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We performed a systematic investigation of the conditions causing or preventing self-ignition of spent palladium on a carbon catalyst after hydrogenation reactions. The solvent used for hydrogenati...

Grindelia squarrosa, known as gumweed, is a shrub that grows in arid lands in North America with up to 8% biocrude (or bio-oil) content that can be extracted by using a common solvent extraction method. This solvent-extracted biocrude (SEB) has nearly 24 wt% oxygen, which is not suitable for direct combustion as a bio-oil or biodiesel. In this study, supercritical water (SCW) upgrading is used to reduce the oxygen of the SEB and increase the fuel value by creating lighter oil fractions. Treatment for 30 min reduces the oxygen content from 24.1 ± 1.6 (for raw SEB) to 7.2 ± 0.7%, 7.1 ± 0.4%, and 6.9 ± 0.6% at 380, 400, and 420 °C respectively. The addition of palladium on carbon (Pd/C) catalyst at 400 °C further reduces the oxygen content to 4.8 ± 0.7%. This removal in oxygen content is shown in the reduction of carboxylic acid compounds in the oils. Without having to use hydrogen, such as with the traditional hydrodeoxygenation process, the SCW upgrading has rather high energy yields for the oils which all have higher heating values between 41.0 and 42.8 MJ kg−1 (with no significant effect of temperature or catalyst). Treatment at 400 °C had the highest energy yield at 76.4 ± 1.7%, and treatment with the Pd/C catalyst at 400 °C had the lowest at 61.4 ± 2.8%. These energy yields, higher heating values, and low oxygen contents show that SCW can effectively be used to convert gumweed-derived SEB into a valuable bio-oil.

A previously developed and industrially feasible process for selective, Pd-mediated, liquid-phase heterogeneous catalytic hydrogenation of nitriles to primary amines was extended to the reduction of 3-phenylpropionitrile (PPN) to 3-phenylpropylamine (PPA). PPN, which belongs to the homologous series of benzonitrile (BN) and benzyl cyanide (BC), was hydrogenated under mild reaction conditions (30–80 °C, 6 bar), over Pd/C, in two immiscible solvents (dichloromethane/water) and using acidic additives (NaH2PO4 and H2SO4). Although relatively high conversion (76%) was achieved, the selectivity to PPA (26%) and its isolated yield (20%) were lesser than those in the case of the hydrogenation of BN or BC reported earlier. However, the purity of PPA was >99% without using any purification method. Quantum chemical calculations using a density functional theory (DFT) method were performed to compare the adsorption interactions of the different imine intermediates on palladium, as well as to clarify the differences observed in the primary amine selectivity. PPA is a valuable intermediate for the synthesis of carboxypeptidase B enzyme inhibitors, antimuscarinic drugs, or potential anticancer agents in the pharmaceutical industry.

Direct C(sp2)–H bond functionalization of indoles with arylboronic acids is achieved using palladium supported on carbon as a reusable heterogeneous catalyst in the presence of an oxidant under mild conditions. The current protocol formed exclusive C-2 selective products without the aid of any ligand or directing group. The catalyst is reusable for up to four catalytic cycles with the retention of catalytic efficiency.

The 2-vinylbenzoic acids have wide applications in the field of polymer chemistry and are key precursors for the synthesis of important bioactive molecules. Herein, an ortho-halogen-induced deoxygenative approach for the generation of 2-vinylbenzoic acids from alkyl aryl ketones by palladium catalysis is discovered and explored. This approach requires no base or stoichiometric additives and can be carried out through a simple one-step process. Furthermore, the present reaction is scalable up to one-gram scale. The commercially available palladium on carbon (5 wt%) was used as a heterogeneous catalyst and showed excellent recyclability (

The Pd/C-catalyzed reactions, including reduction reactions and cross-coupling reactions, play an irreplaceable role in modern organic synthesis. Compared to the homogeneous palladium catalyst system, the heterogeneous Pd/C catalyst system offers an alternative protocol that has particular advantages and applications. Herein, a review on Pd/C-catalyzed reactions is presented. Both the advances in Pd/C-catalyzed methodologies and the application of Pd/C-catalysis in total synthesis are covered in this review.

Effective preparation of olivacine and ellipticine via late-stage D-ring cyclization is described. Key features of the synthetic routes include trifluoroacetic acid-mediated formation of a lactone that is fused to a tetrahydrocarbazole derivative and its one-pot two-step ring opening and aromatization mediated by para-toluenesulfonic acid and palladium on carbon, respectively.

A batch catalytic slurry reactor system was used to study the hydrodeoxygenation (HDO) of pyrolysis oil model compounds at high conversions and conditions similar to petroleum hydrotreatment reactors. The lignin fraction of pyrolysis oil was represented in this study by anisole, m-cresol and phenol, both individually and blended in pairs. Experiments were run from 250 °C to 350 °C using platinum on alumina (Pt/Al2O3) or palladium on carbon (Pd/C) in a Parr reactor at 50 bar. The Pt/Al2O3 catalysts exhibited ring saturation, demethylation and hydrodeoxygenation, with temperature-dependent pathway shifts. Tests with blended pairs yielded no secondary reactions but competitive adsorption for catalyst active sites was observed. Tests with Pd/C showed ring saturation followed by methanol abstraction. Rate constants and adsorption parameters were fitted to a Langmuir-Hinshelwood model for each catalyst and compound. Arrhenius relationships for those rate constants and surface adsorption parameters were then calculated. When used in a slurry reactor model with catalyst-specific reaction data, the product composition, hydrogen consumption, and energy requirements are well predicted for a known feed and set of reactor conditions.

An efficient deracemization method for conversion of the racemate to the desirable (R)-enantiomer of Praziquantel has been developed by coupling incompatible racemization and crystallization processes. By a library approach, a derivative that crystallizes as a conglomerate has been identified. Racemization occurs via reversible hydrogenation over a palladium on carbon (Pd/C) packed column at 130 0C, whereas deracemization is achieved by alternating crystal growth/dissolution steps with temperature cycling between 5-15 0C. These incompatible processes are combined by means of a flow system resulting in complete deracemization of the solid phase to the desired (R)-enantiomer (98 % ee ). Such an unprecedented deracemization by a decoupled crystallization/racemization approach can readily be turned into a practical process and opens new opportunities for the development of essential enantiomerically pure building blocks that require harsh methods for racemization.

We report insights into our observations of the wide variability in quality of palladium catalyst from different suppliers, finding the fundamental differences can be rationalized through a combination of XRD, XPS, and TEM analysis, offering the possibility to predict a catalysts performance prior to the use of valuable synthetic material and save time consuming efforts to identify high quality palladium on carbon catalysts. The synthetic glycan accessed in this study will allow further steps towards the development of semisynthetic vaccines against cryptococcal infections.

A practical and efficient method for scavenging palladium leached into the reaction mixture using thiol-modified dual-pore silica beads has been developed. Reducing the level of metal contamination, especially palladium, in pharmaceutical and bioactive compounds and fine chemicals to below the regulatory value is quite important for the quality assurance of industrial products. We have evaluated the performance of dual-pore silica beads as a palladium scavenger by investigating their ability to eliminate the divalent palladium ions in dilute palladium(II) acetate in methanol (5 and 50 ppm) and ethyl acetate (5 ppm) solutions. The ability of the dual-pore silica beads to eliminate the palladium species leached from a 10% palladium on carbon (Pd/C) catalyst during the ligand- and copper-free 10% Pd/C-catalyzed Sonogashira-type coupling reaction was also investigated. The thiol-modified dual-pore silica beads exhibit a more rapid and effective elimination ability toward leached palladium species in the react...

Compounds such as 3, the product of a palladium[0]-catalyzed Ullmann cross-coupling of o-iodonitrobenzene and 2-iodocyclohex-2-en-1-one, undergo complementary modes of reductive cyclization depending upon the conditions employed. Thus, on treatment with hydrogen in the presence of palladium on carbon, the tetrahydrocarbazole 4 is formed, while reaction of the same substrate (3) with TiCl3 in acetone affords the 1,2,3,9-tetrahydro-4H-carbazol-4-one 6.

In the present work we developed a practical, faster, and more sustainable way to prepare conjugated materials, derived from poly-p-phenylenes (PPPs), using 10% palladium on carbon as catalyst and distilled water as solvent under microwave heating for 3 h. The oligomers were also prepared by the classical Suzuki reaction to enable a comparison of results. All materials were characterized by nuclear magnetic resonance (NMR), infrared (IR), absorption and emission analysis, gel permeation chromatography (GPC), and thermogravimetric analysis. The polymers prepared by the alternative method were obtained in higher yields than the polymers produced by the classical Suzuki reaction. In addition, characterization data showed no significant differences in terms of molecular structures and luminescent properties between the polymers synthesized through the different protocols. Therefore, the alternative method developed was considered appropriated for the synthesis of PPPs derivatives.

A series of phenolic bio-oil components were selectively hydrodearomatized by palladium on carbon into the corresponding ketones or alcohols in excellent yields using polymethylhydrosiloxane and wa ...

This protocol describes an electrochemical synthesis of 1,2-diazides from alkenes. Organic azides are highly versatile intermediates for synthetic chemistry, materials, and biological applications. 1,2-Diazides are commonly reduced to form 1,2-diamines, which are prevalent structural motifs in bioactive natural products, therapeutic agents, and molecular catalysts. The electrochemical formation of 1,2-diazides involves the anodic generation of an azidyl radical from sodium azide, followed by two successive additions of this N-centered radical to the alkene, and is assisted by a Mn catalyst. The electrosynthesis of 1,2-diazides can be carried out using various experimental setups comprising custom-made or commercially available reaction vessels and a direct-current power supply. Readily accessible electrode materials can be used, including carbon (made from reticulated vitreous carbon and pencil lead), nickel foam, and platinum foil. This protocol is also demonstrated using ElectraSyn, a standardized electrochemistry kit. Compared with conventional synthetic approaches, electrochemistry allows for the precise control of the anodic potential input, eliminates the need for stoichiometric and often indiscriminate oxidants, and minimizes the generation of wasteful byproducts. As such, our electrocatalytic synthesis exhibits various advantages over existing methods for alkene diamination, including sustainability, operational simplicity, substrate generality, and exceptional functional-group compatibility. The resultant 1,2-diazides can be smoothly reduced to 1,2-diamines in a single step with high chemoselectivity. To exemplify this, we include a procedure for catalytic hydrogenation using palladium on carbon. This protocol, therefore, constitutes a general approach to accessing 1,2-diazides and 1,2-diamines from alkenes.

Dihydronepetalactone (DHN) is a safe and effective topical insect repellent,(5,6,8) comparable in efficacy to that of N,N-diethyl-m-toluamide (DEET). The latter is the most commonly used active ingredient, found in many commercial insect repellents for a broad range of biting insects. DHN can be produced by hydrogenating nepetalactone (NL), which is the primary ingredient of the essential oil obtained from the renewably sourced catmint plant, Nepeta cataria. Optimizing the hydrogenation reaction to produce DHN from catmint oil is a key economic driver for the process. Prior to the study described here, Six Sigma methodologies were used to select palladium on carbon (5% Pd/C) as the catalyst of choice. The hydrogenation step was studied as a function of critical process variables and the composition of the oil. As described in this article, a robust, two-step hydrogenation process was developed to maximize the yield of the desired DHNs from treated catmint oil. It was observed that the composition of the c...

Transition metal-catalyzed dehydrogenation is a clean oxidation method requiring no additional oxidants. We have accomplished a heterogeneous Pd/C-catalyzed aqueous dehydrogenation of 1,4-cyclohexadienes and cyclohexenes to give the corresponding highly-functionalized arenes. Furthermore, various arenes could be efficiently constructed in a one-pot manner via a Diels–Alder reaction and the following dehydrogenation.

In the presence of either Pd/C or Pt/C, 4-alkoxybenzyl alcohols, 4-alkoxy-phenylalkyl alcohols and cinnamyl alcohols undergo liquid etherification to bis(4-alkoxybenzyl) ethers, bis[(4-alkoxybenzyl)alkyl] ethers and bis(cin-namyl) ethers at temperatures of 100°C - 135°C. In a number of cases, Pt/C and Pd/C as catalysts, also when they are doped with Ru, show distinct differences when the reactions run in air, with an oxidative dehydrogenation of the alcohols as side-reaction, yielding the corresponding ketones and aldehydes as by-products. Also, the reactivity of fluorinated phenylalkenols under these conditions has been investigated. Furthermore, the immobilization of alkyl aryl ethers on silica within a column with passage of hexane as solvent was found to lead to the formation and elution of styrenes from the column in fair yield.

Reaction of methyl-2-(2-formylphenyl)acetate with primary amines in a reductive amination/cyclisation process resulted in N-substituted 1,4-dihydro-3(2H)-isoquinolinones. With H 2NCH 2R sodium borohyride is a suitable reductant (11 examples), but H 2NCHR 1R 2 required a transfer hydrogenation using ammonium formate catalysed by palladium on carbon (9 examples). 4-Substituted-1,4-dihydro-3(2H)-isoquinolinones were synthesised by deprotonation (n-butyllithium) and addition of R 3CH 2Br (12 examples with R 3 = alkyl, Ar, CH[dbnd]CH 2, C[tbnd]CH). Modest diastereoselectivity was achieved with 1,4-dihydro-3(2H)-isoquinolinones derived from H 2NCHMeR 2 [R 2 = (η 5-C 5H 4)Co(η 4-C 4Ph 4) - max. dr = 1.9: 1], but use of H 2NCHMeFc (Fc = ferrocenyl) provided a new method of 1,4-dihydro-3(2H)-isoquinolinone N-deprotection with formic acid.

Hydrogen has attracted much attention as one of the most promising chemical fuel candidates because of its zero emission during consumption. In order to solve the freezing problem of water based hydrolysis process, herein, the Pd/C as an efficient and stable catalyst for the methanolysis, ethanolysis, propanolysis and butanolysis of B2pin2 for the generation of hydrogen has been first developed. The large kinetic isotope effect (KIE) of kH/kD = 5.0, D2 formation from CD3OD and in situ tandem reaction have confirmed that alcohol is the only hydrogen source. Interestingly, the order of Ea of these alcohols in H2 evolution is MeOH (methanol, 29.57 kJ/mol) EtOH > PrOH > nBuOH).

A facile direct deposition approach for the preparation of recyclable Pd/C catalysts simply by stirring a solution of Pd2dba3 with a suitable carbon material was evaluated. An extraordinary rapid catalyst preparation procedure (< 5 min) under mild conditions and its excellent performance in cross-coupling and hydrogenation reactions were demonstrated. The key point for catalyst design was to directly deposit Pd(0) centers onto highly accessible surface area and to avoid ill-defined Pd(II)/Pd(0) states.

In the presence of palladium on carbon (Pd/C) as a catalyst, hydrogenation of aliphatic nitriles in cyclohexane efficiently proceeded at 25-60 °C under ordinary hydrogen gas pressure to afford the corresponding tertiary amines. However, the use of rhodium on carbon (Rh/C) led to the highly selective generation of secondary amines. Hydrogenation of aromatic nitriles and cyclohexanecarbonitrile selectively produced secondary amines in the presence of either Pd/C or Rh/C.

Nucleophilic substitution in nitroarenes to form biaryl ethers is of fundamental importance in organic synthesis. Under non-catalytic conditions, this can occur when a highly activated nitroarenes are used, or the nucleophile is activated by strong stoichiometric base. We have established a new method, using ligand-free palladium on carbon (Pd/C) catalyst, for the cross-coupling of activated nitroarenes with relatively non-nucleophilic phenol derivatives, including naphthol, in the absence of harsh bases. Control experiments, hot-filtration, three-phase test and ICP-AES analysis reveals that the catalysis proceeds via a usual oxidative addition step of nitroarene to Pd/C and releases active palladium particles having an extremely high catalytic activity. DFT calculations were made to realize the origin of selectivity of activated nitroarenes.

The catalytic hydrogenation of cardanol was studied in a stirred three-phase-slurry reactor using palladium on carbon, often referred to as the Pd/C catalyst (5% loading of palladium is supported on activated carbon powder). The effects of various process parameters were examined. The kinetics of hydrogenation, which proceeds through three parallel–series reactions, was investigated. The reaction was observed to be of first order with respect to both hydrogen and cardanol. A simple second-order series reaction model was well fitted to the experimental data. Also, the Langmuir–Hinshelwood–Hougen–Watson approach was used to interpret the possible mechanistic behaviour of the reaction. It was observed that the reaction follows dual site, competitive and dissociative type of adsorption of hydrogen. Surface reaction of the adsorbed reactants was identified as the overall rate controlling step. Various rate constants and adsorption equilibrium constants for the different steps were also estimated. Different thermodynamic parameters associated with these constants were obtained to assess their physical significance. Also, these constants were evaluated statistically using the F-test and t-test.

Palladium nanomaterials have attracted great attention on the development of electrocatalysts for fuel cells. Herein, we depicted a novel strategy in the synthesis of palladium nanoparticles with superior electrocatalytic activity. The new approach, based on the self-assembly of bacitracin biotemplate and palladium salt for the preparation of bacitracin-palladium nanoparticles (Bac-PdNPs), was simple, low-cost, and green. The complex, composed by a series of spherical Bac-PdNPs with a diameter of 70 nm, exhibited a chain-liked morphology in TEM and a face-centered cubic crystal structure in X-Ray diffraction and selected area electron diffraction. The palladium nanoparticles were mono-dispersed and stable in aqueous solution as shown in TEM and zeta potential. Most importantly, compared to the commercial palladium on carbon (Pd/C) catalyst (8.02 m 2 g −1 ), the Bac-PdNPs showed a larger electrochemically active surface area (47.57 m 2 g −1 ), which endowed the products an excellent electrocatalytic activity for ethanol oxidation in alkaline medium. The strategy in synthesis of Bac-PdNPs via biotemplate approach might light up new ideas in anode catalysts for direct ethanol fuel cells.