Raney nickel catalyst

Hie advantages of this catalyst are that it is cheaper and less delicate than platinum, fairly large quantities can be hydrogenated, and the process is reason-aUy rapid. 

It has been stated that the activity of the catalyst in low pressure hydrogenations is enhanced by the addition of small quantities of platinic chloride. 

In the practical applications of Raney nickel it is more convenient to measure the catalyst than to weigh it. The product, prepared as above, contains about 0-6 g. of the catal st per millilitre of settled material a level teaspoonful is about 3 g. of nickel. 

An example of the application of the Raney nickel catalyst is given in Section IV,35 (p-phenylethylamine from benzyl cyanide). 

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P-Phenylethylamine is conveniently prepared by the hydrogenation under pressure of benzyl cyanide with Raney nickel catalyst (see Section VI,5) in the presence of either a saturated solution of dry ammonia in anhydrous methyl alcohol or of liquid ammonia the latter are added to suppress the formation of the secondary amine, di- P phenylethylamine ... 

Nitro groups are efficiently reduced with hydrogen over Raney nickel catalyst (I. Fel-ner, 1967), with hydrides, or with metals. 

Direct hydrohquefaction of biomass or wastes can be achieved by direct hydrogenation of wood chips on treatment at 10,132 kPa and 340 to 350°C with water and Raney nickel catalyst (45). The wood is completely converted to an oily Hquid, methane, and other hydrocarbon gases. Batch reaction times of 4 hours give oil yields of about 35 wt % of the feed the oil contains about 12 wt % oxygen and has a heating value of about 37.2 MJ /kg (16,000 Btu/lb). Distillation yields a significant fraction that boils in the same range as diesel fuel and is completely miscible with it. 

Catalytic methanation processes include (/) fixed or fluidized catalyst-bed reactors where temperature rise is controlled by heat exchange or by direct cooling using product gas recycle (2) through wall-cooled reactor where temperature is controlled by heat removal through the walls of catalyst-filled tubes (J) tube-wall reactors where a nickel—aluminum alloy is flame-sprayed and treated to form a Raney-nickel catalyst bonded to the reactor tube heat-exchange surface and (4) slurry or Hquid-phase (oil) methanation. 

The reduction of nitro alcohols to alkanolamines is readily accompHshed by hydrogenation in the presence of Raney nickel catalyst (1,9,10). 

Xylose is obtained from sulfite Hquors, particularly from hardwoods, such as birch, by methanol extraction of concentrates or dried sulfite lyes, ultrafiltration (qv) and reverse osmosis (qv), ion exchange, ion exclusion, or combinations of these treatments (201). Hydrogenation of xylose is carried out in aqueous solution, usually at basic pH. The Raney nickel catalyst has a loading of 2% at 125°C and 3.5 MPa (515 psi) (202,203). 

Conversion of the nitrile to the amide has been achieved by both chemical and biological means. Several patents have described the use of modified Raney nickel catalysts ia this appHcation (25,26). Also, alkaH metal perborates have demonstrated their utiHty (27). Typically, the hydrolysis is conducted ia the presence of sodium hydroxide (28—31). Owiag to the fact that the rate of hydrolysis of the nitrile to the amide is fast as compared to the hydrolysis of the amide to the acid, good yields of the amide are obtained. Other catalysts such as magnesium oxide (32), ammonia (28,29,33), and manganese dioxide (34) have also been employed. 

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. 

Lubrication AND lubricants). Optimal results are obtained at 130 5°C at a pressure of 1.5—2.0 MPa (15—20 bars) using 0.2 wt % nickel catalyst. Other catalysts and processing parameters may be used to produce unique derivatives. Simple double-bond hydrogenation at 140°C in the presence of Raney nickel catalyst produces glyceryl tris(12-hydroxystearate) [139-44-6], having a melting point of 86°C (46,47). 

Ethylamines. Mono-, di-, and triethylamines, produced by catalytic reaction of ethanol with ammonia (330), are a significant outlet for ethanol. The vapor-phase continuous process takes place at 1.38 MPa (13.6 atm) and 150—220°C over a nickel catalyst supported on alumina, siUca, or sihca—alumina. In this reductive amination under a hydrogen atmosphere, the ratio of the mono-, di-, and triethylamine product can be controlled by recycling the unwanted products. Other catalysts used include phosphoric acid and derivatives, copper and iron chlorides, sulfates, and oxides in the presence of acids or alkaline salts (331). Piperidine can be ethylated with ethanol in the presence of Raney nickel catalyst at 200°C and 10.3 MPa (102 atm), to give W-ethylpiperidine [766-09-6] (332). 

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. 

This procedure is based on the method of Lindsay and Hauser as modified slightly by Osgerby and Pauson. N,N-dimethyl-aminomethylferrocene methiodide has also been prepared by heating formylferrocene with dimethylamine and hydrogen in the presence of Raney nickel catalyst to give dimethylamino-methylferrocene, which was quaternized with methyl iodide. ... 

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. ... 

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. 

Two different sets of experimental conditions have been used. Buu-Hoi et al. and Hansen have employed the method introduced by Papa et using Raney nickel alloy directly for the desulfurization in an alkaline medium. Under these conditions most functional groups are removed and this method is most convenient for the preparation of aliphatic acids. The other method uses Raney nickel catalysts of different reactivity in various solvents such as aqueous ammonia, alcohol, ether, or acetone. The solvent and activity of the catalyst can have an appreciable influence on yields and types of compounds formed, but have not yet been investigated in detail. In acetic anhydride, for instance, desulfurization of thiophenes does not occur and these reaction conditions have been employed for reductive acetylation of nitrothiophenes. Even under the mildest conditions, all double bonds are hydrogenated and all halogens removed. Nitro and oxime groups are reduced to amines. 

The hydrogenation of pyrazolylacetylenes shows no peculiarities. Ethynylpyra-zoles are hydrogenated in high yields to the corresponding ethane derivatives on Raney nickel catalyst, platinum dioxide, or palladium catalyst at room temperature in alcohol solution. 

In 1956 it was found that when pyridine is refluxed with a modified Raney-nickel catalyst, 2,2 -bipyridine (1) is formed in satisfactory yield. The isomeric bipyridines could not be detected, and the product was readily purified. Similar heterocyclic biaryls have been formed in the same way from substituted pyridines and from some related compounds, the yield being dependent on the nature of the compound. The reaction has become the method of choice for the preparation of 2,2 -bipyridine, and it is now used on an industrial scale. Bipyridyls are of particular importance as chelating agents. 

In addition to the Raney nickel catalysts, Raney catalysts derived from iron, cobalt, and copper have been examined for their action on pyridine. At the boiling point of pyridine, degassed Raney iron gave only a very small yield of 2,2 -bipyridine but the activity of iron in this reaction is doubtful as the catalyst was subsequently found to contain 1.44% of nickel. Traces of 2,2 -bipyridine (detected spectroscopically) were formed from pyridine and a degassed, Raney cobalt catalyst but several Raney copper catalysts failed to produce detectable quantities of 2,2 -bipyridine following heating with pyridine. 

Table II shows that, at least for the reactions with quinoline and with 4-methylquinoline (lepidine), nickel-alumina and degassed Raney nickel catalysts are of similar efficiency but better yields have been obtained with degassed Raney nickel, and only this catalyst produces the biaryl from 7-methyIquinoIine.

Sufficient data are not yet available to allow evaluation of the relative merits of palladium-on-carbon and degassed Raney nickel catalysts. Comparable yields of 2,2 -biquinolines have been obtained by both methods under suitable conditions but the percentage conversions with degassed Raney nickel have been found to be much lower, reflecting the extent of side reactions with this catalyst. However, work in this laboratory has shown that the reaction of quinoline with palladium-on-carbon is not free from complications for example, at least three products in addition to 2,2 -biquinoline have been detected by paper chromatography. 

Reaction between Pyridine and W-7 Raney Nickel Catalysts Yields of 2,2 -Bipyridike and of Complex ... 

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