of anisole, phenol, p-xylene and ethylbenzoate is performed under biphasic aqueous/supercritical ethane medium at 36 °C and 10 bar H2. The catalytic system is poorly characterized. The authors report the influence of the solubility of the substrates on the catalytic activity, p-xylene was selectively converted to czs-l,4-dimethylcyclohexane (53% versus 26% trans) and 100 TTO are obtained in 62 h for the complete hydrogenation of phenol, which is very soluble in water. 

Loss of catalytic activity resulting from internal displacements is not usually a serious problem below temperatures of about 100 C. However, highly active R-groups, such as benzyl, methyl and allyl, undergo internal displacement more readily, particularly in the presence of strong nucleopfiles. For instance, the presence phenolates and thiolates may lead to the formation of benzyl alcohol, ethers, or sulphides from benzyl-substituted quaternary ammonium salts. 

Attempts have been made to exploit the intrinsic C2 symmetry of the phenolate-based dinickel core in enantioselective catalytic reactions. Therefore, enantiomerically pure C2-symmetric ligands such as (736a) and the corresponding dinickel systems (736b) have been prepared ( Equation (27)),1890 and (736b) was tested in the epoxidation of unfunctionalized alkenes with sodium hypochlorite as the oxidant. The catalytic reaction was found to be highly pH dependent with an optimum at a pH of 9. While the complex is catalytically active, significant enantioselectivity was not achieved. 

Mg/Me (Me=Al, Fe) mixed oxides prepared from hydrotalcite precursors were compared in the gas-phase m-cresol methylation in order to find out a relationship between catalytic activity and physico-chemical properties. It was found that the regio-selectivity in the methylation is considerably affected by the surface acid-basic properties of the catalysts. The co-existence of Lewis acid sites and basic sites leads to an enhancement of the selectivity to the product of ortho-C-alkylation with respect to the sole presence of basic sites. This derives from the combination of two effects, (i) The H+-abstraction properties of the basic site lead to the generation of the phenolate anion, (ii) The coordinative properties of Lewis acid sites, through their interaction with the aromatic ring, make the mesomeric effect less efficient, with predominance of the inductive effect of the -O species in directing the regio-selectivity of the C-methylation into the ortho position. 

The present work deals with the study of the liquid phase phenol alkylation by (-butanol over the three types of catalysts derived from MWW-precursor MCM-22, MCM-36 and ITQ-2. It was assumed that by pillaring and/or delamination the contribution of acid sites located on the hemicages will increase and it could be evidenced during the alkylation of phenol by (-butanol, process involving large reaction intermediates and products which are difficult to be accommodated within sinusoidal channels. The reaction pathway involves many parallel and/or successive steps, the main reactions being O-alkylation and C-alkylation. The catalytic activity and selectivity of these materials are discussed. A general scheme of the process is proposed on the basis of the structural and acidic features of the catalysts. 

The alkylation of phenol investigated over H-MCM-22, H-ITQ-2 and H-MCM-36 showed that the delamelation and pillaring did not improve the catalytic activity and this was explained on the secondary processes taking place during the preparation of the corresponding materials, and which strongly affect the total acidity and the acidity on the external surface. Also, the composition of the reaction products is not influenced to a considerable extent by product shape selectivity effects. This seems to show that the tert-butylation reaction preferentially proceed at (or close to) the external surface of the zeolite layers. 

In the present work, a Cu-13X zeolite sample was ceramized and used as a catalyst for the wet oxidation of phenol solutions and olive oil mill wastewaters (OOMW). The material showed good catalytic activity for the abatement of phenol and poly-phenols, excellent stability and no leaching of the active species. In this way a real heterogeneously catalyzed reaction was performed. Moreover, the catalyst was reused without special reactivation treatments for different consecutive reaction cycles. 

The ceramized Cu 13X material showed good catalytic activity and stability in the WHPCO of phenol. The performance of the catalyst (reused without any reactivation treatment) during the 10 consecutive reaction cycles proves an outstanding low leaching of copper species. The catalyst was very efficient in poly-phenol and TOC abatement of a real olive oil mill wastewater. 

These telomerization reactions of butadiene with nucleophiles are also catalyzed by nickel complexes. For example, amines (18-23), active methylene compounds (23, 24), alcohols (25, 26), and phenol (27) react with butadiene. However, the selectivity and catalytic activity of nickel catalysts are lower than those of palladium catalysts. In addition, a mixture of monomeric and dimeric telomers is usually formed with nickel catalysts ... 

In hydrogenation, early transition-metal catalysts are mainly based on metallocene complexes, and particularly the Group IV metallocenes. Nonetheless, Group III, lanthanide and even actinide complexes as well as later metals (Groups V-VII) have also been used. The active species can be stabilized by other bulky ligands such as those derived from 2,6-disubstituted phenols (aryl-oxy) or silica (siloxy) (vide infra). Moreover, the catalytic activity of these systems is not limited to the hydrogenation of alkenes, but can be used for the hydrogenation of aromatics, alkynes and imines. These systems have also been developed very successfully into their enantioselective versions. 

The three TS-1 catalysts with similar Ti contents have cuboidal morphology with comparable particle sizes of 0.2-0.3 pum (as shown in SEM pictures, Fig. 53). The EPR spectra of the samples in contact with aqueous H202 (46%) (Fig. 54) indicate that the ratio of the A to B superoxo species in various TS-1 samples increases in the order TS-1 (fluoride) < TS-1 (with anatase) < TS-1 (without anatase). Catalytic activity for phenol hydroxylation and allyl alcohol epoxi-dation (Table LIII) was found to parallel the A/B ratio of the oxo-Ti species (TS-1 (fluoride) < TS-1 (with anatase) < TS-1 (without anatase)). 

Specific catalytic activity of the composites obtained was at least several times higher than the same value for the random copolymer Nafion (even in an esterification reaction considered to be a diffusion-uncontrolled reaction). For the oligomerization reaction of decene-1 with strong diffusion control, the specific catalytic activity of the composites was 35 times higher than that for the random copolymer. Esterification of acrylic acid and alkylation of mesitilene by a substituted phenol were also performed using the composite catalyst. 

Co-catalysts other than water. Trichloro- and monochloro-acetic acids, when used as cocatalysts, induced instantaneous polymerisation at -140°. With the following co-catalysts the rate of polymerisation at -78° decreased in the order acetic acid > nitroethane > nitromethane > phenol > water [75a]. Since this is also the sequence of the acid dissociation constants of these substances in water, it appears that the catalytic activity , as shown by the rate of polymerisation, is correlated with the acidity of the cocatalyst in aqueous solution. Flowever, there are two reasons for questioning the validity of this correlation. 

We were interested in the behaviour of polymeric catalysts in order to confirm that typical polymer effects may occur. Oxidative coupling of 2,6-disubstituted phenols, as developped by Hay (7), was chosen as a model reaction and the catalytic activities of coordination complexes of copper with several polymeric tertiary amines were compared with the activities of their low molecular weight analogs. The overall reaction scheme is presented in scheme 1. 

Transition metal complexes encapsulated in the cavities of zeolites and meso-porous materials exhibit enhanced catalytic activity, compared to their neat analogs. " We had earlier found that Cu(II)-acetate exhibited enhanced regiose-lective orf/zo-hydroxylation of phenols using atmospheric oxygen as the oxidant on encapsulation in molecular sieves Y, MCM-22 or VPI-5. Rao et al. had also found a similar enhancement for encapsulation in Al-MCM-48. 

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