Catalysts clay-supported

Another problem that required solving was the moderate yield obtained in the cyclopropanation reaction when only one equivalent of styrene was used. By increasing the amount of styrene up to its use as the reaction solvent, a noticeable effect on the selectivities was observed when laponite was used as the support [58]. The active role of the clay support was definitely estabhshed when the results in homogeneous and heterogeneous phases were compared (Table 9). These effects involved the reversal of the trans preference in solution to the cis preference with the laponite-supported catalyst in styrene, and also a reversal in the absolute configuration of the major cis enantiomer ob-... 

In the case of the reaction between N-acryloyloxazolidin-2-one and cy-clopentadiene, both catalysts showed activities and enantioselectivities similar to those observed in homogeneous phase. However, a reversal of the major endo enantiomer obtained with the immobilized 6a-Cu(OTf)2 catalyst, with regard to the homogeneous phase reaction, was noted. Although this support effect on the enantioselectivity remains unexplained, it resembles the surface effect on enantioselectivity of cyclopropanation reaction with clay supports [58]. 

Clay-supported heteropoly acids such as H3PW12O40 are more active and selective heterogeneous catalysts for the synthesis of MTBE from methanol and tert-butanol, etherification of phenethyl alcohols with alkanols, and alkylation of hydroquinone with MTBE and tert-butanoi (Yadav and Kirthivasan, 1995 Yadav and Bokade, 1996 Yadav and Doshi, 2000), and synthesis of bisphenol-A (Yadav and Kirthivasan, 1997). 

Glycals can be transformed into 1,6-anhydro sugar derivatives by intramolecular cyclization in the presence of Lewis and Brpnsted acids, a reaction that has been termed the intramolecular Ferrier glycosylation.168 Sharma el al.169 showed that a montmorillonite clay-supported silver reagent can be an efficient catalyst for this transformation. The 1,6-anhydro-2,3-dehydro sugars obtained were then selectively dihydroxylated to furnish 1,6-anhydro saccharides. 

The catalyst pretreatment process for both the clay-supported and the reference catalysts consists of loading into the HDS reactor under N2, purging in N2 at 20°C for 30 min at 1000 cmVmin., drying in N2 at 150°C for 60 min and at 400°C for 60 min, and finally sulfiding in a 5% H2S/H2 mixture at 400°C for two hr prior to use as catalysts. The laboratory scale liquid-phase continuous-flow HDS reactor consists of a thick-walled 0.375" ID 316 SS tube, with 1 g catalyst diluted with 5 g tabular alumina (LaRoche T-1061, 10 m2/g) sitting between plugs of quartz wool. Beneath the lower plug is a 0.125" ID, 0.375" OD deadman used to minimize volume between the reactor and the liquid receiver. The liquid test feed consisted of 0.75 wt % sulfur as dibenzothiophene (DBT), dissolved in hexadecane and is representative of a middle distillate oil. All liquid-filled lines were heated to 50°C. The reaction was carried out at 400°C LHSV = 10-40/hr. 

Mesoporous Synthetic Clays Synthesis, Characterizationand Use as HDS Catalyst 417 Supports... 

The first investigations on iron-catalyzed Michael reactions utilized Fe(acac)3 as catalyst. However, this metal complex is itself catalytically almost inactive. Yields of only up to 63% could be achieved, if BF3OEt2 is used as a co-catalyst [55], Polystyrene-bound Fe(acac)3 catalysts were also reported to give yields up to 63% [56], FeCl3 was used as a co-catalyst for clay-supported Ni(II). Yields achieved with this heterogeneous system ranged from 40 to 98% [57]. The double Michael addition of acrylonitrile to ethyl cyanoacetate is smoothly catalyzed by a complex generated from [Fe(N2) (depe)2] [depe = l,2-bis(diethylphosphano)ethane]. At 23 °C and after 36h, an 88% yield is obtained with 1 mol% of this Fe(0) catalyst [58]. 

Bhattacharjee369, who has brominated acetanilide suspended in aqueous solution of potassium bromide and hydrogen peroxide in presence of vanadium pent oxide catalyst. Chloroperoxidase has been mimicked using supported manganese phorphyrin catalyst in the oxychlorination of dimedone370 and by clay-supported iron(III) chloride in the oxy-chlorination of toluene and anisole371. The kinetics and mechanism of the haloper-oxidases have been studied extensively372,373. 

Ni(II)(OAc)2bpy and Co(II)(OAc)2bpy catalyze the Michael addition of nitro-methane, malononitrile, and aniline to a,j8-unsaturated ketones, methyl acrylate, and acrylonitrile in DMF under neutral conditions [116]. FeCls 6H2O is a highly efficient catalyst of Michael reaction of 1,3-dicarbonyl compounds with a,/3-unsaturated ketones under mild and neutral conditions (Sch. 24) [117]. There is literature precedent for this reaction with dual catalysis Ni(II) immobilized on a clay support and FeCl3 to activate the enone [118]. The mechanism proposed for the single-center catalysis involves coordination of the enone to a diketonato complex [119]. The chemo-... 

The use of pillared clays as metal supports has also been reported. The more defined interlamelar spacing available with these supports should give a more predictable shape selectivity to the resulting supported metal catalysts. Further, since the pillars prevent the collapse of the layers on drying and further heating, the pillared clay supported metals salts can be calcined and reduced under conditions that can give the best metal dispersion without any concern for a change in the structure of the support. ... 

The necessity to develop hydrotreating catalysts with enhanced activity stimulates the search for alternative catalyst supports. It was shown that clay-supported transition metal sulfides can efficiently catalyze hydrodesulfurization (HDS) of thiophene [1-3]. However, the large scale application of the catalysts based on natural clays is still hampered, mainly due to the difficulties in controlling the chemical composition and textural properties. Synthetic clays do not suffer from these drawbacks. Recently, a novel non-hydrothermal approach was proposed for the synthesis of some trioctahedral smectites, namely saponite... 

Supported nickel catalysts and catalyst-clay mixtures are commonly used in hydrogenation processes where completely saturated products are desired. In these processes, residual fatty acid can often remain on the catalyst, causing a substanual reduction in both the process yield and catalyst activity. In addition, residual fatty acid content interferes with the recovery of nickel from spent catalyst. As a result, it is highly desirable to remove residual fatty acids from supported nickel catalysts. 

Cornelius, A., and P. Laszlo, Clay Supported Reagents II. Quaternary Ammonium Exchanged Montmorillonite as Catalyst in the Phase Transfer Preparation of Symmetric Formaldehyde Acetals, Synthesis, 162 (1982). 

A wide range of techniques may be employed for the incorporation of a catalytically active component into clay supports. An outline of the two most important techniques is given below as an introduction to later sections in this chapter, which describe the more important chemical and physical factors involved in the dispersion of metal salts onto clays and their influence on the activity and selectivity of the catalyst system. Methods for supporting species onto high surface area materials are described in some detail in Chapter 4. 

Inorganic supported reagents such as clayzic (add-treated clay supported zinc chloride)42,93-95 have a limited but valuable range of applications, notably in Friedel-Crafts benzylations (Figure 4.8), where a remarkable synergism between the individually weakly active components results in a very active catalyst. 

Other metals can be similarly immobilised. Silica- and clay-supported rhodium complexes, for example, are effective hydrogenation catalysts.160,161 An interesting variant on this involves a heteropolyacid to assist the metal-support binding. The heteropolyadd, such as phosphotungstic add, is attached to the support (e.g. montmorillonite) by the indpient wetting technique. The solid material is then treated with a solution of the homogeneous catalyst such as Rh(DiPamp).162... 

Other Friedel-Crafts catalysts are also being developed these include clay-supported metal halides [32] and mesoporous silica supported systems [33], Even enzymes can be used to perform Friedel-Crafts reactions [34]. 

Yadav, G. D., Asthana, N. S., and Kamble, V. S. 2003. Friedel-Craftsbenzoyla-tion of p-xylene over clay-supported catalysts novelty of cesium-substituted dodecatungstophosphoric acid on K-10 clay. Appl. Catal. A General 240 53-69. 

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