Palladium Raney

N-Methyl-p-nitroaniline Nickel Raney Palladium on carbon Calcium sulfate... 

The INS spectrum of hydrogen adsorbed by Raney palladium at 400 mbar corresponded to a mixture of p-PdH (480 cm ) and a-PdH (565 cm ) [27]. After dihydrogen adsorption at a lower pressure, 2 mbar, the INS showed peaks due both to the palladium hydrides and to adsorbed hydrogen. A broad peak at 975 cm" was assigned to the two unresolved vibrations of three-coordinated (Csv) hydrogen [27]. 

H. Jobic, J.P. Candy, V. Perrichon A. Renouprez (1985). J. Chem. Soc. Farad. Trans. I, 81, 1955-1961. Neutron-scattering and volumetric study of hydrogen adsorbed and absorbed on Raney palladium. 

Hydrogenation catalysts Dichlorotris(triphenylphosphine)ruthenium. Iridium. Iridium tetrachloride-Triethyl phosphite. Iridium-BaSO, or CaC04. Lithium aluminum hydride. Nickel catalyst, Raney. Palladium hydroxide. Platinum catalysts. Potassium hydride. Trihydridobis(triphenyIphosphine)iridium (III). 

An Palladium/Aluminium (Raney-Palladium) laBt sich 2-Methyl-furan quantitativ (Normaldruck/150°) zum 2-Methyl-tetrahydrofuran hydrieren6, wahrend sich beim 2-(l-Hydroxy-2-methyl-propyl)-furan am gleichen Katalysator (Normaldruck/250°) der Furan-Ring der Hydrierung widersetzt [man erhalt zu 75% d. Th. 2-(2-Methyl-propyl)-furanb (vgl. Tab. 65 Nr. 14)]. 

Single-bond cleavage with molecular hydrogen is termed hydrogenolysis. Palladium is the best catalyst for this purpose, platinum is not useful. Desulfurizations are most efficiently per-formed with Raney nickel (with or without hydrogen G.R. Pettit, 1962 A or with alkali metals in liquid ammonia or amines. The scheme below summarizes some classes of compounds most susceptible to hydrogenolysis. 

In past years, metals in dilute sulfuric acid were used to produce the nascent hydrogen reductant (42). Today, the reducing agent is hydrogen in the presence of a catalyst. Nickel, preferably Raney nickel (34), chromium or molybdenum promoted nickel (43), or supported precious metals such as platinum or palladium (35,44) on activated carbon, or the oxides of these metals (36,45), are used as catalysts. Other catalysts have been suggested such as molybdenum and platinum sulfide (46,47), or a platinum—nithenium mixture (48). 

Succinic anhydride is manufactured by catalytic hydrogenation of maleic anhydride [108-31-6]. In the most widely used commercial process this reaction is performed in the Hquid phase, at temperatures of 120—180°C and at moderate pressures, in the range of 500—4000 kPa (72—580 psi). Catalysts mentioned in the patent Hterature include nickel (124), Raney nickel (125,126), palladium on different carriers (127,128), and palladium complexes (129). The hydrogenation of the double bond is exothermic Ai/ = —133.89 kJ/mol (—32 kcal/mol) (130). 

Succinic acid can also be produced by catalytic hydrogenation of aqueous solutions of maleic or fumaric acid in the presence of noble metal catalysts, ie, palladium, rhodium, mthenium, or their mixtures, on different carriers (135—139) or on Raney nickel (140). 

Dry reduced nickel catalyst protected by fat is the most common catalyst for the hydrogenation of fatty acids. The composition of this type of catalyst is about 25% nickel, 25% inert carrier, and 50% soHd fat. Manufacturers of this catalyst include Calsicat (Mallinckrodt), Harshaw (Engelhard), United Catalysts (Sud Chemie), and Unichema. Other catalysts that stiH have some place in fatty acid hydrogenation are so-called wet reduced nickel catalysts (formate catalysts), Raney nickel catalysts, and precious metal catalysts, primarily palladium on carbon. The spent nickel catalysts are usually sent to a broker who seUs them for recovery of nickel value. Spent palladium catalysts are usually returned to the catalyst suppHer for credit of palladium value. 

This reaction is favored by moderate temperatures (100—150°C), low pressures, and acidic solvents. High activity catalysts such as 5—10 wt % palladium on activated carbon or barium sulfate, high activity Raney nickel, or copper chromite (nonpromoted or promoted with barium) can be used. Palladium catalysts are recommended for the reduction of aromatic aldehydes, such as that of benzaldehyde to toluene. 

An acidic solvent is recommended for use with palladium. Other catalysts that have been used for this reduction include copper chromite and any of the three Raney catalysts, cobalt, iron, or nickel. 

Palladium and platinum (5—10 wt % on activated carbon) can be used with a variety of solvents as can copper carbonate on siHca and 60 wt % nickel on kieselguhr. The same is tme of nonsupported catalysts copper chromite, rhenium (VII) sulfide, rhenium (VI) oxide, and any of the Raney catalysts, copper, iron, or nickel. 

Nitropyridazines are reduced catalytically either over platinum, Raney nickel or palladium-charcoal catalyst. When an N-oxide function is present, palladium-charcoal in neutral solution is used in order to obtain the corresponding amino N-oxide. On the other hand, when hydrogenation is carried out in aqueous or alcoholic hydrochloric acid and palladium-charcoal or Raney nickel are used for the reduction of the nitro group, deoxygenation of the N- oxide takes place simultaneously. Halonitropyridazines and their N- oxides are reduced, dehalogenated and deoxygenated to aminopyridazines or to aminopyridazine N- oxides under analogous conditions. 

Reduction of the halogen substituent has been carried out by different procedures such as catalytic hydrogenation using palladium-carbon or Raney nickel, red phosphorus and hydroiodic acid, and zinc and sulfuric acid (66AHQ6)347). 3-Deuteropyrazole has been... 

The reduction does not proceed smoothly at room temperature with the palladium catalyst. Raney nickel may be used as a catalyst with ethanol containing potassium hydroxide at room temperature, but about 15 hours are required for reduction. 

The coupling reaction proceeds better when a rigorously degassed Raney nickel catalyst is used, but a nickel catalyst prepared by a much simplifled procedure (Note 9) is also effective. The coupling may also be promoted by other elements, including copper and palladium. 

Snyder and Smith prepared diethyl acetamidomalonate in 40% yield by reduction of diethyl isonitrosomalonate in ethanol over palladium on charcoal followed by direct acetylation of diethyl aminomalonate in the filtrate with acetic anhydride. Ghosh and Dutta used zinc dust instead of palladium. A modification using Raney nickel is described by Akabori et al. Shaw and Nolan reported a 98% yield by conversion of diethyl oximino-malonate-sodium acetate complex. 

Diethyl isonitrosomalonate has been reduced catalytically, over palladium on charcoal, Raney nickel, and chemically by aluminum amalgam or hydrogen sulfide. ... 

Esters and amides are quite resistant to hydrogenation under almost all conditions so their presence is not expected to cause difficulties. Alkyl ethers and ketals are generally resistant to hydrogenolysis but benzyl ethers are readily cleaved, particularly over palladium or Raney nickel catalysts. ... 

Some interesting results have been obtained from studies on the cleavage of 8,14-epoxides such as (65). In the presence of a A -double bond this epoxide is readily hydrogenolyzed over palladium. In the absence of this olefin, platinum and Raney nickel regenerate the A -olefin. ... 

Replacement of halides with deuterium gas in the presence of a surface catalyst is a less useful reaction, due mainly to the poor isotopic purity of the products. This reaction has been used, however, for the insertion of a deuterium atom at C-7 in various esters of 3j -hydroxy-A -steroids, since it gives less side products resulting from double bond migration. Thus, treatment of the 7a- or 7j5-bromo derivatives (206) with deuterium gas in the presence of 5% palladium-on-calcium carbonate, or Raney nickel catalyst, followed by alkaline hydrolysis, gives the corresponding 3j3-hydroxy-7( -di derivatives (207), the isotope content of which varies from 0.64 to 1.18 atoms of deuterium per mole. The isotope composition and the stereochemistry of the deuterium have not been rigorously established. 

Displacement of aromatic halogen in 2,4-diiodo-estradiol with tritiated Raney nickel yields 2,4-ditritiated estradiol. Aromatic halogen can also be replaced by heating the substrate with zinc in acetic acid-OD or by deuteration with palladium-on-charcoal in a mixture of dioxane-deuterium oxide-triethylamine, but examples are lacking for the application of these reactions in the steroid field. Deuteration of the bridge-head position in norbornane is readily accomplished in high isotopic purity by treatment of the... 

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