Reduction palladium chloride

The solvent is conveniently that in which the hydrogenation is to be done. During the reduction of the palladium chloride, a neutral solvent is to be preferred any acid or alkali needed for the hydrogenation is added after reduction of the catalyst. 

The presence of hydrogen chloride during the hydrogenation of many organic compounds is desirable or without effect, so that the washing operations may be omitted in such cases. Thus, the palladium chloride on carbon may be used in the same manner as the prereduced catalysts, i.e., simply added before reduction to the solvent and the hydrogen acceptor. 

The checkers reduced the palladium chloride, in three batches, in a 500-ml. bottle. The bottle was not shaken, but the contents were rapidly stirred under a pressure of 1.1 atmospheres of hydrogen. The reduction of each batch required about 5 hours. 

Palladium catalysts have been prepared by fusion of palladium chloride in sodium nitrate to give palladium oxide by reduction of palladium salts by alkaline formaldehyde or sodium formate, by hydrazine and by the reduction of palladium salts with hydrogen.The metal has been prepared in the form of palladium black, and in colloidal form in water containing a protective material, as well as upon supports. The supports commonly used are asbestos, barium carbonate, ... 

According to Skita, the reaction proceeds in a different manner if the reduction be effected with palladium chloride and hydrogen. In this case the citral in alcoholic solution is mixed with an aqueous solution of palladium chloride and the whole thickened with gum-arabic. Hydrogen gas is then forced into this solution under pressure. The products of the reduction include citronellal and citronellol and a di-molecular aldehyde, C Hj O, which probably has the following constitution —... 

Skita has studied the reduction of ionone by means of palladium chloride. The reduction-product, dihydroionone, boils at 121° and 122° (14 mm.) it possessed a faint odour of cedarwood. By the same method, /3-ionone yields a dihydroionone boiling at 126° to 129° (12 mm.). When the reduction is continued until hydrogen ceases to be absorbed, both a- and j8-ionone yield tetrahydroionone, boiling at 126° to f27°... 

Chemical reduction is used extensively nowadays for the deposition of nickel or copper as the first stage in the electroplating of plastics. The most widely used plastic as a basis for electroplating is acrylonitrile-butadiene-styrene co-polymer (ABS). Immersion of the plastic in a chromic acid-sulphuric acid mixture causes the butadiene particles to be attacked and oxidised, whilst making the material hydrophilic at the same time. The activation process which follows is necessary to enable the subsequent electroless nickel or copper to be deposited, since this will only take place in the presence of certain catalytic metals (especially silver and palladium), which are adsorbed on to the surface of the plastic. The adsorbed metallic film is produced by a prior immersion in a stannous chloride solution, which reduces the palladium or silver ions to the metallic state. The solutions mostly employed are acid palladium chloride or ammoniacal silver nitrate. The etched plastic can also be immersed first in acidified palladium chloride and then in an alkylamine borane, which likewise form metallic palladium catalytic nuclei. Colloidal copper catalysts are of some interest, as they are cheaper and are also claimed to promote better coverage of electroless copper. 

Reactions. The reduction of arylazoquinoxalines to quinoxalinamines has been covered in Section 6.3.1. The only other reaction reported recently is the formation of metal complexes. Although 6,6, 7,7 -tetraoctyloxy-2,2 -biquinoxaline and palladium chloride formed a complex (306) that proved too insoluble for analytical... 

Alkyl iodides, benzyl chlorides, benzyl bromides, and adamantyl bromides and iodides undergo reduction with triethylsilane/palladium chloride.195 The reduction of a /3-chloro ether occurs in excellent yield with this system (Eq. 56).195... 

Vinyl and Aryl Halides and Triflates. The organosilane reduction of aryl halides is possible in high yields with triethylsilane and palladium chloride.195 The reaction is equally successful with aryl chlorides, bromides, and iodides. Aryl bromides and iodides, but not chlorides, are reduced with PMHS/Pd(PPh3)4 in moderate to excellent yields.199 This system also reduces vinyl bromides.199 p-Chlorobenzophenone is reduced to benzophenone with yym-tetramethyldisilo-xane and Ni/C in excellent yield (Eq. 59).200 There is a report of the organosilane reduction of aryl and vinyl triflates in very high yields with the combination of Et3SiH/Pd(OAc)2/dppp (l,3-bis(diphenylphosphino)propane) (Eq. 60).201... 

Palladium. Palladium catalysts are much like platinum, but a little more versatile. Palladium oxide is made by heating palladium chloride with sodium nitrate to fusion at 575-600°. Use palladium oxide (an equimolar amount) in the formulas already given for reducing with platinum oxide. Below is a reduction with palladium-carbon. 

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). 

The best procedure for most purposes was the treatment with alkali in the presence of sodium borohydride carried out on BSM (42) the dehydroserine linkages were converted to alanine. Since this procedure did not reduce all dehydrothreonine residues, the procedure was modified by a final reduction in the presence of palladium chloride and borohydride (43, 44). The reactions involved are shown in Figure 6. 

Terminal monoalkenes were alkylated by stabilized carbanions (p a 10-18) in the presence of 1 equiv. of palladium chloride and 2 equiv. of triethylamine, at low temperatures (Scheme l).1 The resulting unstable hydride eliminate to give the alkene (path b), or treated with carbon monoxide and methanol to produce the ester (path c).2 As was the case with heteroatom nucleophiles, attack at the more substituted alkene position predominated, and internal alkenes underwent alkylation in much lower (=30%) yield. In the absence of triethylamine, the yields were very low (1-2%) and reduction of the metal by the carbanion became the major process. Presumably, the tertiary amine ligand prevented attack of the carbanion at the metal, directing it instead to the coordinated alkene. The regiochemistry (predominant attack at the more sub-... 

Methods (i) and (ii) require palladium(II) salts as reactants. Either palladium acetate, palladium chloride or lithium tetrachloropalladate(II) usually are used. These salts may also be used as catalysts in method (iii) but need to be reduced in situ to become active. The reduction usually occurs spontaneously in reactions carried out at 100 °C but may be slow or inefficient at lower temperatures. In these cases, zero valent complexes such as bis(dibenzylideneacetone)palladium(0) or tetrakis(triphenylphos-phine)palladium(O) may be used, or a reducing agent such as sodium borohydride, formic acid or hydrazine may be added to reaction mixtures containing palladium(II) salts to initiate the reactions. Triarylphosphines are usually added to the palladium catalysts in method (iii), but not in methods (i) or (ii). Normally, 2 equiv. of triphenylphosphine, or better, tri-o-tolylphosphine, are added per mol of the palladium compound. Larger amounts may be necessary in reactions where palladium metal tends to precipitate prematurely from the reaction mixtures. Large concentrations of phosphines are to be avoided, however, since they usually inhibit the reactions. 

Several examples of the cyclization of indole derivatives with alkenic side chains in the 3-position have been reported.6 In these examples, palladium chloride in combination with silver tetrafluoroborate is the cyclizing agent. The palladium tetrafluoroborate, presumably formed, should be a very reactive palladating species and probably is the reason why these reactions proceed at room temperature, although the mechanism is not yet completely clear. These reactions were worked up reductively (by addition of sodium borohydride) in order to reduce the expected alkenic product or any relatively stable organopalladium complexes that may have been formed (equation 4).6... 

Sodium borohydride-Palladium chloride. Sodium borohydride-Rhodium(lII) chloride. Sodium borohydride-Tin(II) chloride. Sodium cyanoborohydride. Sodium 9-cyano-9-hydrido-9-borabicyclo[3.3.1]nonane. Sodium dithionite. Sodium hydride-Sodium t-amyl oxide-Zinc chloride. Sodium trimethoxyborohydride. Tetra-/i-butylammonium borohydride. Tetra-n-butylammonium cyanoborohydride. Tetra-n-butylammonium octahydrotriborate. Tri-n-butyltin hydride. Triethoxy silane. Triisobutylaluminum-Bis(N-methyl-salicyclaldimine)nickel. Zinc borohydride. REDUCTIVE CYCLIZATION Cobaloximc(I). 

For the isolation of thiophenes from petroleum and other fossil fuels, a number of methods have been reported, including chromatography on silver nitrate (23) or palladium chloride-impregnated silica gel (24), and oxidation to the more polar sulfones followed by chromatographic separation of the sulfones, their reduction back to the thiophenes and chromatographic separation of the thiophenes (25). The... 

Palladium chloride, propylene and carbon monoxide react in benzene solution to form 3-chlorobutyryl chloride in 27% yield 19>. The Markovnikov adduct apparently reacts with carbon monoxide and then the addition product undergoes a reductive elimination of Pd(O). 

In principle, the same methods used for the preparation of platinum catalysts may be applied for palladium catalysts. When palladium chloride is used as a starting material, it is usually dissolved into an aqueous solution as chloropalladic acid by adding hydrochloric acid prior to reduction or formation of precipitates. Unsupported and supported palladium catalysts have been prepared by reduction of palladium salts with alkaline formaldehyde,139 168 sodium formate,169 hydrazine,150 hydrogen,170,171 sodium borohydride,146,172 or sodium hydride-t-AmOH,173 or by reduction of palladium hydroxide174,175 or palladium oxide176 with hydrogen. 

Palladium Black from Palladium Hydroxide. 75 To a 2% aqueous solution of palladium chloride heated to 90-95°C is added with stirring about 5% lithium hydroxide solution drop by drop until the pH of the solution becomes 7.5-7.8 and no more changes occur on further standing. The brown palladium hydroxide thus precipitated is washed with hot distilled water on a filter paper. If the filtrate becomes colloidal, the washing is stopped immediately. The solid is dried between filter papers, and then in a desiccator. A finely ground powder of palladium hydroxide is suspended in water and reduced to the black form at room temperature and atmospheric pressure in a shaking apparatus. As soon as black precipitates are formed and the supernatant water becomes clean, the reduction is interrupted, and the palldium black is washed with water on a filter paper or in an Erlenmeyer flask by decantation. The reduction and washing process is repeated until the pH of the solution after the reduction... 

Unsupported palladium catalysts are often unstable in use at elevated temperatures and/or high hydrogen pressures. Yada et al. obtained a highly stable palladium black by precipitating palladium hydroxide from palladium chloride solution with an aqueous sodium aluminate instead of sodium hydroxide.177 The palladium catalyst obtained by reduction of the palladium hydroxide prepared with a 1M sodium aluminate solution at pH 10, in the same way as described above, kept a high surface area of 139 m2 g 1 even after the reduction at 200°C in a flow of hydrogen, compared to only 2.0 m2 g 1 with the catalyst prepared using a sodium hydroxide solution as precipitant. The thermally stable catalyst was found to contain 13 ppm of sodium and 1400 ppm (0.14%) of aluminum. 

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