Palladium on barium carbonate

An equal weight of precipitated barium carbonate (93 g.) may be substituted for the barium hydro.xide and sulfuric acid to give a palladium on barium carbonate catalyst. The amount of hydrochloric acid should then be reduced to 8.2 ml. 

A suspension of palladium on barium carbonate (3.7 grams of 30%) in water (20 ml) is shaken in an atmosphere of hydrogen at room temperature. The catalyst is then filtered and washed well with water, care being taken that it does not become dry, A solution of the... 

Dihydrophenanthrene has been prepared from 2,2 -bis(bromomethyl)biphenyl and sodium 8 from the reduction of 2,2 -diiodobibenzy 1 in the presence of 1% palladium on barium carbonate catalyst 8 by the hydrogenation of phenanthrene in the presence of nickel8 or copper-chromium oxide catalyst 10 and by the coupling of 2,2 -bis(bromomethyl)biphenyl with lithium phenyl.11... 

Where it is advantageous to maintain the neutrality of the hydrogenation mixture, palladium on barium carbonate catalyst is recommended. For the preparation of this catalyst the experimental details noted above for the barium sulphate based catalyst are used, but the barium hydroxide and sulphuric acid are replaced by 46.5 g of precipitated barium carbonate and the volume of hydrochloric acid is reduced to 4.1 ml. 

For more selective hydrogenations, supported 5—10 wt % palladium on activated carbon is preferred for reductions in which ring hydrogenation is not wanted. Mild conditions, a neutral solvent, and a stoichiometric amount of hydrogen are used to avoid ring hydrogenation. There are also appHcations for 35—40 wt % cobalt on kieselguhr, copper chromite (nonpromoted or promoted with barium), 5—10 wt % platinum on activated carbon, platinum (IV) oxide (Adams catalyst), and rhenium heptasulfide. Alcohol yields can sometimes be increased by the use of nonpolar (nonacidic) solvents and small amounts of bases, such as tertiary amines, which act as catalyst inhibitors. 

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. 

Support has been shown to influence selectivity and some workers have obtained higher yields of cis isomer over palladium-on-calcium carbonate or palladium-on-barium sulfate 21), whereas others find carbon satisfactory. In general, carbon support makes the more active catalyst and it is, therefore, more prone to become hydrogen poor. 

Palladium catalysts resemble closely the platinum catalysts. Palladium oxide (PdO) is prepared from palladium chloride and sodium nitrate by fusion at 575-600° [29,30]. Elemental palladium is obtained by reduction of palladium chloride with sodium borohydride [27, 31], Supported palladium catalysts are prepared with the contents of 5% or 10% of palladium on charcoal, calcium carbonate and barium sulfate [32], Sometimes a special support can increase the selectivity of palladium. Palladium on strontium carbonate (2%) was successfully used for reduction of just y, (5-double bond in a system of oc, / , y, (5-unsaturated ketone [ii]. 

Palladium catalysts are more often modified for special selectivities than platinum catalysts. Palladium prepared by reduction of palladium chloride with sodium borohydride Procedure 4, p. 205) is suitable for the reduction of unsaturated aldehydes to saturated aldehydes [i7]. Palladimn on barium sulfate deactivated with sulfur compounds, most frequently the so-called quinoline-5 obtained by boiling quinoline with sulfur [34], is suitable for the Rosenmund reduction [i5] (p. 144). Palladium on calcium carbonate deactivated by lead acetate Lindlar s catalyst) is used for partial hydrogenation of acetylenes to cw-alkenes [36] (p. 44). 

With most hydrogenation catalysts of the platinum and nickel groups (Sections 4.2.61, p. 459 and 4.2.50, p. 450), a mixture of products is obtained even if an attempt is made to stop the reaction at the half-way stage. An alkene may only be obtained in good yield if particular attention is paid to the selection of a deactivated hydrogenation catalyst. An early, highly effective formulation of a deactivated palladium catalyst is Lindlar s catalyst (Section 4.2.54, p. 453), but palladium-on-barium sulphate in the presence of quinoline, or palladium-on-calcium carbonate, is also recommended. In these cases it is advisable to... 

Another commercial aldehyde synthesis is the catalytic dehydrogenation of primary alcohols at high temperature in the presence of a copper or a copper-chromite catalyst. Although there are several other synthetic processes employed, these tend to be smaller scale reactions. For example, acyl halides can be reduced to the aldehyde (Rosemnund reaction) using a palladium-on-barium sulfate catalyst. Formylation of aryl compounds, similar to hydrofomiylation, using HCN and HQ (Gatterman reaction) or carbon monoxide and HQ (Gatterman-Koch reaction) can be used to produce aromatic aldehydes. 

An acetylene may be reduced to an olefin by sodium in liquid ammonia, ° by electrolytic reduction at a spongy nickel cathode, or by partial hydrogenation over metal catalysts. Catalysts for the hydrogenation include nickel, ° iron, colloidal palladium, and palladium on barium sulfate or calcium carbonate. Pure trans olefins are obtained from dialkylacetylenes by reduction with sodium in liquid ammonia. The yields ate better than 90%. Catalytic hydrogenation leads to mixtures of cis and trans olefins in which the cis isomers predominate. ° Mono- and di-arylacetylenes have also been reduced. ... 

Palladium catalysts can also be used for furan reductions. Depending on the reaction conditions, civ-substituted tetrahydrofurans (e.g., 8)46, as well as ring-cleaved products, can be obtained. Palladium on barium sulfate or calcium carbonate preferentially gives the tetrahydro-furan derivatives46. 

In the first step of the synthesis (the Kiliani portion), the aldose is treated with sodium cyanide and HCl (Section 18.4). Addition of cyanide ion to the carbonyl group creates a new asymmetric carbon. Consequently, two cyanohydrins that differ only in configuration at C-2 are formed. The configurations of the other asymmetric carbons do not change, because no bond to any of the asymmetric carbons is broken during the course of the reaction (Section 5.12). Kiliani went on to hydrolyze the cyanohydrins to aldonic acids (Section 17.18), and Fischer had previously developed a method to convert aldonic acids to aldoses. This reaction sequence was used for many years, but the method currently employed to convert the cyanohydrins to aldoses was developed by Serianni and Barker in 1979 it is referred to as the modified Kiliani-Fischer synthesis. Serianni and Barker reduced the cyanohydrins to imines, using a partially deactivated palladium (on barium sulfate) catalyst so that the imines would not be further reduced to amines. The imines could then be hydrolyzed to aldoses (Section 18.6). 

Hydrogenation of alkynes with this new catalyst gives the Z-alkene as the major product, with only trace amounts of the )-alkene. This selective catalyst is called the Lindlar catalyst and hydrogenation of alkynes using it is called Lindlar hydrogenation or Lindlar reduction, named for its discoverer, H. Lindlar (Switzerland). This catalyst has been supplanted by another version that is easier to prepare and less prone to the oxidation of the lead carbonate and lead oxide constituents. It is now the standard and is formally called the Rosenmund catalyst, but it is commonly referred to as a Lindlar catalyst. The new catalyst is composed of palladium-on-barium sulfate (BaS04) and it... 

Hydrogenation. Hydrogenation is one of the oldest and most widely used appHcations for supported catalysts, and much has been written in this field (55—57). Metals useflil in hydrogenation include cobalt, copper, nickel, palladium, platinum, rhenium, rhodium, mthenium, and silver, and there are numerous catalysts available for various specific appHcations. Most hydrogenation catalysts rely on extremely fine dispersions of the active metal on activated carbon, alumina, siHca-alumina, 2eoHtes, kieselguhr, or inert salts, such as barium sulfate. 

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