- Specifics of the stearic acid deoxygenation reaction on a copper catalyst
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Decarbonylation of stearic acid, which is industrially manufactured from oils and fats, to higher olefins on a Cu/γ-Al2O 3catalyst has been first studied. It has been shown that the selectivity for heptadecenes is 67% and that for CO is close to 100% at 350°C. The activity of this catalyst in the further hydrogenation of resulting heptadecenes to heptadecane is well below that of a palladium catalyst. The conversion is slightly varied when hydrogen pressure increases from 4 to 14 bar; however, the selectivity for olefins increases and the selectivity for paraffins remains low. According to quantum-chemical simulation data, hydrides form on the surface of copper clusters in the presence of hydrogen. It is presumably these compounds that inhibit the side oligomerization reaction of olefins. The hydrogen-to-water concentration ratio does not affect the selectivity for CO and CO2; the only effect of the presence of water is a decrease in the stearic acid conversion rate. Pleiades Publishing, Ltd., 2013.
- Berenblyum,Danyushevsky,Katsman,Shamsiev,Flid
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- Catalytic deoxygenation of bio-based 3-hydroxydecanoic acid to secondary alcohols and alkanes
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This work comprises the selective deoxygenation of bio-derivable 3-hydroxydecanoic acid to either linear alkanes or secondary alcohols in aqueous phase and H2-atmosphere over supported metal catalysts. Among the screened catalysts, Ru-based systems were identified to be most active. By tailoring the catalyst, the product selectivity could be directed to either secondary alcohols or linear alkanes. In the absence of a Br?nsted acidic additive, 2-nonanol and 3-decanol were accessible with a yield of 79% and 6% respectively, both of which can be used in food and perfume industries as flavoring agents and fragrances. To produce alkanes, we successfully synthesized a bifunctional Ru/HZSM-5 catalyst. The acidic zeolite support facilitated the dehydration of the intermediary formed alcohols to alkenes, while the following hydrogenation occurred at the Ru centers. Thus, full 3-hydroxydecanoic acid deoxygenation to nonane and decane, which are both well-established as diesel and jet fuels, was achieved with up to 72% and 12% yield, respectively.
- Artz, Jens,Brosch, Sebastian,Golchert, Christiane,Hergesell, Adrian H.,Mensah, Joel B.,Palkovits, Regina
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- Effect of the presence of ionic liquid during the NiMoS bulk preparation in the transformation of decanoic acid
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The impact of the presence and amount of [BMIM][NTf2] ionic liquid during the preparation of bulk NiMoS catalysts was investigated. It was clearly shown that these factors have a strong influence on both the morphology and specific surface area of the obtained NiMoS samples. Most interestingly the catalytic activity for the transformation of decanoic acid increased up to three times when IL was present during synthesis. In the same time, a greater selectivity towards hydrocarbons was observed. On the whole a clear relationship between catalytic activity, selectivity and NiMoS morphology was demonstrated. Consequently, it is possible to modify the morphology of the materials and impact the catalytic properties by changing the synthesis conditions.
- Leyral, Géraldine,Brillouet, Soizic,Rousseau, Julie,Richard, Frédéric,Mamede, Anne Sophie,Courthéoux, Laurence,Pradel, Annie,Ribes, Michel,Brunet, Sylvette
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- Catalytic Upgrading of 5-Hydroxymethylfurfural to Drop-in Biofuels by Solid Base and Bifunctional Metal-Acid Catalysts
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Design and synthesis of effective heterogeneous catalysts for the conversion of biomass intermediates into long chain hydrocarbon precursors and their subsequent deoxygenation to hydrocarbons is a viable strategy for upgrading lignocellulose into distillate range drop-in biofuels. Herein, we report a two-step process for upgrading 5-hydroxymethylfurfural (HMF) to C9 and C11 fuels with high yield and selectivity. The first step involves aldol condensation of HMF and acetone with a water tolerant solid base catalyst, zirconium carbonate (Zr(CO3)x), which gave 92 % C9-aldol product with high selectivity at nearly 100 % HMF conversion. The as-synthesised Zr(CO3)x was analysed by several analytical methods for elucidating its structural properties. Recyclability studies of Zr(CO3)x revealed a negligible loss of its activity after five consecutive cycles over 120 h of operation. Isolated aldol product from the first step was hydrodeoxygenated with a bifunctional Pd/Zeolite-β catalyst in ethanol, which showed quantitative conversion of the aldol product to n-nonane and 1-ethoxynonane with 40 and 56 % selectivity, respectively. 1-Ethoxynonane, a low oxygenate diesel range fuel, which we report for the first time in this paper, is believed to form through etherification of the hydroxymethyl group of the aldol product with ethanol followed by opening of the furan ring and hydrodeoxygenation of the ether intermediate. Two-stepping to Biofuels! A recyclable and water tolerant heterogeneous base catalyst produced 92 % C9-aldol product from 5-hydroxymethylfurfural and acetone in water. Subsequent hydrogenation of the isolated aldol product with a metal-acid Pd/zeolite-β catalyst produced gasoline and diesel range n-nonane and 1-ethoxynonane with an overall 96 % yield.
- Bohre, Ashish,Saha, Basudeb,Abu-Omar, Mahdi M.
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- Production of high-quality diesel from biomass waste products
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(Chemical Equation Presented) High-quality liquid fuels are obtained from non-edible carbohydrates by energy-efficient processes. 2-Methylfuran, produced by hydrogenation of furfural, is converted into 6-alkyl undecanes in a catalytic solvent-free process (see scheme with 6-butylundecane). A diesel fuel is produced with an excellent motor cetane number (71) and pour point (-90°C) and with global process conversions and selectivities close to 90%.
- Corma, Avelino,De La Torre, Olalla,Renz, Michael,Villandier, Nicolas
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- Hydroxymethylation of organic halides. Evaluation of a catalytic system involving a fluorous tin hydride reagent for radical carbonylation
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Hydroxymethylation of organic halides 2 using a catalytic amount of fluorous tin hydride 1, CO, and NaBH3CN as a reducing agent, proceeded smoothly to give one-carbon homologated alcohols 5 in good yields. Three phase workup (water-dichloromethane-perfluorohexane) was conveniently performed for the separation of 1 and 5.
- Ryu, Ilhyong,Niguma, Tatsuro,Minakata, Satoshi,Komatsu, Mitsuo,Hadida, Sabine,Curran, Dennis P.
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- α-Deuterium and Carbon-13 Kinetic Isotope Effects Associated with the SN2 Displacement of Iodide and Tosylate by Lithium Organocuprates
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The secondary α-deuterium and 13C isotope effects associated with the competitive methylation of two cuprates, (n-C8H17)2CuLi(PBu3) and (n-C8H17)4CuLi3(PBu3), by CH3X-CD3X and 12,13CH3X (X=I or OTs) together with their related temperature dependences are reported.
- Guo, Cong-yuan,Brownawell, Marilyn L.,Filippo, Joseph San, Jr.
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- Alkanes from Bioderived Furans by using Metal Triflates and Palladium-Catalyzed Hydrodeoxygenation of Cyclic Ethers
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Using a metal triflate and Pd/C as catalysts, alkanes were prepared from bioderived furans in a one-pot hydrodeoxygenation (HDO) process. During the reaction, the metal triflate plays a crucial role in the ring-opening HDO of furan compounds. The entire reaction process has goes through two major phases: at low temperatures, saturation of the exocyclic double bond and furan ring are catalyzed by Pd/C; at high temperatures, the HDO of saturated furan compounds is catalyzed by the metal triflate. The reaction mechanism was verified by analyzing the changes of the intermediates during the reaction. In addition, different metal triflates, solvents, and catalyst recycling were also investigated. Fu, Fu, Fu (tri-f): Metal triflates (tri-f) act as an axe (, Fu), cleaving the C-O bond of cyclic ethers and luckily (, Fu) transforming bioderived furans into alkanes in a one-pot (, Fu) process. The mechanism of the reaction is verified by analyzing the changes of the intermediates during the reaction. Different metal triflates, solvents, and catalyst recycling are investigated, also.
- Song, Hai-Jie,Deng, Jin,Cui, Min-Shu,Li, Xing-Long,Liu, Xin-Xin,Zhu, Rui,Wu, Wei-Peng,Fu, Yao
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- Reductive defluorination of fluoroalkanes
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The reaction of an excess of lithium powder and a catalytic amount of DTBB with primary, secondary and tertiary fluoroalkanes in the presence of a substoichiometric amount of 1,2-bis(trimethylsilyl)benzene 1 afforded the corresponding alkanes resulting from a fluorine-hydrogen exchange. The method could be extended to non-geminal difluorides. The effect of the disilylated compound in the naphthalene-catalysed lithiation of fluorobenzene and benzyl fluoride was also studied.
- Guijarro, David,Martínez, Pedro,Yus, Miguel
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- Fabricating nickel phyllosilicate-like nanosheets to prepare a defect-rich catalyst for the one-pot conversion of lignin into hydrocarbons under mild conditions
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The one-pot conversion of lignin biomass into high-grade hydrocarbon biofuels via catalytic hydrodeoxygenation (HDO) holds significant promise for renewable energy. A great challenge for this route involves developing efficient non-noble metal catalysts to obtain a high yield of hydrocarbons under relatively mild conditions. Herein, a high-performance catalyst has been prepared via the in situ reduction of Ni phyllosilicate-like nanosheets (Ni-PS) synthesized by a reduction-oxidation strategy at room temperature. The Ni-PS precursors are partly converted into Ni0 nanoparticles by in situ reduction and the rest remain as supports. The Si-containing supports are found to have strong interactions with the nickel species, hindering the aggregation of Ni0 particles and minimizing the Ni0 particle size. The catalyst contains abundant surface defects, weak Lewis acid sites and highly dispersed Ni0 particles. The catalyst exhibits excellent catalytic activity towards the depolymerization and HDO of the lignin model compound, 2-phenylethyl phenyl ether (PPE), and the enzymatic hydrolysis of lignin under mild conditions, with 98.3% cycloalkane yield for the HDO of PPE under 3 MPa H2 pressure at 160 °C and 40.4% hydrocarbon yield for that of lignin under 3 MPa H2 pressure at 240 °C, and its catalytic activity can compete with reported noble metal catalysts.
- Cao, Meifang,Chen, Bo,He, Chengzhi,Ouyang, Xinping,Qian, Yong,Qiu, Xueqing
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supporting information
p. 846 - 857
(2022/02/09)
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- H2-Free Selective Dehydroxymethylation of Primary Alcohols over Palladium Nanoparticle Catalysts
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The dehydroxymethylation of primary alcohols is a promising strategy to transform biomass-derived oxygenates into hydrocarbon fuels. In this study, a novel, highly efficient, and reusable heterogeneous catalyst system was established for the H2-free dehydroxymethylation of primary alcohol using cerium oxide-supported palladium nanoparticles (Pd/CeO2). A wide range of aliphatic and aromatic alcohols including biomass-derived alcohols were converted into the corresponding one-carbon shorter hydrocarbons in high yields in the absence of any additives, accompanied by the production of H2 and CO. Pd/CeO2 was easily recovered from the reaction mixture and reused, retaining its high activity, thus, providing a simple and sustainable methodology to produce hydrocarbon fuels from biomass-derived oxygenates.
- Yamaguchi, Sho,Kondo, Hiroki,Uesugi, Kohei,Sakoda, Katsumasa,Jitsukawa, Koichiro,Mitsudome, Takato,Mizugaki, Tomoo
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p. 1135 - 1139
(2020/12/29)
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- GAS-TO-GAS REACTOR AND METHOD OF USING
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A device and a process to propagate molecular growth of hydrocarbons, either straight or branched chain structures, that naturally occur in the gas phase of a first gas to gas phase molecules of a second gas having higher molecular chain lengths than the hydrocarbons of the first gas. According to one embodiment, the device includes a grounded reactor vessel having a gas inlet, a product outlet, and an electrode within the vessel; a power supply coupled to the electrode for creating an electrostatic field within the vessel for converting the first gas to a second gas.
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Paragraph 0179-0180
(2021/02/05)
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- Hydrogenation of Alkenes Catalyzed by a Non-pincer Mn Complex
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Hydrogenation of substituted styrenes and unactivated aliphatic alkenes by molecular hydrogen has been achieved using a Mn catalyst with a non-pincer, picolylphosphine ligand. This is the second reported example of alkene hydrogenation catalyzed by a Mn complex. Mechanistic studies showed that a Mn hydride formed by H2 activation in the presence of a base is the catalytically active species. Based on experimental and DFT studies, H2 splitting is proposed to occur via a metal-ligand cooperative pathway involving deprotonation of the CH2 arm of the ligand, leading to pyridine dearomatization.
- Rahaman, S. M. Wahidur,Pandey, Dilip K.,Rivada-Wheelaghan, Orestes,Dubey, Abhishek,Fayzullin, Robert R.,Khusnutdinova, Julia R.
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p. 5912 - 5918
(2020/10/30)
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- Hydrogenation of hydrophobic substrates catalyzed by gold nanoparticles embedded in Tetronic/cyclodextrin-based hydrogels
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Hydrogenation of alkenes, alkynes and aldehydes was investigated under biphasic conditions using Au nanoparticles (AuNP) embedded into combinations of α-cyclodextrin (α-CD) and a poloxamine (Tetronic90R4). Thermo-responsive AuNP-containing α-CD/Tetronic90R4 hydrogels are formed under well-defined conditions of concentration. The AuNP displayed an average size of ca. 7 nm and a narrow distribution, as determined by TEM. The AuNP/α-CD/Tetronic90R4 system proved to be stable over time. Upon heating above the gel-to-sol transition temperature, the studied catalytic system allowed hydrogenation of a wide range of substrates such as alkenes, alkynes and aldehydes under biphasic conditions. Upon repeated heating/cooling cycles, the Au NP/α-CD/Tetronic90R4 catalytic system could be recycled several times without a significant decline in catalytic activity.
- Chevry,Menuel,Léger,No?l,Monflier,Hapiot
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p. 9865 - 9872
(2019/07/04)
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- Molybdenum Oxide-Modified Iridium Catalysts for Selective Production of Renewable Oils for Jet and Diesel Fuels and Lubricants
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Supported inverse metal-metal oxide catalysts have received significant research interest owing to their effective hydrodeoxygenation (HDO) activity toward biomass substrates, but the high cost of the reported catalysts poses a challenge for commercialization. We present the synthesis of a series of metal-metal oxide catalysts, Ir-MOx/SiO2 (M = Re, Mo, W, V, or Nb) and M′-MoOx/SiO2 (M = Rh, Ru, Pt, or Pd) and their HDO performance on multifuran (high carbon) substrates to produce renewable jet and diesel fuels and lubricant base oils. A MoOx-modified Ir/SiO2 catalyst with a Mo/Ir ratio of 0.13 (Ir-MoOx/SiO2) exhibits the highest product yield (78-96%) under mild reaction conditions. Controlled experiments using probe substrates reveal that furan ring hydrogenation and C-O hydrogenolysis of saturated and unsaturated furan rings occur in a sequential manner. The carbon atom adjacent to the furan or saturated furan ring of substrates or intermediate compounds undergoes slow C-C bond scission, resulting in a small fraction of lighter alkanes. Catalyst characterization suggests that Ir is reduced to a fully metallic state to dissociate hydrogen for hydrogenation. Intact MoOx, partly covering the Ir metal surface, promotes ring opening, hydrogenolysis of etheric and alcoholic C-O bonds, and hydrogenation of Ca? O bonds. This study highlights the potential of low-cost metal-metal oxide catalysts with low loading of oxophilic metals to enable cost-competitive production of bioproducts and demonstrates applicability of these catalysts on other substrates, including fatty acids, fatty esters, and lipids.
- Liu, Sibao,Zheng, Weiqing,Fu, Jiayi,Alexopoulos, Konstantinos,Saha, Basudeb,Vlachos, Dionisios G.
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p. 7679 - 7689
(2019/08/20)
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- Decarbonylation through Aldehydic C-H Bond Cleavage by a Cationic Iridium Catalyst
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We report the decarbonylation of aldehydes through an aldehydic C-H bond cleavage catalyzed by a cationic iridium/bisphosphine catalyst. The reaction proceeds under relatively mild conditions to give the corresponding hydrocarbon products in moderate to high yields. In addition, this cationic iridium catalyst system can be applied to an asymmetric hydroacylation of ketones.
- Shirai, Tomohiko,Sugimoto, Kazuki,Iwasaki, Masaya,Sumida, Ryuki,Fujita, Harunori,Yamamoto, Yasunori
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p. 972 - 976
(2019/05/10)
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- Hexadecane Conversion on an Alumina–Nickel Catalyst
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Abstract: The conversion of hexadecane on a 4% Ni/Al2O3 catalyst in a temperature range of 20–300°C was studied using IR spectroscopy and catalytic methods. It was found that the dehydrogenation of hexadecane occurred at 20–100°C with the subsequent formation of aromatic products, but the rates of these processes were very low. As the reaction temperature was increased to 200°C, the 4% Ni/Al2O3 catalyst exhibited a maximum activity and high selectivity for the formation of 1-hexadecene, and aromatic compounds and cracking products were present in the reaction products. As the reaction temperature was further increased, the catalytic activity significantly decreased. This was due to the fact that polyaromatic deposits gradually accumulated on the catalyst surface in a temperature range of 200–300°C.
- Chesnokov,Chichkan,Paukshtis,Chesalov, Yu. A.,Krasnov
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p. 439 - 445
(2019/09/04)
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- Kinetics and chemoselectivity studies of hydrogenation reactions of alkenes and alkynes catalyzed by (benzoimidazol-2-ylmethyl)amine palladium(II) complexes
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A series of (benzoimidazol-2-ylmethyl)amine palladium(II) complexes have been employed as catalysts in the homogeneous hydrogenation of alkenes and alkynes under mild conditions. A correlation between the catalytic activity and the nature of the ligand was established. Kinetic studies of the hydrogenation reactions of styrene established pseudo-first-order dependence on styrene substrate. On the other hand, partial orders with respect to H2 and catalyst concentrations were obtained. The nature of the solvent used influenced the hydrogenation reactions, where coordinating solvents resulted in lower catalytic activities. Kinetics and mechanistic studies performed were consistent with the formation of palladium monohydride intermediates as the active species.
- Tshabalala, Thandeka A.,Ojwach, Stephen O.
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supporting information
p. 148 - 155
(2018/08/23)
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- Reevaluation of the Palladium/Carbon-Catalyzed Decarbonylation of Aliphatic Aldehydes
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An improved method for the decarbonylation of aliphatic aldehydes by using a commercially available Pd/C catalyst is described. The reaction conditions are suitable for linear, cyclic, or sterically demanding substrates, as they afford the corresponding alkanes in yields of up to 99%. In addition, this Pd/C-catalyzed method exhibits good functional-group tolerance. A comparison of previously reported methods with the present one showed that the reaction conditions play a crucial role in the outcome of the reaction. The method can also be applied in a two-step reaction sequence for the synthesis of industrially important compounds.
- Ajda?i?, Vladimir,Nikoli?, Andrea,Kerner, Michael,Wipf, Peter,Opsenica, Igor M.
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supporting information
p. 1781 - 1785
(2018/08/12)
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- Hydrodeoxygenation of Fatty Acids, Triglycerides, and Ketones to Liquid Alkanes by a Pt–MoOx/TiO2 Catalyst
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Various supported metal catalysts are screened for hydrogenation of lauric acid and 2-octanone as model reactions for the transformation of biomass-derived oxygenates to liquid alkanes (biofuels) in a batch reactor under solvent-free conditions. Among the catalysts tested, Pt and MoOx co-loaded on TiO2 (Pt–MoOx/TiO2) shows the highest yields of n-alkanes for both of the reactions. Pt–MoOx/TiO2 selectively catalyzes the hydrodeoxygenation of various fatty acids and triglycerides to n-alkanes without C?C bond cleavage under 50 bar H2 and shows higher turnover numbers than the catalysts in the literature. Pt–MoOx/TiO2 is effective also for the hydrodeoxygenation of various ketones to the corresponding alkanes. In situ IR study of the reaction of adsorbed acetone under H2 suggests that the high activity of Pt–MoOx/TiO2 is attributed to the cooperation between Pt and Lewis acid sites of the MoOx/TiO2 support.
- Kon, Kenichi,Toyao, Takashi,Onodera, Wataru,Siddiki,Shimizu, Ken-Ichi
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p. 2822 - 2827
(2017/07/28)
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- Ruthenium-Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols
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Dehydrogenative decarbonylation of a primary alcohol involves the release of both dihydrogen and carbon monoxide to afford the by one carbon unit shorter product. The transformation has now been achieved with a ruthenium-catalyzed protocol by using the complex Ru(COD)Cl2 and the hindered monodentate ligand P(o-tolyl)3 in refluxing p-cymene. The reaction can be applied to both benzylic and long-chain linear aliphatic alcohols. The intermediate aldehyde can be observed during the transformation, which is therefore believed to proceed through two separate catalytic cycles involving first dehydrogenation of the alcohol and then decarbonylation of the resulting aldehyde.
- Mazziotta, Andrea,Madsen, Robert
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p. 5417 - 5420
(2017/10/06)
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- Metathesis of renewable polyene feedstocks – Indirect evidences of the formation of catalytically active ruthenium allylidene species
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Cross-metathesis (CM) of conjugated polyenes, such as 1,6-diphenyl-1,3,5-hexatriene (1) and α-eleostearic acid methyl ester (2) with several olefins, including 1-hexene, dimethyl maleate and cis-stilbene as model compounds has been carried out using (1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)-dichloro(o-isopropoxyphenylmethylene)ruthenium (Hoveyda-Grubbs 2nd generation, HG2) catalyst. The feasibility of these reactions is demonstrated by the observed high conversions and reasonable yields. Thus, regardless of the relatively low electron density, =CH–CH= conjugated units of molecules, including compound 2 as a sustainable, non-foodstuff source, can be utilized as building blocks for the synthesis of various value-added chemicals via olefin metathesis. DFT-studies and the product spectrum of the self-metathesis of 1,6-diphenyl-1,3,5-hexatriene suggest that a Ru η1-allylidene complex is the active species in the reaction.
- Kovács, Ervin,Sághy, Péter,Turczel, Gábor,Tóth, Imre,Lendvay, Gy?rgy,Domján, Attila,Anastas, Paul T.,Tuba, Róbert
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supporting information
p. 213 - 217
(2017/09/12)
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- Insight into forced hydrogen re-arrangement and altered reaction pathways in a protocol for CO2 catalytic processing of oleic acid into C8-C15 alkanes
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A new vision of using carbon dioxide (CO2) catalytic processing of oleic acid into C8-C15 alkanes over a nano-nickel/zeolite catalyst is reported in this paper. The inherent and essential reasons which make this achievable are clearly resolved by using totally new catalytic reaction pathways of oleic acid transformation in a CO2 atmosphere. The yield of C8-C15 ingredients reaches 73.10 mol% in a CO2 atmosphere, which is much higher than the 49.67 mol% yield obtained in a hydrogen (H2) atmosphere. In the absence of an external H2 source, products which are similar to aviation fuel are generated where aromatization of propene (C3H6) oxidative dehydrogenation (ODH) involving CO2 and propane (C3H8) and hydrogen transfer reactions are found to account for hydrogen liberation in oleic acid and achieve its re-arrangement in the final alkane products. The reaction pathway in the CO2 atmosphere is significantly different from that in the H2 atmosphere, as shown by the presence of 8-heptadecene, γ-stearolactone, and 3-heptadecene as reaction intermediates, as well as a CO formation pathway. Because of the highly dispersed Ni metal center on the zeolite support, H2 spillover is observed in the H2 atmosphere, which inhibits the production of short-chain alkanes and reveals the inherent disadvantage of using H2. The CO2 processing of oleic acid described in this paper will significantly contribute to future CO2 utilization chemistry and provide an economical and promising approach for the production of sustainable alkane products which are similar to aviation fuel.
- Xing, Shiyou,Lv, Pengmei,Yuan, Haoran,Yang, Lingmei,Wang, Zhongming,Yuan, Zhenhong,Chen, Yong
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supporting information
p. 4157 - 4168
(2017/09/07)
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- Ligand-free nickel-catalyzed semihydrogenation of alkynes with sodium borohydride: A highly efficient and selective process for: Cis -alkenes under ambient conditions
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We report a low-cost and efficient catalytic system, involving in situ generated ligand-free Ni NPs, methanol and sodium borohydride, for the semihydrogenation of alkynes under ambient conditions. This catalytic system exhibits remarkably high activity, satisfactory cis-selectivity for internal alkynes, good stability and general applicability.
- Wen, Xin,Shi, Xiaozhen,Qiao, Xianliang,Wu, Zhilei,Bai, Guoyi
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supporting information
p. 5372 - 5375
(2017/07/06)
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- COMPOSITIONS AND METHODS FOR CO2 ADSORPTION AND CONVERSION TO LONG-CHAIN HYDROCARBONS
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The invention provides novel, low-cost catalysts and methods for their preparation and application in CO2 adsorption and conversion to long-chain hydrocarbons via photosynthesis with ambient CO2 and solar energy.
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Paragraph 0059-0065
(2017/03/21)
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- Noble metal-free catalytic decarboxylation of oleic acid to n-heptadecane on nickel-based metal-organic frameworks (MOFs)
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Nickel based metal organic frameworks (Ni-MOFs) were successfully synthesized using new conjugated carboxylic acid linkers. These conjugated carboxylic acid linkers were synthesized using mild Heck coupling that led to the incorporation of functional groups not possible by traditional synthetic methods. Control of linker size allows for porosity tuning of the crystalline network and high surface area, that, in theory, results in the increased accessibility to Ni metal centers for catalysis. The resultant crystalline Ni-MOFs displayed BET areas as high as ~314 m2 g-1. To investigate their catalytic activity for conversion of oleic acid to liquid hydrocarbons, Ni-MOFs were grown on zeolite 5A beads that served as catalytic supports. The resultant catalysts displayed heptadecane selectivity as high as ~77% at mild reaction conditions, one of the highest yields for non-noble metal containing catalysts. The catalytic activity correlated to the concentration of acid sites. A slight decrease in catalytic activity was observed after catalysts recycling.
- Yang,McNichols,Davidson,Schweitzer,Gómez-Gualdrón,Trewyn,Sellinger,Carreon
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p. 3027 - 3035
(2017/08/01)
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- In Situ Generation and Immobilization of an Activated Rh Complex Catalyst in a Metal–Organic Framework for Hydrogenation at Low H2 Pressure
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Hydrogenation reactions under low-pressure H2 atmosphere are highly relevant from the safety viewpoint, because H2 gas is highly flammable in air and explosions can be triggered by spark, heat, or sunlight. In this work, an Rh complex/MOF hybrid was synthesized and used as catalyst for the hydrogenation of alkene substrates. Thanks to the activation of the Rh complex catalyst during the immobilization process and the intrinsic gas-condensation property of MOFs, the resulting composite showed much higher catalytic activity than the complex catalyst itself. Moreover, the composite can maintain its catalytic activity even at low H2 pressures that cannot support the reaction with the complex catalyst alone. Furthermore, in contrast to the complex catalyst, the composite maintained its catalytic activity even without solvent, and thus provides an environmentally friendly approach to catalysis.
- Takashima, Yohei,Fukuhara, Yoshimasa,Sato, Yasushi,Tsuruoka, Takaaki,Akamatsu, Kensuke
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p. 5344 - 5349
(2017/12/04)
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- GAS-TO-LIQUID REACTOR AND METHOD OF USING
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A device and a process to propagate molecular growth of hydrocarbons, either straight or branched chain structures, that naturally occur in the gas phase to a molecular size sufficient to shift the natural occurring phase to a liquid or solid state is provided. According to one embodiment, the device includes a grounded reactor vessel having a gas inlet, a liquid outlet, and an electrode within the vessel; a power supply coupled to the electrode for creating an elecirostatic field within the vessel for converting the gas to a liquid and or solid state.
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Paragraph 0143; 0144
(2019/08/15)
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- A simple, phosphine free, reusable Pd(ii)-2,2′-dihydroxybenzophenone-SBA-15 catalyst for arylation and hydrogenation reactions of alkenes
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An efficient, simple, phosphine and co-catalyst free C-C coupling reaction heterogeneous catalyst via a post grafting method is developed and reported. A covalently anchored phosphine free Pd(ii) based 2,2′-dihydroxybenzophenone (DHBP) complex over organofunctionalized SBA-15 has been synthesized by the reaction between aminofunctionalized SBA-15 (NH2SBA-15) and a 2,2′-dihydroxybenzophenone (DHBP) ligand, and further complexation with Pd(ii)Cl2 to get Pd(ii)-DHBP@SBA-15. The synthesized catalysts were characterized by elemental analysis, XRD, N2 sorption analyses, TG, DTA, FT-IR, solid state 13C and 29Si NMR spectra, XPS, UV-Visible, SEM, EDAX and TEM. The synthesized catalysts were screened in arylation (Heck reactions) and hydrogenation reactions of alkenes, and the results show that Pd(ii)-DHBP@SBA-15 exhibits high conversion and selectivity towards arylation and hydrogenation reactions of alkenes with high stability. The anchored solid catalysts can be recycled effectively and reused several times without major loss in activity.
- Lazar, Anish,Vinod, Chathakudath P.,Singh, Anand Pal
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p. 2423 - 2432
(2016/03/19)
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- Alkene hydrogenation over palladium supported on a carbon–silica material
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Palladium catalysts supported on a carbon–silica material were synthesized. Hydrogenation by molecular hydrogen was studied in the presence of straight-chain and cyclic olefins. As distinct from what is observed for olefins having a phenyl substituent, for aliphatic alkenes the reaction rate decreases with an increasing conversion due to the accumulation of hydrogenation products. The synthesized palladium catalysts show a higher hydrogenation activity than Pd/C.
- Akchurin,Baibulatova,Grabovskii,Talipova,Galkin,Dokichev
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p. 586 - 591
(2016/10/18)
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- An: In situ approach to preparing Ni2P/SiO2 catalyst under mild conditions and its performance for the deoxygenation of methyl laurate to hydrocarbons
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Ni2P/SiO2 was in situ prepared from Ni/SiO2via a phosphorization process using a dodecane solution containing triphenylphosphine (TPP) as the phosphorus source on a fixed-bed reactor. The influence of the phosphorization condition (nominal P/Ni molar ratio, temperature, WHSV of TPP and atmosphere) on the structure of the phosphorized samples was investigated. The sample structure was characterized by means of XRD, TEM, ICP-AES, TGA, N2 sorption, and FT-IR and magnetic property. It was found that the phosphorization of metallic Ni to Ni2P was promoted by increasing the phosphorization temperature and nominal P/Ni molar ratio and decreasing the WHSV of TPP. The phosphorization rate was much faster in the H2 atmosphere than the N2 one, ascribed to the formation of reactive H atoms on the Ni atoms that facilitated the cleavage of the P-C bond in PPT releasing more reactive PH3/P. To prepare the well-crystallized Ni2P/SiO2 in the H2 atmosphere, the minimum temperature (250 °C) and nominal P/Ni ratio (0.67) were necessary. Also, the Ni2P crystallite size in Ni2P/SiO2 was determined by the Ni one in Ni/SiO2, and no sintering took place during the phosphorization even at 400 °C. It is worth stating that there was a carbonaceous deposit formed on the in situ prepared catalysts, which was harmful for the catalyst activity for the deoxygenation of methyl laurate to hydrocarbons. The phosphorization condition greatly affected the performance of the resulting catalysts. On the whole, the Ni2P/SiO2 catalyst with good performance was prepared under a suitable phosphorization condition (i.e., 300 °C, nominal P/Ni ratio of 0.75, TPP WHSV of 0.5 h-1, and H2 atmosphere). Under the reaction conditions of 340 °C, 3.0 MPa, methyl laurate WHSV of 5 h-1 and H2/methyl laurate molar ratio of 25, it gave the conversion of methyl laurate and the total selectivity for C11 and C12 hydrocarbons higher than 98% and 96% during 100 h, respectively, exhibiting good stability. Finally, we propose a mechanism for the phosphorization of Ni/SiO2.
- Chen, Jixiang,Han, Mengmeng,Zhao, Sha,Pan, Zhengyi,Zhang, Zhena
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p. 3938 - 3949
(2016/06/13)
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- Fischer–Tropsch synthesis with cobalt catalyst and zeolite multibed arrangement
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The role of zeolite in transformations of hydrocarbons produced from CO and H2 over a Fischer–Tropsch cobalt catalyst under the conditions of multibed arrangement of the cobalt catalyst and the zeolite has been determined. Hydrocarbon conversion over the HBeta zeolite occurs via the bimolecular mechanism, as evidenced by a low methane yield and a high yield of unsaturated gaseous and liquid hydrocarbons. The conversion over the CaA zeolite obeys the unimolecular mechanism, as evidenced by the formation of increased amounts of methane and saturated gaseous C2–C4 hydrocarbons.
- Asalieva, E. Yu.,Kul’chakovskaya,Sineva,Mordkovich,Bulychev
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p. 275 - 280
(2016/06/09)
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- Production of liquid hydrocarbon fuels with acetoin and platform molecules derived from lignocellulose
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Acetoin, a novel C4 platform molecule derived from new ABE (acetoin-butanol-ethanol) type fermentation via metabolic engineering, was used for the first time as a bio-based building block for the production of liquid hydrocarbon fuels. A series of diesel or jet fuel range C9-C14 straight, branched, or cyclic alkanes were produced in excellent yields by means of C-C coupling followed by hydrodeoxygenation reactions. Hydroxyalkylation/alkylation of acetoin with 2-methylfuran was investigated over a series of solid acid catalysts. Among the investigated candidates, zirconia supported trifluoromethanesulfonic acid showed the highest activity and stability. In the aldol condensation step, a basic ionic liquid [H3N+-CH2-CH2-OH][CH3COO-] was identified as an efficient and recyclable catalyst for the reactions of acetoin with furan based aldehydes. The scope of the process has also been studied by reacting acetoin with other aldehydes, and it was found that abnormal condensation products were formed from the reactions of acetoin with aromatic aldehydes through an aldol condensation-pinacol rearrangement route when amorphous aluminium phosphate was used as a catalyst. And the final hydrodeoxygenation step could be achieved by using a simple and handy Pd/C + H-beta zeolite system, and no or a negligible amount of oxygenates was observed after the reaction. Excellent selectivity was also observed using the present system, and the clean formation of hydrocarbons with a narrow distribution of alkanes occurred in most cases.
- Zhu, Chenjie,Shen, Tao,Liu, Dong,Wu, Jinglan,Chen, Yong,Wang, Linfeng,Guo, Kai,Ying, Hanjie,Ouyang, Pingkai
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p. 2165 - 2174
(2016/04/19)
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- Selective Catalytic Hydrogenolysis of Carbon-Carbon σ Bonds in Primary Aliphatic Alcohols over Supported Metals
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The selective scission of chemical bonds is always of great significance in organic chemistry. The cleavage of strong carbon-carbon σ bonds in the unstrained systems remains challenging. Here, we report the selective hydrogenolysis of carbon-carbon σ bonds in primary aliphatic alcohols catalyzed by supported metals under relatively mild conditions. In the case of 1-hexadecanol hydrogenolysis over Ru/TiO2 as a model reaction system, the selective scission of carbon-carbon bonds over carbon-oxygen bonds is observed, resulting in n-pentadecane as the dominant product with a small quantity of n-hexadecane. Theoretical calculations reveal that the 1-hexadecanol hydrogenolysis on flat Ru (0001) undergoes two parallel pathways: i.e. carbon-carbon bond scission to produce n-pentadecane and carbon-oxygen bond scission to produce n-hexadecane. The removal of adsorbed CO on a flat Ru (0001) surface is a crucial step for the 1-hexadecanol hydrogenolysis. It contributes to the largest energy barrier in n-pentadecane production and also retards the rate for n-hexadecane production by covering the active Ru (0001) surface. The knowledge presented in this work has significance not just for a fundamental understanding of strong carbon-carbon σ bond scission but also for practical biomass conversion to fuels and chemical feedstocks.
- Di, Lu,Yao, Sikai,Li, Mengru,Wu, Guangjun,Dai, Weili,Wang, Guichang,Li, Landong,Guan, Naijia
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p. 7199 - 7207
(2015/12/11)
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- Decarboxylation of Oleic Acid to Heptadecane over Pt Supported on Zeolite 5A Beads
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The synthesis of Pt supported on zeolite 5A beads for the decarboxylation of oleic acid to heptadecane is demonstrated. The use of a microporous ZIF-67 crystalline layer on zeolite 5A beads not only improved the heptadecane selectivity but also, most importantly, improved the stability of the resultant catalyst. Heptadecane yields as high as ~81% were observed for the fresh catalysts. The catalysts displayed only low to moderate loss of catalytic activity after two rounds of recycle. To our best knowledge, the catalytic performance of these catalysts is superior to those of the state-of-the-art catalysts at mild reaction conditions. In addition, as compared to powders, beads are much easier to recycle, can be fully recovered, and are more amenable for potential scale-up. The resultant catalysts are promising for the catalytic conversion of fatty acid molecules into gasoline/diesel-range hydrocarbons.
- Yang, Liqiu,Tate, Kirby L.,Jasinski, Jacek B.,Carreon, Moises A.
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p. 6497 - 6502
(2015/11/23)
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- Catalytic Production of Branched Small Alkanes from Biohydrocarbons
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Squalane, C30 algae-derived branched hydrocarbon, was successfully converted to smaller hydrocarbons without skeletal isomerization and aromatization over ruthenium on ceria (Ru/CeO2). The internal CH2-CH2 bonds located between branches are preferably dissociated to give branched alkanes with very simple distribution as compared with conventional methods using metal-acid bifunctional catalysts.
- Oya, Shin-Ichi,Kanno, Daisuke,Watanabe, Hideo,Tamura, Masazumi,Nakagawa, Yoshinao,Tomishige, Keiichi
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p. 2472 - 2475
(2015/08/24)
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- Cu, Al and Ga based metal organic framework catalysts for the decarboxylation of oleic acid
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Herein we demonstrate the catalytic decarboxylation and conversion of oleic acid to paraffins and hydrocarbons over bare and Pt supported Cu, Al and Ga based metal organic frameworks. Moderate degrees of decarboxylation were observed for all metal organic framework catalysts. The incorporation of Pt with the porous frameworks resulted in high degrees of decarboxylation. All MOF catalysts showed high thermal stability, resulting in recyclable catalysts displaying low catalytic activity loss. Of all studied catalysts, Ga-MOF catalysts were the most effective catalysts, displaying moderate to high degrees of decarboxylation. In addition, the Pt-Ga-MOF catalyst displayed selectivity to heptadecane, an important industrial chemical. Octadecane, heptadecane, dodecane, undecane, decane, nonane, octane, and heptane were observed as the main side products. To our best knowledge, the catalytic ability of a metal organic framework both as catalyst and support for the decarboxylation of a model fatty acid molecule is reported for the first time.
- Yang,Ruess,Carreon
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p. 2777 - 2782
(2015/07/22)
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- Z -selective olefin synthesis via iron-catalyzed reductive coupling of alkyl halides with terminal arylalkynes
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Selective catalytic synthesis of Z-olefins has been challenging. Here we describe a method to produce 1,2-disubstituted olefins in high Z selectivity via reductive cross-coupling of alkyl halides with terminal arylalkynes. The method employs inexpensive and nontoxic catalyst (iron(II) bromide) and reductant (zinc). The substrate scope encompasses primary, secondary, and tertiary alkyl halides, and the reaction tolerates a large number of functional groups. The utility of the method is demonstrated in the synthesis of several pharmaceutically relevant molecules. Mechanistic study suggests that the reaction proceeds through an iron-catalyzed anti-selective carbozincation pathway.
- Cheung, Chi Wai,Zhurkin, Fedor E.,Hu, Xile
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supporting information
p. 4932 - 4935
(2015/05/05)
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- METHOD FOR PRODUCING ORGANIC COMPOUND
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PROBLEM TO BE SOLVED: To provide a method of subjecting a compound having on one carbon atom a carbon atom constituting a carbon-carbon double bond and a functional group such as a hydroxyl group to a reductive reaction condition and producing an organic compound having the functional group substituted with a hydrogen atom. SOLUTION: There is provided a method for producing a compound represented by a formula (50) from a raw material compound represented by a formula (10). The method includes a step of irradiating a reaction system with light, the reaction system comprising the raw material compound, a hydrogen source compound, and a catalyst having a palladium component supported by a carrier containing titanium oxide. (R11 to R15 are a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a cyclic structure or a derivative group thereof, or a heteroatom-containing group having 1 to 20 carbon atoms which may have a cyclic structure or a derivative group thereof; and R16 is a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms or an acyl group having 1 to 20 carbon atoms which may have a cyclic structure, or -CH(CH2OH)2).) COPYRIGHT: (C)2015,JPO&INPIT
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-
Paragraph 0111-0112; 0115
(2018/10/16)
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- Conversion of levulinic acid derived valeric acid into a liquid transportation fuel of the kerosene type
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In the transformation of lignocellulosic biomass into fuels and chemicals carboncarbon bond formations and rising hydrophobicity are highly desired. The ketonic decarboxylation fits these requirements perfectly as it converts carboxylic acids into ketones forming one carboncarbon bond and eliminates three oxygen atoms as carbon dioxide and water. This reaction is used, in a cascade process, together with a hydrogenation and dehydration catalyst to obtain hydrocarbons in the kerosene range from hexose-derived valeric acid. It is shown that zirconium oxide is a very selective and stable catalyst for this process and when combined with platinum supported on alumina, the oxygen content was reduced to almost zero. Furthermore, it is demonstrated that alumina is superior to active carbon, silica, or zirconium oxide as support for the hydrogenation/dehydration/hydrogenation sequence and a palladium-based catalyst deactivated more rapidly than the platinum catalyst. Hence, under optimized reaction conditions valeric acid is converted into n-nonane with 80% selectivity (together with a 10% of C10-C15 hydrocarbons) in the organic liquid phase upto a 100:1 feed to catalyst ratio [w/w]. The oxygen free hydrocarbon product mixture (85% yield) meets well with the boiling point range of kerosene as evidenced by a simulated distillation. In the gas phase, butane was detected together with mainly carbon dioxide.
- Corma, Avelino,Oliver-Tomas, Borja,Renz, Michael,Simakova, Irina L.
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p. 116 - 122
(2014/06/09)
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- Supported Rh-phosphine complex catalysts for continuous gas-phase decarbonylation of aldehydes
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Heterogeneous silica supported rhodium-phosphine complex catalysts are employed for the first time in the catalytic decarbonylation of aldehydes in continuous gas-phase. The reaction protocol is exemplified for the decarbonylation of p-tolualdehyde to toluene and further extended to other aromatic and aliphatic aldehydes achieving excellent results in terms of both conversion and selectivity. This journal is
- Malcho, Phillip,Garcia-Suarez, Eduardo J.,Mentzel, Uffe Vie,Engelbrekt, Christian,Riisager, Anders
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p. 17230 - 17235
(2015/01/09)
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- Borohydride-mediated radical addition reactions of organic iodides to electron-deficient alkenes
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Cyanoborohydrides are efficient reagents in the reductive addition reactions of alkyl iodides and electron-deficient olefins. In contrast to using tin reagents, the reaction took place chemoselectively at the carbon-iodine bond but not at the carbon-bromine or carbon-chlorine bond. The reaction system was successfully applied to three-component reactions, including radical carbonylation. The rate constant for the hydrogen abstraction of a primary alkyl radical from tetrabutylammonium cyanoborohydride was estimated to be 4 M-1 s-1 at 25 °C by a kinetic competition method. This value is 3 orders of magnitude smaller than that of tributyltin hydride.
- Kawamoto, Takuji,Uehara, Shohei,Hirao, Hidefumi,Fukuyama, Takahide,Matsubara, Hiroshi,Ryu, Ilhyong
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supporting information
p. 3999 - 4007
(2014/05/20)
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- Promotional effect of Fe on performance of Ni/SiO2 for deoxygenation of methyl laurate as a model compound to hydrocarbons
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Ni/SiO2, Fe/SiO2 and bimetallic FeNi/SiO2 catalysts with different Fe/Ni weight ratios were prepared by incipient-wetness impregnation method for the deoxygenation of methyl laurate to hydrocarbons. It was found that a suitable amount of Fe enhanced the activity of Ni/SiO2 for the deoxygenation of methyl laurate, and FeNi(0.25)/SiO2 with a Fe/Ni weight ratio of 0.25 showed the best activity. Moreover, the addition of Fe to Ni/SiO2 significantly promoted the hydrodeoxygenation pathway to produce more C12 hydrocarbon and suppressed the activity for C-C hydrogenolysis. The effect of Fe on the performance of Ni/SiO2 is ascribed the formation of the NiFe alloy particles, particularly with the Fe-enriched surface at low Fe content, and the existence of oxygen vacancies in Fe oxides. A mechanism is proposed to explain the promoting effect of Fe, which involves the synergism between iron sites with strong oxophilicity and nickel sites with high ability to activate hydrogen. Besides, the effect of reaction conditions and catalyst stability were also investigated.
- Yu, Xinbin,Chen, Jixiang,Ren, Tianyu
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p. 46427 - 46436
(2015/01/09)
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- Copper-catalyzed alkyl-alkyl cross-coupling reactions using hydrocarbon additives: Efficiency of catalyst and roles of additives
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Cross-coupling of alkyl halides with alkyl Grignard reagents proceeds with extremely high TONs of up to 1230000 using a Cu/unsaturated hydrocarbon catalytic system. Alkyl fluorides, chlorides, bromides, and tosylates are all suitable electrophiles, and a TOF as high as 31200 h-1 was attained using an alkyl iodide. Side reactions of this catalytic system, i.e., reduction, dehydrohalogenation (elimination), and the homocoupling of alkyl halides, occur in the absence of additives. It appears that the reaction involves the β-hydrogen elimination of alkylcopper intermediates, giving rise to olefins and Cu-H species, and that this process triggers both side reactions and the degradation of the Cu catalyst. The formed Cu-H promotes the reduction of alkyl halides to give alkanes and Cu-X or the generation of Cu(0), probably by disproportionation, which can oxidatively add to alkyl halides to yield olefins and, in some cases, homocoupling products. Unsaturated hydrocarbon additives such as 1,3-butadiene and phenylpropyne play important roles in achieving highly efficient cross-coupling by suppressing β-hydrogen elimination, which inhibits both the degradation of the Cu catalyst and undesirable side reactions.
- Iwasaki, Takanori,Imanishi, Reiko,Shimizu, Ryohei,Kuniyasu, Hitoshi,Terao, Jun,Kambe, Nobuaki
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p. 8522 - 8532
(2015/01/08)
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- Decarboxylation and further transformation of oleic acid over bifunctional, Pt/SAPO-11 catalyst and Pt/chloride Al2O3 catalysts
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Catalytic decarboxylation and further conversion of oleic acid to branched and aromatic hydrocarbons in a single process step, over Pt-SAPO-11 and Pt/chloride Al2O3 is presented. An increase of both reaction time and temperature increase the selectivity to heptadecane. Higher selectivity to heptadecane was observed in the presence of hydrogen. Decarboxylation of oleic acid was as high as ~98 wt% (selectivity for heptadecane >30%) at 325 C in the presence of hydrogen. Branched isomers, alkyl aromatics, like dodecyl benzene and cracked (17) paraffins were the other products.
- Ahmadi, Masoudeh,Macias, Eugenia E.,Jasinski, Jacek B.,Ratnasamy, Paul,Carreon, Moises A.
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- Methylformate as replacement of syngas in one-pot catalytic synthesis of amines from olefins
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A new general approach for the one-pot hydroaminomethylation of olefins using methylformate as formylating agent instead of synthesis gas (syngas) has been proposed. Herein we report that a Ru-Rh catalytic system demonstrates high activity in a tandem conversion of a series of n-alkenes into amines using methylformate with yields 58-92% (6 h). The selectivity for the normal amine reached 96% with catalysis by the Ru carbonyl complex Ru3(CO) 12, with an overall yield of 55% with respect to amine in this instance. The addition of the Rh complex to Ru catalytic system, sharply increased the hydroaminomethylation rate of both the terminal and internal alkenes and increased the yield of amines to 82-93% (6-12 h). The Royal Society of Chemistry.
- Karakhanov, Eduard,Maksimov, Anton,Kardasheva, Yulia,Runova, Elena,Zakharov, Roman,Terenina, Maria,Kenneally, Corey,Arredondo, Victor
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p. 540 - 547
(2014/02/14)
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- Molecular sieving carbon catalysts for liquid phase reactions: Study of alkene hydrogenation using platinum embedded nanoporous carbon
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We present a simple method to synthesize shape selective carbon catalysts for large alkene hydrogenation reactions by tailoring porosity of platinum embedded in polyfurfuryl alcohol derived carbons. A small amount of mesoporosity, in addition to the intrinsic microporous nature of the carbon, shortens the diffusion length for the reactant molecule, enabling these materials to be used for catalysis in the liquid phase. A systematic study of hydrogenation reactions of liquid phase alkenes is reported. The molecular sieving effect of the catalyst was examined by varying molecular length, size, double bond position, stereoregularity and the number of double bonds in the alkenes.
- Holbrook, Billy Paul M.,Rajagopalan, Ramakrishnan,Dronvajjala, Krishna,Choudhary, Yogesh Kumar,Foley, Henry C.
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- Copper nanoparticle-catalyzed cross-coupling of alkyl halides with Grignard reagents
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A cross-coupling reaction between alkyl bromides and chlorides and various Grignard reagents was carried out in the presence of commercially available copper or copper oxide nanoparticles as a catalyst and an alkyne additive. The catalytic system shows high activity, a broad scope, and good functional group tolerance.
- Kim, Ju Hyun,Chung, Young Keun
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supporting information
p. 11101 - 11103
(2013/11/19)
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- Reactivities of mixed organozinc and mixed organocopper reagents: 9. Solvent dependence of group transfer selectivity in sp3C coupling and acylation of mixed diorganocuprates and diorganozincs
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The selectivity and/or reactivity of organyl group transfer of mixed diorganocuprates in their alkyl coupling in THF depends on N- or O-donor solvents as cosolvents. Selective n-Bu group transfer is observed in room temperature alkylation of Grignard reagent derived stoichiometric n-BuPhCuMgBr reagent in THF:cosolvent and solvation effects do not change the group transfer ability. However, in the alkylation of catalytic mixed cuprates derived from CuI catalyzed n-BuPh2ZnMgBr and n-Bu2PhZnMgBr, group transfer ability depends on the solvation effect and it can be controlled by using N- or O-donor solvents. In alkylation of CuI catalyzed mixed zincate n-BuPh 2ZnMgBr and also n-Bu2PhZnMgBr in THF at reflux temperature Ph group transfer takes place (n-Bu/Ph transfer ratio is 1:9 and 4:6, respectively) whereas n-Bu transfer increases in THF:NMP (1:1) resulting n-Bu/Ph transfer ratio of 4:6 and 8:2, respectively. Group transfer ability in allylation of n-BuPhZn seems not to be solvent dependent. The solvent effect on the group transfer ability has been found to be dependent also on the R 1 and R2 partnership in room temperature benzoylation of catalytic mixed cuprates, R1R2CuZnI, derived from CuI catalyzed R1R2Zn. These results are briefly discussed in terms of solvation of mixed diorganocuprate and diorganozinc reagents and provide useful information in their atom-economic alkyl, allyl and acyl coupling reactions.
- Erdik, Ender,Ero?lu, Fatma,Kalkan, Melike,Pekel, ?zgen ?mür,?zkan, Duygu,Serdar, Ebru Z.
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p. 235 - 241
(2013/10/01)
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- The hydrodeoxygenation of bioderived furans into alkanes
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The conversion of biomass into fuels and chemical feedstocks is one part of a drive to reduce the world's dependence on crude oil. For transportation fuels in particular, wholesale replacement of a fuel is logistically problematic, not least because of the infrastructure that is already in place. Here, we describe the catalytic defunctionalization of a series of biomass-derived molecules to provide linear alkanes suitable for use as transportation fuels. These biomass-derived molecules contain a variety of functional groups, including olefins, furan rings and carbonyl groups. We describe the removal of these in either a stepwise process or a one-pot process using common reagents and catalysts under mild reaction conditions to provide n-alkanes in good yields and with high selectivities. Our general synthetic approach is applicable to a range of precursors with different carbon content (chain length). This allows the selective generation of linear alkanes with carbon chain lengths between eight and sixteen carbons.
- Sutton, Andrew D.,Waldie, Fraser D.,Wu, Ruilian,Schlaf, Marcel,'Pete'Silks, Louis A.,Gordon, John C.
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p. 428 - 432
(2013/07/05)
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- SYNTHESIS OF HIGH CALORIC FUELS AND CHEMICALS
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In one embodiment, the present application discloses methods to selectively synthesize higher alcohols and hydrocarbons useful as fuels and industrial chemicals from syngas and biomass. Ketene and ketonization chemistry along with hydrogenation reactions are used to synthesize fuels and chemicals. In another embodiment, ketene used to form fuels and chemicals may be manufactured from acetic acid which in turn can be synthesized from synthesis gas which is produced from coal, biomass, natural gas, etc.
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Paragraph 0096
(2013/05/23)
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- COMPOUNDS AND METHODS FOR THE PRODUCTION OF LONG CHAIN HYDROCARBONS FROM BIOLOGICAL SOURCES
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The present invention is directed to the preparation of oxygenated, unsaturated hydrocarbon compounds, such as derivatives of furfural or hydroxymethyl furfural produced by aldol condensation with a ketone or a ketoester, as well as methods of deoxidatively reducing those compounds with hydrogen under acidic conditions to provide saturated hydrocarbons useful as fuels.
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Paragraph 0098
(2013/03/28)
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- Decarbonylation of water insoluble carboxaldehydes in aqueous microemulsions by some sol-gel entrapped catalysts
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In the course of our attempts to replace harmful solvents in organic processes by environmentally favored media, we investigated the use of aqueous microemulsions for catalytic decarbonylation of different kinds of aldehydes. The aldehydes were solubilized in the microemulsions with the aid of the cationic surfactant, cetyltrimethylammonium bromide. The aldehydes were transferred into CO-free products by sol-gel entrapped catalysts. The best results were obtained in the presence of nanoparticles of Pd(0). The heterogenized catalyst could usually be recycled 7-8 times without loss of catalytic activity. At relatively low temperatures (140°C) the decarbonylation proceeds stepwise. Initially a mixture of saturated and unsaturated products is formed. At 180°C however, fast hydrogenation of the unsaturated compounds takes place. These investigations may be regarded as model studies for the conversion of biomass derived intermediates to fuels and chemicals.
- Dahoah, Shirel,Nairoukh, Zackaria,Fanun, Monzer,Schwarze, Michael,Schom?cker, Reinhard,Blum, Jochanan
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- Catalytic aminomethylation of alkenes in a dimethylformamide medium
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The hydroaminomethylation of alkenes with dimethylamine catalyzed by rhodium and ruthenium complexes in a dimethylformamide medium under synthesis-gas pressures of 2 MPa has been studied. It has been shown that the combined use of these metals leads to a significant increase in the rate of formation of amines and selectivity for n-alkyldimethylamine. It has been found that the reaction can proceed with dimethylformamide used as an aminating agent without the addition of dimethylamine. Pleiades Publishing, Ltd., 2012.
- Karakhanov,Runova,Kardasheva,Losev,Maksimov,Terenina
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experimental part
p. 179 - 185
(2012/07/28)
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