Heterogeneous asymmetric hydrogenation of ethyl pyruvate on chirally modified Pt/Al2O3 catalyst with fixed-bed reactor

The enantioselective hydrogenation of ethyl pyruvate on the cinchonidine modified Pt/Al2O3 catalyst was investigated using a high-pressure reaction system with a fixed-bed reactor for the purpose to produce the,chiral product without separating the catalyst from the reaction system. The reaction was also investigated in a batch reactor for comparison. About 60% e. e. and 90% e. e. were obtained with the fixed-bed reactor and the batch reactor respectively, demonstrating the possibility for the heterogeneous asymmetric hydrogenation in the fixed-bed reactor. Some adsorbed chiral modifier, cinchonidine, can be slowly removed from the surface of Pt/Al2O3 under the continuous flow reaction, as a result, the e, e, values drops with the reaction time in the fixed-bed reactor. The enantio-selectivity is higher in the fixed-bed reactor, but lower in the batch reactor when ethanol was used as solvent than that when acetic acid as solvent. CO was used as molecular probe to characterize the adsorption of cinchonidine an the catalyst surface by IR spectroscopy, A red shift observed in IR spectra of coadsorbed CO with cinchonidine suggests that the cinchonidine adsorption is mainly through the pi -interaction with platinum surface and donating electron to the platinum surface.

Extremely active catalysts for the hydrogenation of terminal alkenes

Titanocene complexes combined with nanometer-size sodium hydride are extremely active and selective catalysts for the hydrogenation of terminal alkenes under normal pressure. The initial turnover frequencies (TOFinitial) may reach 100-300 s(-1) in the hydrogenation of 1-hexene. The highest catalytic efficiency turnover (TO) reaches 1.5 x 10(5) in 2 h for the hydrogenation of styrene. These catalytic systems exhibit specific selectivity toward alkene substrates. Only terminal alkenes can be hydrogenated. No isomerization of carbon-carbon double bonds occurs during hydrogenation. A suitable substituent on the cyclopentadienyl ring of titanocene and the use of nanometric sodium hydride are key factors in the high efficiency of these catalytic systems. (C) 2002 Elsevier Science.

A remarkable synergic effect of water-soluble bimetallic catalyst in the hydrogenation of aromatic nitrocompounds

Hydrogenation of nitrobenzene can be catalyzed by the water-soluble catalyst PdCl2(TPPTS)(2) (TPPTS = tris(m-sulfonatophenyl)phosphine trisodium salt) under normal pressure at 65 degrees C in H2O/toluene biphasic solvent system. The exhibits higher catalytic activity and selectivity for the hydrogenation of aromatic nitrocompounds, compared with PdCl2(TPPTS)(2) or H2PtCl6 alone. The transmission electron micrographs demonstrate that the monometallic catalyst is composed of ultrafine palladium particles of almost uniform size while the particles of bimetallic catalyst are more widely distributed in size than those of the monometallic ones. (C) 1999 Elsevier Science B.V. All rights reserved.

Simultaneous hydrodesulfurization of thiophene and hydrogenation of cyclohexene over dimolybdenum nitride catalysts

A series of unsupported dimolybdenum nitride (gamma-Mo(2)N) catalysts differing in surface area were prepared by temperature programmed reduction of MoO(3) with a mixture of NH(3):N(2) (90:10). Characterization of catalysts by BET, XRD, TPR and XPS techniques was carried out. The samples were used as catalysts in hydrotreating reactions (simultaneous hydrodesulfurization of thiophene and hydrogenation of cyclohexene). Low surface area gamma-Mo(2)N materials show much higher specific conversions than those with higher surface area. These results indicate that HDS and HYD reactions over gamma-Mo(2)N seem to be structure-sensitive. The relative exposure extent of crystalline planes (111) and (200) over the different catalysts can be associated with their hydrogen adsorption capacities and with their catalytic performances. The catalytic activities are significantly affected by the catalyst pretreatment conditions. (C) 1999 Elsevier Science B.V. All rights reserved.