Zeolites organic reactions

Xu T, Munson E J and Flaw J F 1994 Toward a systematic chemistry of organic reactions in zeolites in situ NMR studies of ketones J. Am. Chem. Soc. 116 1962-72... 

One-step hydroxylation of aromatic nucleus with nitrous oxide (N2O) is among recently discovered organic reactions. A high eflSciency of FeZSM-5 zeolites in this reaction relates to a pronounced biomimetic-type activity of iron complexes stabilized in ZSM-5 matrix. N2O decomposition on these complexes produces particular atomic oj gen form (a-oxygen), whose chemistry is similar to that performed by the active oxygen of enzyme monooxygenases. Room temperature oxidation reactions of a-oxygen as well as the data on the kinetic isotope effect and Moessbauer spectroscopy show FeZSM-5 zeolite to be a successfiil biomimetic model. 

Shape selective catalysis as typically demonstrated by zeolites is of great interest from scientific as well as industrial viewpoint [17], However, the application of zeolites to organic reactions in a liquid-solid system is very limited, because of insufficient acid strength and slow diffusion of reactant molecules in small pores. We reported preliminarily that the microporous Cs salts of H3PW12O40 exhibit shape selectivity in a liquid-solid system [18]. Here we studied in more detail the acidity, micropore structure and catal3rtic activity of the Cs salts and wish to report that the acidic Cs salts exhibit efficient shape selective catalysis toward decomposition of esters, dehydration of alcohol, and alkylation of aromatic compound in liquid-solid system. The results were discussed in relation to the shape selective adsorption and the acidic properties. 

Y. I2umi, K Urabe and M. Onaka, Zeolite, Clay, and Heteropoly Add in Organic Reactions, Kodansha, Tokyo and VCH, Weinheim, New York, 1992. 

Pentene oxidation over TS-1 catalyst is a fast reaction and hence fulfils a basic requirement for being suited to micro-channel processing [30]. Thus, it can serve as a model reaction to demonstrate the benefits of micro chemical engineering, particularly for zeolite-catalyzed reactions. Apart from this, epoxidations are an important class of organic reactions, also of industrial importance. 

In this chapter, we demonstrate the potential of such agents as catalysts/promoters in key steps for the derivatization of sugars. The most significant catalytic approaches in carbohydrate chemistry that use aluminosilicate porous materials, namely zeolites and montmorillonite clays, are reviewed and discussed. Silica gel is a porous solid silicate that has also been used for heterogeneous catalysis of organic reactions in general. We include here its usefulness as promoter and reagent support for the reactions under consideration. 

Among the wide variety of organic reactions in which zeolites have been employed as catalysts, may be emphasized the transformations of aromatic hydrocarbons of importance in petrochemistry, and in the synthesis of intermediates for pharmaceutical or fragrance products.5 In particular, Friede 1-Crafts acylation and alkylation over zeolites have been widely used for the synthesis of fine chemicals.6 Insights into the mechanism of aromatic acylation over zeolites have been disclosed.7 The production of ethylbenzene from benzene and ethylene, catalyzed by HZSM-5 zeolite and developed by the Mobil-Badger Company, was the first commercialized industrial process for aromatic alkylation over zeolites.8 Other typical examples of zeolite-mediated Friedel-Crafts reactions are the regioselective formation of p-xylene by alkylation of toluene with methanol over HZSM-5,9 or the regioselective p-acylation of toluene with acetic anhydride over HBEA zeolites.10 In both transformations, the p-isomers are obtained in nearly quantitative yield. 

Another silicon-based porous solid which has been used in heterogeneous catalysis of organic reactions is silica gel. However, unlike zeolites and clays, silica gel is... 

Microwave processing of zeolites and their application in the catalysis of synthetic organic reactions has recently been excellently reviewed by Cundy [23] and other authors [24], The microwave synthesis of zeolites and mesoporous materials was surveyed, with emphasis on those aspects which differ from conventional thermal methods. The observed rate enhancement of microwave-mediated organic synthesis... 

Zhou, W. and Clennan, E.L. (1999). Organic reactions in zeolites. 1. Photooxidations of sulfides in methylene blue doped zeolite Y. J. Am. Chem. Soc. 121, 2915-2916... 

Table 4.1 Zeolite-Catalyzed Reactions toward Organic Products...

Figure 4.20 MTG/MTO reaction path and aromatics distribution with different zeolites as catalysts. (Reprinted from C.D. Chang, W.H. Lang, W.K. Bell, Catalysis in Organic Reactions, Molecular Shape-Selective Catalysis in Zeolites, pp. 93-94. Copyright 1981. With permission from Marcel Dekker.)...

Izumi, Y. Urabe, K. Onaka, A. Zeolite, Clay, and Heteropolyacids in Organic Reactions, Kodansha, Tokio-VCH Weinheim, 1992, pp. 1-106. 

Alkali metal ion-exchanged zeolites and occluded alkali metal oxide zeolites have been investigated extensively and applied as basic catalysts for a variety of organic transformations (1,41,221,222). Zeolites modified with alkaline earth compounds have been applied much less frequently as base catalysts for organic reactions. 

The performance of organic reactions in organized media, e.g. by zeolite confinement, and the use of zeolites as selective and green catalysts for organic transformations, have been popularized in recent years. The main advantage of the zeolites to be tested as media or catalysts for carrying out organic reactions is the so-called shape selectivity . ... 

Zeolites, which are aluminosilicates that can be regarded as being derived from AI2O3 and SiC>2, function as acidic catalysts in much the same way (Section 7.3). In addition, they catalyze isomerization, cracking, alkylation, and other organic reactions. A structurally related class of micro-porous materials based on aluminum phosphate (AIPO4) has also been developed (Section 7.7) like zeolites, they have cavities and channels at the molecular level and can function as shape-selective catalysts. 

Hunger and Wang provide an account of advances in the characterization of solid catalysts in the functioning state by nuclear magnetic resonance spectroscopy. Examples include investigations of zeolite-catalyzed reactions with isotopic labels that allow characterization of transition states and reaction pathways as well as characterization of organic deposits, surface complexes, and reaction intermediates formed in catalyst pores. 

The presence of solids such as clays, zeolites, silica or ion-exchange resins may allow catalysis or control of organic reactions. Often, yields are higher and work-up procedures simpler than for the corresponding homogeneous reactions, and product distributions may also be improved. Examples of selective substitution reactions in aromatic and heteroaromatic systems and of selective reactions of alkenes are discussed, and the wider potential for synthesis of fine chemicals is discussed. 

The use of zeolites as selective catalysts in organic syntheses is a field of growing importance. Zeolites are salts of solid silicoaluminic acids characterized by a strictly regular structure of their crystalline lattice (ref. 1) and by their high acidity and shape selectivity (ref. 2). Attention to the broad potential of zeolites in organic reactions was first drawn in the sixties by Venuto (ref. 3) and various applications of their catalytic properties have been recently reviewed (ref. 4). 

Since the early works on zeolite catalysed organic reactions (reviewed in 1968 by Venuto and Landis[1]), an incredibly large number of organic reactions was shown to be catalysed by microporous and mesoporous molecular sieves. Three main factors contribute to this broad applicability of zeolite catalysts ... 

There are indeed significant fundamental and practical differences between classical organic reactions (either stoichiometric or homogeneously catalysed ones) and those catalysed by solids and especially zeolites (Table 2.1). It is also the case when one compares the relatively simple transformations generally studied by the specialists in Heterogeneous Catalysis and the transformation of complex molecules involved in the synthesis of Fine Chemicals. The operating conditions are very different high temperature, gas phase, fixed bed reactors on the one hand low... 

Table 2.1 Fundamental and practical differences between homogeneous and zeolite catalysed organic reactions...

The characteristics of the solid particles of catalyst (size, mechanical resistance, etc.) have to be adapted to the reactor. In many organic reactions catalysed by acid zeolites, the catalytic act is concentrated in the outer rim of the crystals and decreasing the zeolite particle size generates a significant gain in activity. However, the use of small particles in batch reactors causes serious drawbacks in the separation of the zeolite from the reaction mixture for the recovery of reaction products and the eventual reuse of the catalyst. Also, small particles cannot be used in fixed bed reactors because of excessive pressure drops. 

Large differences were shown to exist between zeolite catalysed and homogeneous organic reactions. These differences can generate problems and pitfalls in the... 

An additional difficulty in the determination of actual TOF values for zeolite catalysed reactions deals with the accessibility by reactant molecules to the narrow micropores in which most of the potential active sites are located. The didactic presentation in Khabtou et al.[37] of the characterization of the protonic sites of FAU zeolites by pyridine adsorption followed by IR spectroscopy shows that the concentration of protonic sites located in the hexagonal prisms (not accessible to organic molecules) and in the supercages (accessible) can be estimated by this method. Base probe molecules with different sizes can also be used for estimating the concentrations of protonic sites located within the different types of micropores, which are presented by many zeolites (e.g. large channels and side pockets of mordenite1381). The concentration of acid sites located on the external surface of the... 

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