Lanthanum catalysts

The catalytic activity of a lanthanum (R)-BINOL complex tethered either on silica (62a) or MCM-41 (62b) was evaluated for the enantioselective nitroaldol reaction of cyclohexanecarboxaldehyde (Se), hexanal (Sf), iso-butyraldehyde (Sg) and hydro-cinnamaldehyde (Sh) with nitromethane inTHF (Scheme 12.22) [166]. The silica-anchored lanthanum catalyst 62a gave 55-76% e.e. and yields up to 87%, while the PMS-immobilized catalyst 62b revealed slightly higher e.e.s (57-84%) for the same aldehydes. The homogeneous counterparts showed similar catalytic performance, albeit within a shorter reaction time. The increased enantioselectivity observed for the MCM-41 hybrid catalyst 62b was explained by transformations inside the channels, which is also reflected by lower yields due to hindered diffusion. The recyclability of the immobilized catalysts 62b was checked with hydrocin-namaldehyde (Ph). It was found that the reused catalyst gave nearly the same enantioselectivities after the fourth catalytic run, although the time period for achieving similar conversion increased from initially 30 to 42 h. 

This type of chiral lanthanum catalyst was found to be applicable for epoxidation of a range of enone substrates. Thus 35 was converted to 36 with 86% ee and in 93% yield, and 37 was transformed to 38 with 85% ee in 85% yield (Table 2, entries 1,4, and 6). The enantioselectivity of the asymmetric epoxidations could be substantially improved by the use of (/ )-3-hydroxymethyl-BINOL (32) instead of 17 (Table 2, entries 2, 3, 5, and 7). Namely, 34, 36, and 38 were obtained in excellent yields with 91, 94, and 83% ee, respectively. 

Lanthanum catalysts were generated by Shibasaki and coworkers from lithium binaphthoxide and LaCl3 in the presence of NaOH and water [847, 848, 849], These reagents catalyze asymmetric nitroaldol reactions with a good enantioselec-tivity, but are less efficient in promoting asymmetric additions of dialkylphosphites to aldehydes [850],... 

Scheme 8 Catalytic asymmetric Michael addition reactions of nitroethane to nitroalkenes promoted by a lanthanum catalyst...

Two samples of poly D, L-lactic acid (lot 931040201 L/D=50/50, Lanthanum catalyst and lot 930500201, L/D=98/2, Tin catalyst) were procured from DuPont... 

Fig. 16 Stereomodel for enantioselective hydroamination/cyclization using bisoxazolinate lanthanum catalyst 58 [219]. The structure of the bisoxazolinate ligand is simplified for clarity...

Scheme 5.18 Multitopic ligands 27 employed for the generation of heterogeneous lanthanum catalysts 35.

The base-catalyzed reaction of acetaldehyde with excess formaldehyde [50-00-0] is the commercial route to pentaerythritol [115-77-5]. The aldol condensation of three moles of formaldehyde with one mole of acetaldehyde is foUowed by a crossed Cannizzaro reaction between pentaerythrose, the intermediate product, and formaldehyde to give pentaerythritol (57). The process proceeds to completion without isolation of the intermediate. Pentaerythrose [3818-32-4] has also been made by condensing acetaldehyde and formaldehyde at 45°C using magnesium oxide as a catalyst (58). The vapor-phase reaction of acetaldehyde and formaldehyde at 475°C over a catalyst composed of lanthanum oxide on siHca gel gives acrolein [107-02-8] (59). 

Catalysts used for preparing amines from alcohols iaclude cobalt promoted with tirconium, lanthanum, cerium, or uranium (52) the metals and oxides of nickel, cobalt, and/or copper (53,54,56,60,61) metal oxides of antimony, tin, and manganese on alumina support (55) copper, nickel, and a metal belonging to the platinum group 8—10 (57) copper formate (58) nickel promoted with chromium and/or iron on alumina support (53,59) and cobalt, copper, and either iron, 2iac, or zirconium (62). 

Reduction of sulfur dioxide by methane is the basis of an Allied process for converting by-product sulfur dioxide to sulfur (232). The reaction is carried out in the gas phase over a catalyst. Reduction of sulfur dioxide to sulfur by carbon in the form of coal has been developed as the Resox process (233). The reduction, which is conducted at 550—800°C, appears to be promoted by the simultaneous reaction of the coal with steam. The reduction of sulfur dioxide by carbon monoxide tends to give carbonyl sulfide [463-58-1] rather than sulfur over cobalt molybdate, but special catalysts, eg, lanthanum titanate, have the abiUty to direct the reaction toward producing sulfur (234). 

B lanthanum concentrate. La—Ln chloride FCC catalysts b minor component... 

This tread has iaflueaced the supply and availability of cerium, particularly ia comparison to the availability of lanthanum-rich cerium-poor materials. The iacrease ia La demand for ECC catalysts up to the mid-1980s, together with the need to separate out cerium ia order to make the La-rich Ce-poor compositions increasingly preferred, led to a glut of Ce-based raw materials at that time. Ia 1991, the La-rich Ce-poor portioa of the raw material was ia excess supply over demand. 

Polyisoprenes of 94—98% as-1,4 content were obtained with lanthanum, cerium, praseodymium, neodymium, and other rare-earth metal ions (eg, LnCl ) with trialkyl aluminum (R3AI) (34). Also, a NdCl 2THF(C2H3)3A1 catalyst has been used to prepare 95% <7j -l,4-polyisoprene (35). <7j -l,4-Polyisoprene of 98% as-1,4 and 2% 3,4 content was obtained with organoalurninum—lanthariide catalysts, NdCl where L is an electron-donor ligand such as ethyl alcohol or butyl alcohol, or a long-chain alcohol, and is 1 to 4 (36). 

The relatively high cost and lack of domestic supply of noble metals has spurred considerable efforts toward the development of nonnoble metal catalysts for automobile exhaust control. A very large number of base metal oxides and mixtures of oxides have been considered, especially the transition metals, such as copper, chromium, nickel, manganese, cobalt vanadium, and iron. Particularly prominent are the copper chromites, which are mixtures of the oxides of copper and chromium, with various promoters added. These materials are active in the oxidation of CO and hydrocarbons, as well as in the reduction of NO in the presence of CO (55-59). Rare earth oxides, such as lanthanum cobaltate and lanthanum lead manganite with Perovskite structure, have been investigated for CO oxidation, but have not been tested and shown to be sufficiently active under realistic and demanding conditions (60-63). Hopcalities are out-... 

The catalyst was prepared by impregnating porous alumina particles with a solution of nickel and lanthanum nitrates. The metal loading was 20 w1% for nickel and 10 wt% for lanthanum oxide. The catalyst particles were A group particles [8], whereas they were not classified as the AA oup [9]. The average particle diameter was 120 pm, and the bed density was 1.09 kg m . The minimum fluidization velocity was 9.6 mm s. The settled bed height was around 400 mm. The superficial gas velocity was 40-60 mm s. The reaction rate was controlled by changing the reaction temperature. 

To finish with another trend for NO removal consisting in NO direct decomposition, we would like to depict the infrared study of NO adsorption and decomposition over basic lanthanum oxide La203 [78], In this case, the basic oxygens are proposed to lead to N02 and N03 spectator species, whereas the active sites for effective NO decomposition are described as anion vacancies, which are often present in transition metal oxides. This last work makes the transition with the study of DeNO, catalysts from the point of view of their ability to transfer electrons, i.e. their redox properties. 

The rare earth oxides of lanthanum, samarium and gadolinium were converted into soluble nitrate salts by dissolving them in the minimum amount of concentrated nitric acid. Then two sets were prepared by adding 2.0 ml of aqueous solution of La(N03)3.6H20 [0.2 M] and 0.01 ml of (n-BuO)4Ti to 25 ml of aqueous solution of Cu(N03)2 [1.0 M]. Similarly, two sets were prepared with Co(N03)3. Same procedures were followed for Sm(N03)3 [0.2 M] and Gd(N03)3 [0.2 M], One set of all these solutions were sonicated under ultrasonic bath (Model - Meltronics, 20 kHz, 250 W) for half an hour. The solutions prepared in normal and sonicated conditions were kept in muffle furnace (Model - Deluxe Zenith) first at 100°C for 2 h and then the temperature of the furnace was raised up to 900°C and calcined for 2 h. The solid composites prepared were then cooled to room temperature and treated as catalyst for phenol degradation. 

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