Supported catalytic hydrogenation

Dinitrotoluenes can be catalytically hydrogenated to toluenediamines under a wide variety of temperatures, pressures, and solvents the catalyst can be supported noble metal, eg, Pd/C or nickel, either supported or Raney type. The reduction requires six moles of hydrogen per mole of DNT and produces four moles of water. 

The low yields of 6,6 -disubstituted-2,2 -bipyridincs recorded in Table I are probably the result of steric retardation of the adsorption of 2-substituted pyridines. This view is supported by the observation that 2-methylpyridine is a much weaker poison for catalytic hydrogenations than pyridine. On the other hand, the quinolines so far examined (Table II) are more reactive but with these compounds the steric effect of the fused benzene ring could be partly compensated by the additional stabilization of the adsorbed species, since the loss of resonance energy accompanying the localization of one 71-electron would be smaller in a quinoline than in a pyridine derivative. 

The literature on catalytic hydrogenation is very extensive, and it is tempting to think that after all this effort there must now exist some sort of cosmic concept that would allow one to select an appropriate catalyst from fundamentals or from detailed knowledge of catalyst functioning. For the synthetic chemist, this approach to catalyst selection bears little fruit. A more reliable, quick, and useful approach to catalyst selection is to treat the catalyst simply as if it were an organic reagent showing characteristic properties in its catalytic behavior toward each functionality. For this purpose, the catalyst is considered to be only the primary catalytic metal present. Support and... 

There are several sources of potential danger in catalytic hydrogenations these are failure of equipment because of excessive pressures, solvent fires, explosions and fires from mixtures of hydrogen in air, and, with finely divided carbon supports, dust explosions. None of these should cause concern, for all may be avoided easily. 

It can be summarized from the available data in Table 3 that supported palladium catalysts selectively hydrogenated carbon-carbon double bonds in the presence of the nitrile group in NBR. However, there is no detailed fundamental study on heterogeneous catalytic hydrogenation of nitrile rubber in the literature that can provide an insight into the reaction. The available information is limited since most of the literature is patented. 

The reactor system works nicely and two model systems were studied in detail catalytic hydrogenation of citral to citronellal and citronellol on Ni (application in perfumery industty) and ring opening of decalin on supported Ir and Pt catalysts (application in oil refining to get better diesel oil). Both systems represent very complex parallel-consecutive reaction schemes. Various temperatures, catalyst particle sizes and flow rates were thoroughly screened. 

The most widely used method for adding the elements of hydrogen to carbon-carbon double bonds is catalytic hydrogenation. Except for very sterically hindered alkenes, this reaction usually proceeds rapidly and cleanly. The most common catalysts are various forms of transition metals, particularly platinum, palladium, rhodium, ruthenium, and nickel. Both the metals as finely dispersed solids or adsorbed on inert supports such as carbon or alumina (heterogeneous catalysts) and certain soluble complexes of these metals (homogeneous catalysts) exhibit catalytic activity. Depending upon conditions and catalyst, other functional groups are also subject to reduction under these conditions. 

In continuation of a previous work (1), catalytic hydrogenation of cinnamaldehyde has been studied in slurry phase using a high-pressure autoclave. A series of carbon powder (CP)-supported Pt catalysts with widely varying Pt dispersion and Pt location on the support has been used in the study. The purpose has been to find out how the location of the metal on the support and its dispersion affect the two parallel reaction paths, namely the hydrogenation of the C=0 and C=C bonds. 

Three-phase slurry reactors are commonly used in fine-chemical industries for the catalytic hydrogenation of organic substrates to a variety of products and intermediates (1-2). The most common types of catalysts are precious metals such as Pt and Pd supported on powdered carbon supports (3). The behavior of the gas-liquid-sluny reactors is affected by a complex interplay of multiple variables including the temperature, pressure, stirring rates, feed composition, etc. (1-2,4). Often these types of reactors are operated away from the optimal conditions due to the difficulty in identifying and optimizing the critical variables involved in the process. This not only leads to lost productivity but also increases the cost of down stream processing (purification), and pollution control (undesired by-products). 

We recently reported that Cu/Si02 is an effective catalyst for the hydrogenation of cyclohexanones under very mild experimental conditions. Thus, a series of cyclohexanones with different substituents, including 3-oxo-steroids, could be reduced under 1 atm of H2 at 40-90°C, with excellent selectivity (5). The catalyst is non-toxic and reusable. This prompted us to investigate the reduction of cyclohexanones over a series of supported copper catalysts under hydrogen transfer (h.t.) conditions (2-propanol, N2, 83 °C) and to compare the results with those obtained under catalytic hydrogenation (n-heptane, 1 atm H2, 40-90°C) conditions. Here we report the results obtained in the hydrogenation of 4-tert-butyl-cyclohexanone, a molecule whose reduction,... 

If we compare these productivities with those obtained under catalytic hydrogenation conditions (Table 2, Figure 3), we can see that the trend is different Cu/MgO shows very low activity, particularly if compared with that of the catalyst supported on silica and modified silicas. 

The type of catalyst strongly influences the enantioselectivity of heterogeneous catalytic hydrogenations (1). In the enantioselective saturation of the C=C bond of isophorone over (-)-dihydroapovincaminic acid ethyl ester ((-)-DHVIN) modified Pd catalysts (scheme 1) the optical purity strongly depended on the type and properties of the support used (2, 3, 4). 

In a somewhat different approach, supported-aqueous-phase-catalysts (SAPC, see Chapter 5, Section 5.2.5 of this book) have been combined with supercritical CO2 in catalytic hydrogenation [55], Ruthenium was supported on silica and combined with the ligand TPPTS in water, after which a scC02/H2 phase was applied together with the substrate. Better levels of conversion were obtained using scC02 than the equivalent system with toluene for the hydrogenation of cinnamaldehyde. 

Some general reviews on hydrogenation using transition metal complexes that have appeared within the last five years are listed (4-7), as well as general reviews on asymmetric hydrogenation (8-10) and some dealing specifically with chiral rhodium-phosphine catalysts (11-13). The topic of catalysis by supported transition metal complexes has also been well reviewed (6, 14-29), and reviews on molecular metal cluster systems, that include aspects of catalytic hydrogenations, have appeared (30-34). 

These results establish catalytic hydrogenation as a powerful and mechanistically novel means of catalytic C-C bond formation, and support the feasibility... 

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