Palladium catalysts liquid-phase

Production of acetaldehyde from oxidation of C H. In a solution of CuCU containing PdCU as a catalyst Liquid-phase esterification of terephthallc acTd lth methanol Hydrogenation of methyl llnoleate In the presence of a palladium catalyst Oxidation of sodium sulfite with cobaltous sulfate catalyst... 

Xia, M. and Wang, Y.G. (2001) Polyethylene glycol as support and phase transfer catalyst in aqueous palladium-catalyzed liquid-phase S3mthesis. Chin. Chem. Lett., 12, 941-2. 

Vapor-phase oxidation over a promoted vanadium pentoxide catalyst gives a 90% yield of maleic anhydride [108-31-6] (139). Liquid-phase oxidation with a supported palladium catalyst gives 55% of succinic acid [110-15-6] (140). 

A route to phenol has been developed starting from cyclohexane, which is first oxidised to a mixture of cyclohexanol and cyclohexanone. In one process the oxidation is carried out in the liquid phase using cobalt naphthenate as catalyst. The cyclohexanone present may be converted to cyclohexanol, in this case the desired intermediate, by catalytic hydrogenation. The cyclohexanol is converted to phenol by a catalytic process using selenium or with palladium on charcoal. The hydrogen produced in this process may be used in the conversion of cyclohexanone to cyclohexanol. It also may be used in the conversion of benzene to cyclohexane in processes where benzene is used as the precursor of the cyclohexane. 

The kinetics of hydrogenation of phenol has already been studied in the liquid phase on Raney nickel (18). Cyclohexanone was proved to be the reaction intermediate, and the kinetics of single reactions were determined, however, by a somewhat simplified method. The description of the kinetics of the hydrogenation of phenol in gaseous phase on a supported palladium catalyst (62) was obtained by simultaneously solving a set of rate equations for the complicated reaction schemes containing six to seven constants. The same catalyst was used for a kinetic study also in the liquid phase (62a). 

Babcock et al. (Bl) examined the hydrogenation of a-methylstyrene catalyzed by palladium and platinum catalysts in a reactor of 1 -in. diameter under countercurrent flow. Flow rates were above 1500 kg/m2-hr for the liquid phase and above 15 kg/m2-hr for the gas, and it was concluded from the experimental results that mass transfer was not of rate-determining influence under these conditions. 

This reaction is similar to 13-1 and, like that one, generally requires activated substrates. With unactivated substrates, side reactions predominate, though aryl methyl ethers have been prepared from unactivated chlorides by treatment with MeO in HMPA. This reaction gives better yields than 13-1 and is used more often. A good solvent is liquid ammonia. The compound NaOMe reacted with o- and p-fluoronitrobenzenes 10 times faster in NH3 at — 70°C than in MeOH. Phase-transfer catalysis has also been used. The reaction of 4-iodotoluene and 3,4-dimethylphenol, in the presence of a copper catalyst and cesium carbonate, gave the diaryl ether (Ar—O—Ar ). Alcohols were coupled with aryl halides in the presence of palladium catalysts to give the Ar—O—R ether. Nickel catalysts have also been used. ... 

Terephthalic acid (p-TA or TA), a raw material for polyethylene terephthalate (PET) production, is one of the most important chemicals in petrochemical industry. Crude terephthalic acid (CTA), commonly produced by homogeneous liquid phase p-xylene oxidation, contains impurities such as 4-carboxybenzaldehyde (4-CBA, 2000-5000 ppm) and several colored polyaromatics that should be removed to obtain purified terephthalic acid (PTA). PTA is manufactured by hydropurification of CTA over carbon supported palladium catalyst (Pd/C) in current industry [1]. 

The chemistry of vinyl acetate synthesis from the gas-phase oxidative coupling of acetic acid with ethylene has been shown to be facilitated by many co-catalysts. Since the inception of the ethylene-based homogeneous liquid-phase process by Moiseev et al. (1960), the active c ytic species in both the liquid and gas-phase process has always been seen to be some form of palladium acetate [Nakamura et al, 1971 Augustine and Blitz, 1993]. Many co-catalysts which help to enhance the productivity or selectivity of the catalyst have appeared in the literature over the years. The most notable promoters being gold (Au) [Sennewald et al., 1971 Bissot, 1977], cadmium acetate (Cd(OAc)j) [Hoechst, 1967], and potassium acetate (KOAc) [Sennewald et al., 1971 Bissot, 1977]. 

The catalysts most frequently used are based on noble metals (mainly palladium and platinum) on various supports, or on nickel catalysts (mainly Raney type). Hydrogenations are generally performed in the liquid phase, under relatively mild conditions of temperature and pressure (1—40 bar). Most processes are performed batch-wise using powder catalysts in stirred tank or loop-type reactors with sizes up to 10 m . 

Gomez-Sainero et al. (11) reported X-ray photoelectron spectroscopy results on their Pd/C catalysts prepared by an incipient wetness method. XPS showed that Pd° (metallic) and Pdn+ (electron-deficient) species are present on the catalyst surface and the properties depend on the reduction temperature and nature of the palladium precursor. With this understanding of the dual sites nature of Pd, it is believed that organic species S and A are chemisorbed on to Pdn+ (SI) and H2 is chemisorbed dissociatively on to Pd°(S2) in a noncompetitive manner. In the catalytic cycle, quasi-equilibrium ( ) was assumed for adsorption of reactants, SM and hydrogen in liquid phase and the product A (12). Applying Horiuti s concept of rate determining step (13,14), the surface reaction between the adsorbed SM on site SI and adsorbed hydrogen on S2 is the key step in the rate equation. 

Several microwave-assisted protocols for soluble polymer-supported syntheses have been described. Among the first examples of so-called liquid-phase synthesis were aqueous Suzuki couplings. Schotten and coworkers presented the use of polyethylene glycol (PEG)-bound aryl halides and sulfonates in these palladium-catalyzed cross-couplings [70]. The authors demonstrated that no additional phase-transfer catalyst (PTC) is needed when the PEG-bound electrophiles are coupled with appropriate aryl boronic acids. The polymer-bound substrates were coupled with 1.2 equivalents of the boronic acids in water under short-term microwave irradiation in sealed vessels in a domestic microwave oven (Scheme 7.62). Work-up involved precipitation of the polymer-bound biaryl from a suitable organic solvent with diethyl ether. Water and insoluble impurities need to be removed prior to precipitation in order to achieve high recoveries of the products. 

Reaction of organic halides with alkenes catalyzed by palladium compounds (Heck-type reaction) is known to be a useful method for carbon-carbon bond formation at unsubstituted vinyl positions. The first report on the application of microwave methodology to this type of reaction was published by Hallberg et al. in 1996 [86], Recently, the palladium catalyzed Heck coupling reaction induced by microwave irradiation was reported under solventless liquid-liquid phase-transfer catalytic conditions in the presence of potassium carbonate and a small amount of [Pd(PPh3)2Cl2]-TBAB as a catalyst [87]. The arylation of alkenes with aryl iodides proceeded smoothly to afford exclusively trans product in high yields (86-93%) (Eq. 61). 

Herrmann WA, Brossmer C, Reisinger CP, Riermaier T, Ofele K, Beller M (1997) Coordination chemistry and mechanisms of metal-catalyzed C-C coupling reactions. Part 10. Palladacycles efficient new catalysts for the Heck vinylation of aryl halides. Chem Eur J 3 1357-1364 Iyer S, Jayanthi A (2001) Acetylferrocenyloxime palladacycle-catalyzed Heck reactions. Tetrahedron Lett 42 7877-7878 Iyer S, Ramesh C (2000) Aryl-Pd covalently bonded palladacycles, novel amino and oxime catalysts di- x-chlorobis(benzaldehydeoxime-6-C,AT)dipalla-dium(II), di- x-chlorobis(dimethylbenzylamine-6-C,A)dipalladium(II) for the Heck reaction. Tetrahedron Lett 41 8981-8984 Jeffery T (1984) Palladium-catalysed vinylation of organic halides under solid-liquid phase transfer conditions. J Chem Soc Chem Commun 1287-1289 (b) idem,... 

J. P. Boitiaux, J. Cosyns, and E. Robert, Hydrogenation of unsaturated hydrocarbons in liquid phase on palladium, platinum and rhodium catalysts, Appl. Catal. 35, 193 (1987). 

Both uncalcined and calcined LDHs have also been shown to be effective supports for noble metal catalysts [18-25]. For example, palladium supported on Cu/Mg/Al LDHs has been used in the liquid phase oxidation of limonene [24], and on calcined Mg/Al LDHs for the one-pot synthesis of 4-methyl-2-pentanone (methyl isobutyl ketone) from acetone and hydrogen at atmospheric pressure [25]. In the latter case, the performance depends on the interplay between the acid-base and hydrogenation properties. More recently. 

More recently Hartog and Zwietering (103) used a bromometric technique to measure the small concentrations of olefins formed in the hydrogenation of aromatic hydrocarbons on several catalysts in the liquid phase. The maximum concentration of olefin is a function of both the catalyst and the substrate for example, at 25° o-xylene yields 0.04, 1.4, and 3.4 mole % of 1,2-dimethylcyclohexene on Raney nickel, 5% rhodium on carbon, and 5% ruthenium on carbon, respectively, and benzene yields 0.2 mole % of cyclohexene on ruthenium black. Although the cyclohexene derivatives could not be detected by this method in reactions catalyzed by platinum or palladium, a sensitive gas chromatographic technique permitted Siegel et al. (104) to observe 1,4-dimethyl-cyclohexene (0.002 mole %) from p-xylene and the same concentrations of 1,3- and 2,4-dimethylcyclohexene from wi-xylene in reductions catalyzed by reduced platinum oxide. 

The hydrogenation of acetic anhydride was also performed in the vapor phase over a supported palladium catalyst resulting in acetaldehyde and acetic acid in high yields (36). To avoid recycling, the reactor was designed for complete reaction of acetic anhydride. Minor selectivity loss was found in formation of ethyl acetate (0.5-1.5%) and methane (0.5%). Typical reaction conditions were 160-200 C, 30-100 psi, with a hydrogen-anhydride ratio of 3 1 to 10 1. A similar catalyst was used in the liquid phase (37). The simplicity and high selectivity of this process is certainly attractive. 

The transformation of alcohols to the corresponding carbonyl compounds or carboxylic acids is one of the few examples in which a heterogeneous (solid) catalyst is used in a selective, liquid phase oxidation (7,2). The process, which is usually carried out in an aqueous slurry, with supported platinum or palladium catalysts and with dioxygen as oxidant, has limited industrial application due to deactivation problems. 

The homogeneous palladium-catalyzed process for acetoxylation was never commercialized because of low selectivity and the difficulty in separating the catalyst from the reaction mixture. Heterogeneous palladium catalysts applied in the gas phase, in turn, quickly lose activity caused by buildup of polybutadiene. The Mitsubishi process uses a Pd-Te-on-active-carbon catalyst in the liquid phase. Tellurium apparently prevents palladium elution to acetic acid. 

Two selective processes are important in the oxidation of ethylene the production of ethylene oxide and acetaldehyde. The first process is specifically catalyzed by silver, the second one by palladium-based catalysts. Silver catalysts are unique and selective for the oxidation of ethylene. No similar situation exists for higher olefins. The effect of palladium catalysts shows a resemblance to the liquid phase oxidation of ethylene in the Wacker process, in which Pd—C2H4 coordination complexes are involved. The high selectivity of the liquid phase process (95%), however, is not matched by the gas phase route at present. 

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