Alumina-montmorillonite

The strong adsorption of pyrethroids for minerals, especially minerals coated with natural organic matter such as are found in soils, is illustrated in our studies by the behaviour of tefluthrin. Thus Figure 9.3 shows sorption of tefluthrin onto organic-free kaolinite, alumina (aluminium oxide) and montmorillonite. Clearly the sorptive capacity of the minerals varies in the order montmorillonite > alumina > kaolinite but all three... 

Aluminum chlorite, (Al,Fe)4(Si,Al)402Q(0H)g, in which a gibbsitelike interlayer proxies in part for the bmcitelike interlayer, is being discovered in increasing occurrences and abundance (11,141). Chloritelike stmctures have been synthesi2ed by precipitation of Mg and Al between montmorillonite sheets (143). Cookite [1302-92-7], an aluminous chlorite containing lithium, has been found in high alumina refractory clays and bauxite [1318-16-7] (139). 

A broad study on the MW-assisted Diels Alder reactions of 2H-pyran-2-ones 50 and 51 with 1,4-naphthoquinone 52 and N-phenylmaleimide 53 (Equations 4.3) supported on silica-gel, K-10 montmorillonite, fitrol and alumina was carried out by Samant and colleagues [41]. 

The synthesis of imidazoles is another reaction where the assistance of microwaves has been intensely investigated. Apart from the first synthesis described since 1995 [40-42], recently a combinatorial synthesis of 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted imidazoles has been described on inorganic solid support imder solvent-free conditions [43]. Different aldehydes and 1,2 dicarbonyl compounds 42 (mainly benzil and analogues) were reacted in the presence of ammonium acetate to give the trisubstituted ring 43. When a primary amine was added to the mixture, the tetrasubstituted imidazoles were obtained (Scheme 13). The reaction was done by adsorption of the reagent on a solid support, such as silica gel, alumina, montmorillonite KIO, bentonite or alumina followed by microwave irradiation for 20 min in an open vial (multimode reactor). The authors observed that when a non-acid support was used, addition of acetic acid was necessary to obtain good yields of the products. 

Experiments were carried out using isotopically labelled methanol (97% 0) and ethanol (98% purchased from MSD Isotopes. Anhydrous isobutanol was purchased from Aldrich Chemical Co., Inc. and contained the natural abimdances of orygen isotopes, i.e. 99.8% and 0.2% O. Nafion-H was obtained fi om C. G. Processing, Inc. and Amberlyst resins were provided by Rohm and Haas. The 2SM-5 zeolite was provided by Mobil Research Development Corp. H-Mordenite, montmorillonite K-10, and silica-alumina 980 were obtained firom Norton, Aldrich, and Davison, respectively. y-AIumina was prepared from Catapal-B fi om Vista. 

A new synthetic route for functionalized polyhydroxyalkyl-pyrimidines starting from unprotected aldoses and based on montmorillonite K-10 catalysis and solvent-free microwave irradiation conditions, has been reported by Yadav et al,m Thus, reaction of D-glucose and D-xylose with semicarbazide or thiosemicarbazide (186) in the presence of montmorillonite K-10, under microwave irradiation, proceeded via domino cycloisomerization, dehydrazination, and dehydration of the intermediate semi- or thiosemicarbazones (187) to afford l,3-oxazin-2-ones or l,3-oxazine-2-thiones (188) in one single step and in yields between 79% and 85% (Scheme 34). Other mineral catalysts tested, such as silica gel and basic alumina, were far less effective for this transformation and only silica gel was active at all, giving low yields (15-28%) of compounds 188a-d. The l,3-oxazin-2-ones(thiones) thus synthesized were subsequently converted into the target pyrimidines by reaction with aromatic... 

Alumina, silica, clays, and zeolites are increasingly used as acidic or basic supports [26], Cycloaddition reactions often require Lewis-acid catalysts if good yields are to be obtained. Clay and doped silica gel catalysts have emerged as useful alternatives to the use of Lewis acids. Cycloaddition offuran (5) under solvent-free conditions, catalyzed by K10 montmorillonite, results in a decrease in the reaction time the endo-exo relationship is no different that obtained by use of classical heating (Scheme 9.2) [27]. 

Reaction of pyrones under dassical conditions requires the use of high temperatures to obtain low to moderate yields. The Diels-Alder reaction of pyrones has been performed in a commercial microwave oven under solvent-free conditions on solid supports such as silica gel, montmorillonite, fitrol clay and alumina. The reaction time was dramatically reduced - from 4 h to 4 min (Scheme 9.9) [50],... 

In 1990, Choudary [139] reported that titanium-pillared montmorillonites modified with tartrates are very selective solid catalysts for the Sharpless epoxidation, as well as for the oxidation of aromatic sulfides [140], Unfortunately, this research has not been reproduced by other authors. Therefore, a more classical strategy to modify different metal oxides with histidine was used by Moriguchi et al. [141], The catalyst showed a modest e.s. for the solvolysis of activated amino acid esters. Starting from these discoveries, Morihara et al. [142] created in 1993 the so-called molecular footprints on the surface of an Al-doped silica gel using an amino acid derivative as chiral template molecule. After removal of the template, the catalyst showed low but significant e.s. for the hydrolysis of a structurally related anhydride. On the same fines, Cativiela and coworkers [143] treated silica or alumina with diethylaluminum chloride and menthol. The resulting modified material catalyzed Diels-Alder reaction between cyclopentadiene and methacrolein with modest e.s. (30% e.e.). As mentioned in the Introduction, all these catalysts are not yet practically important but rather they demonstrate that amorphous metal oxides can be modified successfully. 

Commercial synthetic catalysts are amorphous and contain more silica than is called for by the preceding formulas they are generally composed of 10 to 15% alumina (AI2O3) and 85 to 90% silica (Si02). The natural materials—montmorillonite, a nonswelling bentonite, and halloysite—are hydrosilicates of aluminum, with a... 

The low H/C-ratio of FCC feed derived from liquefied biomass led to low conversion and poor gasoline selectivity. Addition of alumina to the matrix resulted in a catalyst more active for heavy oil cracking but with a poor selectivity. Alumina-montmorillonite catalysts showed activities for heavy oil cracking comparable to that of a conventional, zeolite based, cracking catalyst. Effects of matrix composition and zeolite type on the heavy oil cracking performance are discussed. 

Table VIII. Catalytic cracking over alumina-montmorillonite complexes...

The importance of diffusion enhancement to heavy oil cracking is further illustrated by the alumina-montmorillonite complexes which crack heavier feeds, i.e. Wilmington fraction No. 6, more effectively than REY. When used as matrices for REY, the alumina-montmorillonites results in considerably more active catalysts, at the same zeolite content, compared with a catalyst having a kaolin-binder matrix, while the selectivity properties differs very little between the two types of catalysts (Sterte, 3. Otterstedt, 3-E. Submitted to Appl.Catal.). 

Rare-earth exchanged [Ce ", La ", Sm"" and RE (RE = La/Ce/Pr/Nd)] Na-Y zeolites, K-10 montmorillonite clay and amorphous silica-alumina have also been employed as solid acid catalysts for the vapour-phase Beckmann rearrangement of salicylaldoxime 245 to benzoxazole 248 (equation 74) and of cinnamaldoxime to isoquinoline . Under appropriate reaction conditions on zeolites, salicyl aldoxime 245 undergoes E-Z isomerization followed by Beckmann rearrangement and leads to the formation of benzoxazole 248 as the major product. Fragmentation product 247 and primary amide 246 are formed as minor compounds. When catalysts with both Br0nsted and Lewis acidity were used, a correlation between the amount of Br0nsted acid sites and benzoxazole 248 yields was observed. 

Oxidation of sulfides and sulfoxides using Oxone dispersed on silica gel or alumina was reported . A study of surface mediated reactivity of Oxone compared its reactivity with that of ferf-butyl hydroperoxide. Oxidation of sulfides to sulfones in aprotic solvents mediated by Oxone on wet montmorillonite or clay minerals proceeds in high yields. Interestingly, when Oxone on alumina is applied for selective oxidation of sulfides in aprotic solvents, the product distribution is temperature-dependent and sulfoxides or sulfones are obtained in good to excellent yields (equation 56) . ... 

There has been an enormous technological interest in tertfa/j-butanol (tBA) dehydration during the past thirty years, first as a primary route to methyl te/f-butyl ether (MTBE) (1) and more recently for the production of isooctane and polyisobutylene (2). A number of commercializable processes have been developed for isobutylene manufacture (eq 1) in both the USA and Japan (3,4). These processes typically involve either vapor-phase tBA dehydration over a silica-alumina catalyst at 260-370°C, or liquid-phase processing utilizing either homogenous (sulfonic acid), or solid acid catalysis (e.g. acidic cationic resins). More recently, tBA dehydration has been examined using silica-supported heteropoly acids (5), montmorillonite clays (6), titanosilicates (7), as well as the use of compressed liquid water (8). 

---