Montmorillonite activation

On the other hand, we have compared the yield and selectivity in the reactions of acetophenone oxime with Al3 and Cr3 exchanged montmorillonites activated thermically and by microwaves (Fig. 2). From the obtained results, we can deduce that microwaves enhance significatively the conversion rate, being the conversion practically quantitative for only 10 minutes of treatment at 600W. The selectivity of the reaction can be directly correlated with that of the thermal treatment at 160°C. The effect of microwaves could be attributed, as we have previously demonstrated (ref.8) to the rapid... 

B. Tyagi, C. D. Chudasama, and R. V. Jasra. Characterization of surface acidity of an acid montmorillonite activated with hydrothermal, ultrasonic and micro-wave techniques. Applied Clay Science, 31 (2006), 16-28. 

Vinyl acetate reacts with the alkenyl triflate 65 at the /3-carbon to give the 1-acetoxy-1,3-diene 66[68]. However, the reaction of vinyl acetate with 5-iodo-pyrimidine affords 5-vinylpyrimidine with elimination of the acetoxy group[69]. Also stilbene (67) was obtained by the reaction of an excess of vinyl acetate with iodobenzene when interlamellar montmorillonite ethylsilyl-diphenylphosphine (L) palladium chloride was used as an active catalyst[70]. Commonly used PdCl2(Ph3P)2 does not give stilbene. 

A wide range of clay materials have been used for decolorizing. These may be substantially cmde clay such as fuller s earth, which largely contains montmorillonite as the active clay ingredient, or specially treated attapulgites, montmorillonites, and kaolinites. Proprietary acid activation processes are frequentiy used for production of clay-derived materials of superior performance. 

E. C. Taylor and C.-S. Chiang, Synthesis, 467 (1977). Montmorillonite clay is activated Al203/Si02/H20. 

It is believed that clay minerals promote organic reactions via an acid catalysis [2a]. They are often activated by doping with transition metals to enrich the number of Lewis-acid sites by cationic exchange [4]. Alternative radical pathways have also been proposed [5] in agreement with the observation that clay-catalyzed Diels-Alder reactions are accelerated in the presence of radical sources [6], Montmorillonite K-10 doped with Fe(III) efficiently catalyzes the Diels-Alder reaction of cyclopentadiene (1) with methyl vinyl ketone at room temperature [7] (Table 4.1). In water the diastereoselectivity is higher than in organic media in the absence of clay the cycloaddition proceeds at a much slower rate. 

Good results were obtained with (R)-0-acryloylpantolactone (4) in which the dienophile was incorporated with a smaller chiral auxiliary. Some results are reported in Table 4.4, where the cycloadditions catalyzed by Zn(II)-, Fe(II)- and Ti(IV)-K-10 exchanged montmorillonite calcined at 120 °C and 550 °C are compared with those that were not catalyzed and with TiCU- and EtAlCh-catalyzed reactions. Among the metal-clays activated, the Ti(IV)-K-10 was the best catalyst with high conversion and acceptable enantioselectivity obtained after 2 h. 

The performance of clay materials (Halloysite, Pyrophyllite, Montmorillonite K-30) in the degradation of polystyrene (PS) was investigated in this study. The catalysts showed good catalytic activity for the degradation of PS with high selectivity to aromatics liquids. Styrene is the major product, and ethylbenzene is the second most abundant one in the liquid product. 

Bioreactors containing an nndefined anaerobic consortinm rednced TNT to 2,4,6-triaminotoluene (TAT) in the presence of glncose (Dann et al. 1998). The sorption of TAT to montmorillonite clay was irreversible, and the snbstrate conld not be released by solvent extraction or by acid or alkaline treatment. Similar resnlts were obtained with humic acids in which covalent reactions with carbonyl or activated C=C bonding presumably occurred. Results from laboratory experiments nsing i C-labeled TNT in reactors to which... 

Vaccari (1983,1999) has given a state-of-the-art account of the preparation and catalytic properties of cationic and anionic clays. Some examples of industrial importance have also been reported. Clays exhibit many desirable features, such as low cost, wide range of preparation variables, ease of set-up and wOrk-up, high selectivity, and environmental friendliness. Cationic clays are widespread in nature, whereas anionic clays are rarely found in nature, but they can be synthesized cheaply. Cationic clays are prepared from the minerals but industrial anionic clays are generally synthetic. Smectite clays exhibit both Brpnsted and Lewis acid sites on the edges of the crystals. Hammet s acidity function values are as follows Na -montmorillonite (M), -3 to t- 1.5 NH4VM -3 to 1.5 H M -8.2 to -5.6 acid activated clay less than -8.2. Laporte also has a synthetic version of cationic clays, Laponite. The acid... 

Zinc chloride exchanged clay catalysts have been reported to be highly active for the Friedel-Crafts alkylation and acylation reactions these are commercially sold by Contract Catalysts under the name Envirocats. These are montmorillonite catalysts modified by ZnCU and FeCli. Some of the reported examples of Friedel-Crafts reactions are given below there are claims that some of the processes are commercially practised. 

Helgeson (1967) constructed an activity diagram depicting chemical equilibrium points (albite-sericite-K-feldspar and albite-sericite-Na-montmorillonite) of NazO-K20-Si02-Al203-H20 system at elevated temperatures. At these points,... 

This equation shows that activity of Ca + is related to pH, concentration of H2CO3 and temperature. Because pH is related to the concentration of Cl for the equilibrium curves 1 and 2 in Fig. 2.14, the relationship between the concentrations of Ca " " and Cl" can be derived for calcite-albite-sericite-K-feldspar-quartz equilibrium (curves 4 and 7 in Fig. 2.14) and calcite-albite-sericite-Na-montmorillonite-quartz equilibrium (curves 5 and 8 in Fig. 2.14) with constant w2h2C03- The range of zh2C03 in the solution in equilibrium with calcite is assumed to be 10 to 10 . The other equilibrium curves for the assemblage including Ca minerals are also drawn (Fig. 2.14). These assemblages are wairakite-albite-sericite-K-feldspar-quartz (curve 3), Ca-montmotillonite-albite-sericite-Na-montmorillonite-quartz (curve 6), Ca-montmorillonite-albite-sericite-K-feldspar-quartz (curve 9) and anhydrite (curve 10). The effect of solid solution on the equilibrium curves is not considered because of the lack of thermochemical data of solid solution. 

Montmorillonite K10 was also used for aldol the reaction in water.280 Hydrates of aldehydes such as glyoxylic acid can be used directly. Thermal treatment of K10 increased the catalytic activity. The catalytic activity is attributed to the structural features of K10 and its inherent Bronsted acidity. The aldol reactions of more reactive ketene silyl acetals with reactive aldehydes proceed smoothly in water to afford the corresponding aldol products in good yields (Eq. 8.104).281... 

Other studies use soil or sediment samples for a more accurate indication of microbial activity in natural environments. In these samples, organic matter and clay particles play a role in metal toxicity.76112113 Both organic material and clay particles in soil can bind metals and reduce their bioavailability. For example, Pardue et al.87 demonstrated that much less solution-phase cadmium was required to inhibit trichloroaniline (TCA) dechlorination in a mineral-based soil than in a soil containing a higher concentration of organic matter. Other studies have shown that adding clay minerals to a medium mitigates toxicity. Clay minerals, such as kaolinite, montmorillonite, bentonite, and vermiculite, can bind to metals to decrease the amount that is bioavailable.112 115... 

As noted above, adsorption isotherms are largely derived empirically and give no information on the types of adsorption that may be involved. Scrivner and colleagues39 have developed an adsorption model for montmorillonite clay that can predict the exchange of binary and ternary ions in solution (two and three ions in the chemical system). This model would be more relevant for modeling the behavior of heavy metals that actively participate in ion-exchange reactions than for organics, in which physical adsorption is more important. 

The intercalated catalysts can often be regarded as biomimetic oxidation catalysts. The intercalation of cationic metal complexes in the interlamellar space of clays often leads to increased catalytic activity and selectivity, due to the limited orientations by which the molecules are forced to accommodate themselves between sheets. The clays have electrostatic fields in their interlayer therefore, the intercalated metal complexes are more positively charged. Such complexes may show different behavior. For example, cationic Rh complexes catalyze the regioselective hydrogenation of carbonyl groups, whereas neutral complexes are not active.149 Cis-Alkenes are hydrogenated preferentially on bipyridyl-Pd(II) acetate intercalated in montmorillonite.150 The same catalyst was also used for the reduction of nitrobenzene.151... 

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