Search results for " Hydrogenation"
showing 10 items of 45 documents
Synthese und Eigenschaften molekulareinheitlicher n-Paraffine bis zum C140H282
1972
Die Umsetzung von α,ω-Dihalogenalkanen mit Natrium fuhrt nach anschliesender katalytischer Hydrierung zu einem Paraffingemisch mit diskontinuierlicher Molekulargewichtsverteilung. So enthalt das aus 1.10-Dibromdecan hergestellte Produkt nur Paraffine mit 10, 20, 30 usw. C-Atomen, ein aus 1.20-Dibromeicosan hergestelltes Produkt dagegen nur die Paraffine mit 20, 40, 60 usw. C-Atomen. Diese Paraffingemische wurden gelchromatographisch in die molekulareinheitlichen Verbindungen zerlegt und Paraffine bis C140H282 isoliert. Am Beispiel des C70H142 wurde die Temperaturabhangigkeit der Rontgenkleinwinkelstreuung gemessen. Aus Intensitat und Lage der Langperiodenreflexe liesen sich die Anderungen v…
DFT studies on catalytic properties of isolated and carbon nanotube supported Pd9 cluster. Part II. Hydro-isomerization of butene isomers
2010
The processes involved in the butene hydro-isomerization, occurring on a small palladium cluster in the presence of dissociated hydrogen, have been investigated by means of DFT and DFT/MM approaches. This study has been performed both on an isolated (unsupported) Pd(9) cluster and on the same cluster when it is supported on a portion of a single-walled armchair(6,6) carbon nanotube. The study follows another investigation which has already been published concerning the adsorption, fragmentation and diffusion of hydrogen on the same metal cluster. The main aspects involved in the parallel reaction steps of the whole hydro-isomerization mechanisms are not strongly affected by the presence of …
Functionalized 2-azabicyclo[3.3.1]nonanes. IV. synthesis of the indolo[3,2-f]morphan system.
1982
Abstract A short route to the 2-azabicyclo[3.3.1]nonan-7-one system is described. Condensation of 4-piperidones with diethyl 2-oxopropylphosphonate, followed by catalytic hydrogenation furnished the corresponding piperidylpropanones 6 which were cyclized with mercuric acetate in acetic acid to the target target bicyclic ketones 1 . The Fischer indole synthesis from 1 a afforded regioselectively the indole [3,2-f]morphan 2 , a new heteromorphan type.
Supramolecular hydrogen-bonding tautomeric sulfonamido-phosphinamides: a perfect P-chirogenic memory
2011
P-chirogenic, supramolecular hydrogen-bonding C1-symmetrical sulfonamido–phosphinamides (METAMORPhos) have been successfully prepared. They were all found to possess a characteristic prototropic equilibrium between the PIII and the PV tautomers that is slow on the NMR spectroscopic timescale. Despite the dynamic and reversible protonation of the P centre, the P-chirogenic information was found to be retained in the tautomerization process, even in a protic solvent environment. Several strategies to access the corresponding enantiopure compounds were investigated, such as diastereoselective crystallization, or enantioselective synthesis. It was possible to resolve such a class of chiral liga…
Gas-phase hydrogenation of propionitrile on copper-lanthanide oxides
2009
Abstract The hydrogenation of propionitrile on copper-lanthanide oxide catalysts (2Cu·CeO 2 and 4Cu·Ln 2 O 3 (Ln = La, Pr, Nd)) was studied in the gas phase. The activity of the catalysts varies with the lanthanide in the order 2Cu·CeO 2 > 4Cu·Pr 2 O 3 > 4Cu·La 2 O 3 ≥ 4Cu·Nd 2 O 3 , while the activation energies varies in the opposite order, except for 2Cu·CeO 2 . The main product was the primary amine, n -propylamine. The formation of the unstable imine CH 3 CH 2 N CHCH 3 as a major product over 2Cu·CeO 2 seems to be consistent with the acidity of the catalyst. The catalysts were more selective than conventional copper impregnation catalysts, Cu (10 wt.%) on SiO 2 , La 2 O 3 or CeO 2 ,…
Optically Active Titanium Complexes Containing Linked Amido‐cyclopentadienyl Ligands: Their Use as Asymmetric Hydrogenation Catalysts
1996
Optically active titanium complexes of the formula Ti(η5:η1−C5R4SiMe2NCHMePh)Cl2 (R = H, Me), containing the cyclopentadienyl ligand linked to a chiral 1-phenylethylamido moiety, were synthesized and characterized in both enantiomerically pure forms. A single-crystal X-ray structural analysis of (S)()Ti(η5:η1−C5H4SiMe2NCHMePh)Cl2 shows a conformation in which the phenyl group is turned away from the metal center. NOE measurements suggest that a related structure is retained in solution. Upon activation with n-butyllithium, these complexes show hydrogenation activity toward imines with slight enantioselectivity.
Atomically Precise, Thiolated Copper–Hydride Nanoclusters as Single-Site Hydrogenation Catalysts for Ketones in Mild Conditions
2019
Copper-hydrides are known catalysts for several technologically important reactions such as hydrogenation of CO, hydroamination of alkenes and alkynes, and chemoselective hydrogenation of unsaturated ketones to unsaturated alcohols. Stabilizing copper-based particles by ligand chemistry to nanometer scale is an appealing route to make active catalysts with optimized material economy; however, it has been long believed that the ligand-metal interface, particularly if sulfur-containing thiols are used as stabilizing agent, may poison the catalyst. We report here a discovery of an ambient-stable thiolate-protected copper-hydride nanocluster [Cu25H10(SPhCl2)18]3- that readily catalyzes hydrogen…
Superior Fischer-Tropsch performance of uniform cobalt nanoparticles deposited into mesoporous SiC
2020
Electrochemically-derived well-crystalline mesoporous silicon carbide (pSiC) was used as a host for cobalt nanoparticles to demonstrate superior catalytic performance during the CO hydrogenation according to Fischer-Tropsch. Colloidal Co nanoparticles (9 ± 0.4 nm) were prepared independently using colloidal recipes before incorporating them into pSiC and, for comparison purposes, into commercially available silica (Davisil) as well as foam-like MCF-17 supports. The Co/pSiC catalyst demonstrated the highest (per unit mass) catalytic activity of 117 µmol.g(CO)-1.g-1(Co).s-1 at 220 °C which was larger by about one order of magnitude as compared to both silica supported cobalt catalysts. Furthe…
Asymmetric hydrogenation of ethyl pyruvate over aqueous dispersed Pt nanoparticles stabilized by a cinchonidine-functionalized β-cyclodextrin
2021
International audience; Cinchonidine-functionalized β-cyclodextrin was used as stabilizing agent for platinum nanoparticles dispersed in water, but also as chiral modifier for the asymmetric hydrogenation of ethyl pyruvate at 30 °C under 40 bar of hydrogen. This functionalized cyclodextrin allowed getting more stable, more catalytically active and also more enantioselective Pt nanoparticles compared to control catalytic systems. NMR and MALDI-MS analyses clearly showed the reduction of the vinyl group of the cinchonidine graft during the nanoparticles preparation. Under hydrogen pressure, the hydrogenation of the quinolinic moiety was also proven and can be responsible for the difficul…
Enantioselective Synthesis of Tetrahydroprotoberberines and Bisbenzylisoquinoline Alkaloids from a Deprotonated α-Aminonitrile
2011
Under controlled conditions, 6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline-1-carbonitrile can be quantitatively deprotonated in the α-position. Its alkylation directly furnishes 3,4-dihydroisoquinolines which can serve as starting materials for the preparation of various alkaloids. Here, the preparation of the benzylisoquinolines (+)-laudanidine, (+)-armepavine, and (+)-laudanosine as well as the tetrahydroprotoberberines (-)-corytenchine and (-)-tetrahydropseudoepiberberine using Noyori's asymmetric transfer hydrogenation are described. The dimeric alkaloids (+)-O-methylthalibrine and (+)-tetramethylmagnolamine were obtained from nonracemic precursors in Ullmann diaryl ether syntheses.