Rhodium on aluminum oxide

For example, the reaction of nitronates (123) with a zinc copper pair in ethanol followed by treatment of the intermediate with aqueous ammonium chloride a to give an equilibrium mixture of ketoximes (124) and their cyclic esters 125. Heating of this mixture b affords pyocoles (126). Successive treatment of nitronates (123) with boron trifluoride etherate and water c affords 1,4-diketones (127). Catalytic hydrogenation of acyl nitronates (123) over platinum dioxide d or 5% rhodium on aluminum oxide e gives a-hydroxypyrrolidines (128) or pyrrolidines 129, respectively. Finally, smooth dehydration of a-hydroxypyrrolidines (128) into pyrrolines (130f) can be performed. 

We begin with the structure of a noble metal catalyst. The emphasis is on the preparation of rhodium on aluminum oxide and the nature of the metal-support interaction. Next we focus on a promoted surface in a review of potassium on noble metals. This section illustrates how single crystal techniques have been applied to investigate to what extent promoters perturb the surface of a catalyst. The third study deals with the sulfidic cobalt-molybdenum catalysts used in hydrotreating reactions. Here we are concerned with the composition and structure of the catalytically active... 

In a lOOmL round-bottomed flask equipped with a magnetic stirrer bar were placed (7/f)-2-chloro-7-isopropyl-6,7-dihydro-5//-l-pyrindine (1.28 g), distilled methanol (16.5 mL), distilled ethyl acetate (16.5 mL) and rhodium on aluminum oxide (64.0 mg). The flask was connected to a hydrogen balloon and flushed with hydrogen. 

Rhodium on aluminum oxide is characterized by active isomerization of methyl-cyclohexane with contraction of the ring to 1,2- and 1,3-dimethylcyclopentanes. It was found that this reaction increases with increasing pressure, other conditions being equal. 

Catalytic hydrogenation of 1 in the presence of rhodium on aluminum oxide proceeds smoothly to afford (5)-hexahydromandelic acid (3) [2]. Subsequent treatment of 3 with ethyllithium provides in 75% yield the ketone 4, which is 0-silylated to afford 5. Generated in situ with the appropriate dialkylboron triflate and 5, the boron enolates 6a—c react with a variety of aldehydes to provide exclusively a mixture of syn-d o products 7 and 8 in 70-80% yields, often with excellent stereoselectivities. 

For a simple example of heterogeneous catalysis, think of the catalytic converter in your car. It s made of a platinum-rhodium alloy that is finely deposited on aluminum oxide (specifically y-alumina) to decompose nitrogen oxides to less toxic nitrogen, as well as promote the combination of O2 with toxic CO and hydrocarbons to form CO2. 

The search is on for catalysts to replace those containing toxic heavy metals. The addition of hydrogen chloride to acetylene to form vinyl chloride is catalyzed by mercuric chloride. Rhodium (III) chloride on activated carbon works just as well and is much less toxic 97 It should be tried also in other addition reactions of acetylene as well as in trans-esteriflcation reactions of vinyl acetate. The reduction of 2 ethyl-2-hexenal to 2-ethylhexanol can be catalyzed by a mixture of copper, zinc, manganese, and aluminum oxides in 100% yield.98 This is said to be a replacement for carcinogenic copper chromite. In Reaction 4.15, the amount of toxic chromium(II) chloride has been reduced from stoichiometric to catalytic (9-15 mol% chromium(II) chloride) by the addition of manganese metal.99... 

In general the reduction of a pyridine side-chain acid or ester using platinum oxide, Raney Nickel, rhodium-on-carbon, rhodium-on-alumina, or ruthenium oxide as the catalyst gives the piperidine acid or ester. Partial reduction of the pyridine ring to a tetrahydropyridine usually occurred when palladium-on-carbon was employed as the catalyst, although two exceptions were reported. Either a mixture of the piperidine and the tetrahydropyridine ester or the tetrahydropyridine ester alone was formed when sodium borohydride was used at room temperature in the reduction of pyridine side-chain ester salts. When the free bases were employed, reduction of the ester group occurred instead of nuclear reduction. The use of lithium aluminum hydride gave the same results (see Table XI-18). Many acetamides... 

Gasolines contain a small amount of sulfur which is emitted with the exhaust gas mainly as sulfur dioxide. On passing through the catalyst, the sulfur dioxide in exhaust gas is partially converted to sulfur trioxide which may react with the water vapor to form sulfuric acid (1,2) or with the support oxide to form aluminum sulfate and cerium sulfate (3-6). However, sulfur storage can also occur by the direct interaction of SO2 with both alumina and ceria (4,7). Studies of the oxidation of SO2 over supported noble metal catalysts indicate that Pt catalytically oxidizes more SO2 to SO3 than Rh (8,9) and that this reaction diminishes with increasing Rh content for Pt-Rh catalysts (10). Moreover, it was shown that heating platinum and rhodium catalysts in a SO2 and O2 mixture produces sulfate on the metals (11). 

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