- Development and mechanistic study of a new aldehyde decarbonylation catalyst
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Rh2(PMe3)2(CO)2Cl2 (2) has been found to catalyze the decarbonylation of aldehydes to give the corresponding alkanes. Reaction rates are comparable to those of the most active nonradical systems previously reported. A mechanistic study indicates that the turnover-limiting reaction step includes addition of the aldehydic C-H bond to an intact molecule of 2; ligand dissociation or cleavage of the chloride bridge does not occur prior to the C-H addition step. This conclusion is based on kinetic studies (d[R′H]/dt = kobs[2[R′CHO]; R′ = n-C11H23; kobs = 2.2 × 10-4 M-1 s-1; ΔS? = -26 eu) and the observation of a significant kinetic isotope effect (kRCHO/RCDO > 1.8).
- Abu-Hasanayn, Faraj,Goldman, Martin E.,Goldman, Alan S.
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- ETUDE DES REACTIONS DE SUBSTITUTION HOMOLITIQUE SUR LE NOYAU PYRIDINIQUE; INFLUENCE DE L'ACIDITE DU MILIEU
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Homolytic substitution by the 1-n-undecyl radical at positions 2 and 4 of the pyridine nucleus results from thermal decomposition of dodecanoyl peroxide in acetic acid.Rate dependence on pH shows that pyridine protonation increases the rate of addition of the alkyl radical to the pyridine ring but decreases the rate of the reaction of the intermediate radical with the peroxide.Results are interpreted in terms of orbital interaction theory.
- Sebedio, J. L.,Sorba, J.,Fossey, J.,Lefort, D.
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- Rate Constants for the Reaction of Acyl Radicals with Bu3SnH and (TMS)3SiH
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The rate constants for the hydrogen abstraction from Bu3SnH and (TMS)3SiH by acyl radicals have been measured by using competing decarbonylation reactions as timing devices.
- Chatgilialoglu, Chryssostomos,Lucarini, Marco
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- Hydrogenation of quinolines, alkenes, and biodiesel by palladium nanoparticles supported on magnesium oxide
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A new catalyst composed of Pd nanoparticles supported on MgO has been prepared by the room temperature NaBH4 reduction of Na 2PdCl4 in methanol in the presence of the support. TEM measurements reveal well-dispersed Pd particles of mean diameter 1.7 nm attached to the MgO surface. Further characterization was achieved by ICP-AES, XPS, XRD, H2 pulse chemisorption and H2-TPR. The new catalyst is efficient for the regioselective hydrogenation of the heterocyclic ring of quinolines, as well as for the mild reduction of a variety of alkenes representative of fuel components, and the partial saturation of biodiesel. The new material is considerably more reactive than commercial Pd/SiO2 and Pd/Al2O3 catalysts under analogous reaction conditions.
- Rahi, Reena,Fang, Minfeng,Ahmed, Atif,Sánchez-Delgado, Roberto A.
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- Potassium on Alumina as a Reagent for Reductive Decyanation of Alkylnitriles.
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Highly dispersed potassium over neutral alumina (K/Al2O3), easily prepared by melting potassium over alumina in an inert atmosphere, is capable of effecting reductive cleavage of the cyano group in alkylnitriles in hexane at room temperature in 70-91percent yield.This decyanation method is applied in the key step of a novel synthesis of (Z)-9-dodecen-1-yl acetate, the sex pheromone of Paralobesia viteana.
- Savoia, Diego,Tagliavini, Emilio,Trombini, Claudio,Umani-Ronchi, Achille
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- Fatty methyl ester hydrogenation to fatty alcohol part I: Correlation between catalyst properties and activity/selectivity
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Fatty alcohols, derived from natural sources, are commercially produced by hydrogenation of fatty acids or methyl esters in slurry-phase or fixed-bed reactors. One slurry-phase hydrogenation of methyl ester process flows methyl esters and powdered copper chromite catalyst into tubular reactors under high hydrogen pressure and elevated temperature. In the present investigation, slurry-phase hydrogenations of C12 methyl ester were carried out in semi-batch reactions at non-optimal conditions (i.e., low hydrogen pressure and elevated temperature). These conditions were used to accentuate the host of side reactions that occur during the hydrogenation. Some 14 side reaction routes are outlined. As an extension of this study, copper chromite catalyst was produced under a number of varying calcination temperatures. Differences in catalytic activity and selectivity were determined by closely following side reaction products. Both activity and selectivity correlate well with the crystallinity of the copper chromite surface; they increase with decreasing crystallinity. The ability to follow the wide variety of side reactions may well provide an additional tool for the optimized design of hydrogenation catalysts.
- Rieke, Ross D.,Thakur, Deepak S.,Roberts, Brian D.,White, Geoffrey T.
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- Synthesis of renewable diesel range alkanes by hydrodeoxygenation of furans over Ni/Hβ under mild conditions
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Diesel range branched alkanes were synthesized by the solvent-free hydrodeoxygenation of 5,5′-(butane-1,1-diyl)bis(2-methylfuran), the hydroxyalkylation/alkylation product of 2-methylfuran and butanal. Over the non-noble metal catalyst Ni/Hβ-(394), ~90% carbon yield of diesel range alkanes was achieved at a much lower temperature (503 K) than the temperature (623 K) used in the literature over noble metal catalysts.
- Li, Guangyi,Li, Ning,Yang, Jinfan,Li, Lin,Wang, Aiqin,Wang, Xiaodong,Cong, Yu,Zhang, Tao
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- Cross-coupling of alkyl halides with Grignard reagents using nickel and palladium complexes bearing η3-allyl ligand as catalysts
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The cross-coupling of Grignard reagents with alkyl bromides and tosylates has been achieved by the use of η3-allylnickel and η3-allylpalladium complexes as catalysts. The Royal Society of Chemistry.
- Terao, Jun,Naitoh, Yoshitaka,Kuniyasu, Hitoshi,Kambe, Nobuaki
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- Catalyst-free synthesis of biodiesel precursors from biomass-based furfuryl alcohols in the presence of H2O and air
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Production of biodiesel from biomass resources usually requires elongation of carbon numbers from typical C5 and C6 platform molecules through C-C coupling reactions, which were catalyzed by acid, base or metal catalysts traditionally. Herein, a catalyst-free method was developed to produce bis(furan-2-yl)methane derivatives (BFMs) from furfuryl alcohol derivatives (FAs) in the presence of H2O and air without any other additional catalysts. An 81% yield of bis(5-methylfuran-2-yl)methane (BMFM) can be obtained from 5-methylfurfuryl alcohol (5-MFA) and a 59% total yield of C11 biodiesel was obtained from 5-methylfurfural (5-MF). In addition, a H2O and air mediated free radical decarboxylation mechanism was proposed based on the detailed mechanistic studies. This strategy offers a green, low-cost and environmentally friendly approach to synthesize biodiesel precursors from biomass based platform molecules.
- Qin, Shengxiang,Li, Teng,Zhang, Man,Liu, Hongyu,Yang, Xin,Rong, Nianxin,Jiang, Jun,Wang, Yalin,Zhang, Hua,Yang, Weiran
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- Hydrothermal decarboxylation and hydrogenation of fatty acids over Pt/C
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We report herein on the conversion of saturated and unsaturated fatty acids to alkanes over Pt/C in high-temperature water. The reactions were done with no added H2. The saturated fatty acids (stearic, palmitic, and lauric acid) gave the corresponding decarboxylation products (n-alkanes) with greater than 90% selectivity, and the formation rates were independent of the fatty acid carbon number. The unsaturated fatty acids (oleic and linoleic acid) exhibited low selectivities to the decarboxylation product. Rather, the main pathway was hydrogenation to from stearic acid, the corresponding saturated fatty acid. This compound then underwent decarboxylation to form heptadecane. On the basis of these results, it appears that this reaction system promotes in situ H 2 formation. This hydrothermal decarboxylation route represents a new path for using renewable resources to make molecules with value as liquid transportation fuels.
- Fu, Jie,Lu, Xiuyang,Savage, Phillip E.
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- Nanoparticle-based catalysis using supramolecular hydrogels
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A thermoregulated catalytic process has been elaborated using a ruthenium-nanoparticle catalyst embedded into a supramolecular cyclodextrin-based hydrogel matrix. Upon heating, the gel phase turned into a sol phase in which alkenes could be efficiently hydrogenated. Upon cooling, the reaction products and the metallic catalyst could be easily separated. The reusability of the system was clearly demonstrated. Copyright
- Leger, Bastien,Menuel, Stephane,Ponchel, Anne,Hapiot, Frederic,Monflier, Eric
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- Ni- or Cu-catalyzed cross-coupling reaction of alkyl fluorides with grignard reagents
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n-Octyl fluoride underwent a cross-coupling reaction with n-propylmagnesium bromide in the presence of 1,3-butadiene using NiCl2 as a catalyst at room temperature to give undecane in moderate yields. This alkyl-alkyl cross-coupling proceeded more efficiently when CuCl2 was employed instead of NiCl2. Addition of 1,3-butadiene dramatically improved the yields of the coupling products from primary alkyl Grignard reagents in both Ni- and Cu-catalyzed reactions. Alkyl fluorides efficiently reacted with tertiary alkyl and phenyl Grignard reagents using CuCl2 in the absence of 1,3-butadiene to afford the coupling products in high yields. The competitive reaction of a mixture of alkyl halides (R-X; X = F, Cl, Br) with nC5H11MgBr showed that the reactivities of the halides increase in the order R-Cl R-F R-Br. In contrast, in the Cu-catalyzed reaction with PhMgBr, the reactivities increase in the order R-Cl R-Br R-F. Copyright
- Terao, Jun,Ikumi, Aki,Kuniyasu, Hitoshi,Kambe, Nobuaki
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- Kinetic studies of the ni-catalyzed cross-coupling of alkyl halides and a tosylate with butyl grignard reagent in the presence of 1,3-butadiene
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Kinetic studies of the nickel-catalyzed cross-coupling reaction of alkyl bromides, iodides, and tosylates with butyl Grignard reagents in the presence of butadiene were performed. The reaction rate was first order with respect to the halides and the nickel catalyst. The butyl Grignard reagent, at concentrations of ca. 0.4M or higher, had little effect on the reaction rate. The relative reactivities and activation parameters were determined for these alkyl halides and a tosylate.
- Iwasaki, Takanori,Tsumura, Asako,Omori, Takehiro,Kuniyasu, Hitoshi,Terao, Jun,Kambe, Nobuaki
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- Evidence for a NiI active species in the catalytic cross-coupling of alkyl electrophiles
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Addition of terpyridine to (TMEDA)Ni(CH3)2 results in the high-yield formation of (terpyridyl)NiMe (3). This NiI organometallic complex was found to be capable of transferring its methyl group to iodocyclohexane to produce methylcyclohexane in high yield. Compound 3 can also serve as an initiator for the catalytic cross-coupling of alkyl electrophiles performed under Negishi-like conditions. Copyright
- Anderson, Thomas J.,Jones, Gavin D.,Vicic, David A.
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- Light-Driven Enzymatic Decarboxylation of Fatty Acids
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The photoenzymatic decarboxylation of fatty acids to alkanes is proposed as an alternative approach for the synthesis of biodiesel. By using a recently discovered photodecarboxylase from Chlorella variabilis NC64A (CvFAP) we demonstrate the irreversible preparation of alkanes from fatty acids and triglycerides. Several fatty acids and their triglycerides are converted by CvFAP in near-quantitative yield and exclusive selectivity upon illumination with blue light. Very promising turnover numbers of up to 8000 were achieved in this proof-of-concept study.
- Huijbers, Mieke M. E.,Zhang, Wuyuan,Tonin, Fabio,Hollmann, Frank
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- Diesel and alkane fuels from biomass by organocatalysis and metal-acid tandem catalysis
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Combo deal: Biomass furaldehydes are upgraded into oxygenated diesel and high-quality C10-12 linear alkane fuels. The first of two steps involves solvent-free self-condensation (Umpolung) through organocatalysis using an N-heterocyclic carbene
- Liu, Dajiang,Chen, Eugene Y.-X.
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- A novel photoinduced reduction system of low-valent samarium species: Reduction of organic halides and chalcogenides, and its application to carbonylation with carbon monoxide
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Visible light irradiation is found to enhance the reducing ability of samarium diiodide (SmI2) dramatically. Organic halides (RCl, RBr, RI) and chalcogenides (RSPh, RSePh, RTePh) are smoothly reduced to the corresponding hydrocarbons by using this SmI2-hv system. The photoactivation can be also applied to ytterbium diiodide (YbI2) successfully. When the reduction of alkyl chlorides (RCl) by using the SmI 2-hv system is conducted under the pressure of carbon monoxide, unsymmetric ketones (RC(O)CH2R) are obtained as carbonylating products. A mechanistic pathway may involve the formation of acylsamarium species (RC(O)SmI2), which undergo dimerization, followed by reduction with SmI2, leading to the unsymmetric ketones.
- Sumino, Yukihito,Harato, Nami,Tomisaka, Yuri,Ogawa, Akiya
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- Radical deoxygenation of alcohols and vicinal diols with N-ethylpiperidine hypophosphite in water
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Radical deoxygenation of alcohols and vicinal diols with N-ethylpiperidine hypophosphite both in alcohols and in water is described. S-Methyl dithiocarbonate and bis-S-methyl dithiocarbonate of carbohydrates and nucleosides were deoxygenated efficiently under reaction conditions.
- Jang, Doo Ok,Cho, Dae Hyan
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- Novel enhancement of the reducing ability of ytterbium diiodide by irradiation with near-UV light
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Irradiation with near-UV light dramatically enhances the reducing ability of ytterbium diiodide (Ybl2). Organic bromides, iodides, tosylates, and tellurides are reduced efficiently by a YbI2-hv system, while these can not be reduced with YbI2 in the dark.
- Ogawa, Akiya,Ohya, Syoji,Sumino, Yukihito,Sonoda, Noboru,Hirao, Toshikazu
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- Synthesis of Diesel and Jet Fuel Range Alkanes with Furfural and Angelica Lactone
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A route was developed for the synthesis of diesel and jet fuel range C9 and C10 alkanes with furfural and angelica lactone, which can be obtained from hemicellulose and cellulose. It was found that angelica lactone is more reactive than levulinic acid or its other derivates in the aldol condensation with furfural. Among the investigated catalysts, Mn2O3 was found to be the most active and was very stable for the aldol condensation of furfural and angelica lactone. Over Mn2O3, a high carbon yield of C10 oxygenates (about 96%) can be achieved by the aldol condensation of furfural and angelica lactone under mild conditions (353 K, 4 h). By the hydrogenation and hydrodeoxygenation of the aldol condensation product over the Pd/C and Pd-FeOx/SiO2 catalysts, high carbon yields (~96%) of C9 and C10 alkanes were obtained.
- Xu, Jilei,Li, Ning,Yang, Xiaofeng,Li, Guangyi,Wang, Aiqin,Cong, Yu,Wang, Xiaodong,Zhang, Tao
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- Intramolecular homolytic displacements. 30. Functional decarbonylative transformations of aldehydes via homolytically induced decomposition of unsaturated peroxyacetals
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Homolytically induced decompositions of unsaturated peroxyacetals, synthesized from aldehydes, gave alkoxyalkoxyl radicals that yielded alkyl radicals by rapid β-scission. The latter radicals could react with several types of "transfer agents" to smoothly bring about homolytic decarbonylative functional group transformations of aldehydes into halides, hydrocarbons, xanthates, alkanenitriles, 2-alkyl-3-chloromaleic anhydrides, 1-phenylalk-1-ynes, and ethyl 2-alkylpropenoates.
- Degueil-Castaing, Marie,Moutet, Laurent,Maillard, Bernard
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- Desulphurization of benzothiophene derivatives with nickel boride
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Nickel boride, conveniently generated in situ from nickel chloride hexahydrate and sodium borohydride, has been used to desulphurize a variety of benzothiophene derivatives to the corresponding hydrocarbons under exceptionally mild conditions.
- Back, Thomas G.,Yang, Kexin
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- Soluble Polyethylene- and Polystyrene-Bound Tin Halides as Catalysts for Reductions of Alkyl and Aryl Bromides and Iodides by Sodium Borohydride
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The synthesis, characterization, and use of soluble polyethylene- and polystyrene-bound tin chlorides as catalysts for the reduction of alkyl halides using a suspension of sodium borohydride in toluene and a crown ether as a phase-transfer catalyst are described.These tin-containing soluble macromolecules were synthesized by anionic oligomerization of ethylene or styrene followed by electrophilic substitution of the resulting "living" oligomer with various organic tin halides including tin tetrachloride, n-butyltin trichloride, di-n-butyltin dichloride, and diphenyltin dichloride.The resulting oligomer-bound tin reagents were characterized by 1H and 119Sn NMR spectroscopy, and the tin content of the oligomers was analyzed by ICP analysis.Typically the tin reagents were used as cocatalysts (ca. 10percent) along with 10-20percent of a crown ether as a phase-transfer catalyst in reductions of primary, secondary, and aryl halides using a suspension of sodium borohydride in hot toluene at 110 deg C.Kinetic studies showed that the reaction rate was dependent on the concentration of the tin catalyst and the secondary halides reacted slightly faster than primary halides.
- Bergbreiter, David E.,Walker, Samuel A.
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- Metal-Organic Framework-Confined Single-Site Base-Metal Catalyst for Chemoselective Hydrodeoxygenation of Carbonyls and Alcohols
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Chemoselective deoxygenation of carbonyls and alcohols using hydrogen by heterogeneous base-metal catalysts is crucial for the sustainable production of fine chemicals and biofuels. We report an aluminum metal-organic framework (DUT-5) node support cobalt(II) hydride, which is a highly chemoselective and recyclable heterogeneous catalyst for deoxygenation of a range of aromatic and aliphatic ketones, aldehydes, and primary and secondary alcohols, including biomass-derived substrates under 1 bar H2. The single-site cobalt catalyst (DUT-5-CoH) was easily prepared by postsynthetic metalation of the secondary building units (SBUs) of DUT-5 with CoCl2 followed by the reaction of NaEt3BH. X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy (XANES) indicated the presence of CoII and AlIII centers in DUT-5-CoH and DUT-5-Co after catalysis. The coordination environment of the cobalt center of DUT-5-Co before and after catalysis was established by extended X-ray fine structure spectroscopy (EXAFS) and density functional theory. The kinetic and computational data suggest reversible carbonyl coordination to cobalt preceding the turnover-limiting step, which involves 1,2-insertion of the coordinated carbonyl into the cobalt-hydride bond. The unique coordination environment of the cobalt ion ligated by oxo-nodes within the porous framework and the rate independency on the pressure of H2 allow the deoxygenation reactions chemoselectively under ambient hydrogen pressure.
- Antil, Neha,Kumar, Ajay,Akhtar, Naved,Newar, Rajashree,Begum, Wahida,Manna, Kuntal
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supporting information
p. 9029 - 9039
(2021/06/28)
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- Highly stable and selective catalytic deoxygenation of renewable bio-lipids over Ni/CeO2-Al2O3 for N-alkanes
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Ni-based catalysts are easy deactivated in bio-lipids deoxygenation due to metal aggregation and Ni leaching. They also suffer from the hydrocracking of C–C bonds due to strong acidity at high reaction temperature (≥ 300 ℃). Herein, a series of Ni/CeO2-Al2O3 catalysts with different Ce/Al ratio were prepared by one-pot sol-gel method. The characteristic results showed that an appropriate addition of Ce both increase the catalytic activity and stability in bio-lipids deoxygenation. The oxygen vacancies formed by Ce introduction weaken the strong interaction of Ni-Al, thus improving Ni sites dispersion. Additional, Ce-addition in NiCeAl system increases weak and medium acidity and decreases strong acidity, preventing the C–C bond cleavage of hydrocarbon. As the result, the Ni/CeAl-3.0 catalyst afforded a 97.1 % n-C17 yield at 99.9 % MO conversion under 2.5 MPa H2 at 300 ℃ for 6 h. Minor C15-16 alkanes (17 yield). After simple regeneration, n-C17 yield was recovered to 95 %. Furthermore, non-edible bio-lipids (JO and WCO) can be converted to C13-18 alkanes with 95.2 % and 93.8 % yields, respectively.
- Ba, Wenxia,Cui, Huamin,Fu, Lin,Li, Yongfei,Liu, Yuejin
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- CONTINUOUS PROCESS FOR THE PRODUCTION OF ALKANES
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Continuous reductive dehydroxymethylation process for the preparation of alkanes from primary aliphatic alcohols, having 3 to 25 carbon atoms, in the presence of hydrogen and a catalyst in a reactor at a pressure of ≥ 2 bar, characterized in that the dehydroxymethylation takes place in the vapor phase.
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Page/Page column 12-13
(2021/11/13)
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- A New Protocol for Catalytic Reduction of Alkyl Chlorides Using an Iridium/Bis(benzimidazol-2′-yl)pyridine Catalyst and Triethylsilane
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The reduction of alkyl chlorides using triethylsilane is investigated. Primary, secondary, tertiary, and benzylic C-Cl bonds are effectively converted into C-H bonds using an [IrCl(cod)] 2/2,6-bis(benzimidazol-2′-yl)pyridine catalyst system. This catalyst system is quite simple since the tridentate N-ligand can be easily prepared in one step from commercially available reagents.
- Fukuyama, Takahide,Hamada, Yuki,Ryu, Ilhyong
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p. 3404 - 3408
(2021/07/14)
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- Acidic metal-organic framework empowered precise hydrodeoxygenation of bio-based furan compounds and cyclic ethers for sustainable fuels
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Target synthesis of hydrocarbons from abundant biomass is highly desired for sustainable aviation fuels (SAFs) to meet the need for both net zero carbon emission and air pollution control. However, precise hydrodeoxygenation (PHDO) of bio-based furan compounds and cyclic ethers to isomerically pure alkanes remains a challenge in heterogenous catalysis, which usually requires delicate control of the distribution of acid and metal catalytic sites in nanoconfined space. Here we show that a nanoporous acidic metal-organic framework (MOF), namely MIL-101-SO3H, enables one-pot PHDO reactions from furan-derivative oxygenates to solely single-component alkanes by just mechanical mixing with commercial Pd/C towards highly efficient and highly selective hydrocarbon production. The superior performance of such tandem catalysts can be attributed to the preferential adsorption of oxygenate precursors and expulsion of deoxygenated intermediates benefiting from Lewis acid sites embedded in the MOF. The strong Br?nsted acidity of MIL-101-SO3H is contributed by both the -SO3H groups and the adsorbed H2O, which makes it a water-tolerant solid acid for durable PHDO processes. The simplicity of mechanical mixing of different heterogenous catalysts allows the modulation of the tandem catalysis system for optimization of the ultimate catalytic performance. This journal is
- Gao, Xiang-Yu,He, Hai-Long,Li, Zhi,Liu, Dong-Huang,Wang, Jun-Jie,Xiao, Yao,Yi, Xianfeng,Zeng, Tengwu,Zhang, Yue-Biao,Zheng, Anmin,Zhou, Si-Yu
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supporting information
p. 9974 - 9981
(2021/12/27)
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- One-pot reductive amination of carboxylic acids: a sustainable method for primary amine synthesis
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The reductive amination of carboxylic acids is a very green, efficient and sustainable method for the production of (bio-based) amines. However, with current technology, this reaction requires two to three reaction steps. Here, we report the first (heterogeneous) catalytic system for the one-pot reductive amination of carboxylic acids to amines, with solely H2 and NH3 as the reactants. This reaction can be performed with relatively cheap ruthenium-tungsten bimetallic catalysts in the green and benign solvent cyclopentyl methyl ether (CPME). Selectivities of up to 99% for the primary amine could be achieved at high conversions. Additionally, the catalyst is recyclable and tolerant for common impurities such as water and cations (e.g. sodium carboxylate).
- Coeck, Robin,De Vos, Dirk E.
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supporting information
p. 5105 - 5114
(2020/08/25)
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- Normal Alpha Olefin Synthesis Using Dehydroformylation or Dehydroxymethylation
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The present invention discloses processes for producing normal alpha olefins, such as 1-hexene, 1-octene, 1-decene, and 1-dodecene in a multistep synthesis scheme from another normal alpha olefin. Also disclosed are reactions for converting aldehydes, primary alcohols, and terminal vicinal diols into normal alpha olefins.
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Paragraph 0127; 0128
(2019/09/06)
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- Oxidative Dehydroxymethylation of Alcohols to Produce Olefins
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Catalyst compositions for the conversion of aldehyde compounds and primary alcohol compounds to olefins are disclosed herein. Reactions include oxidative dehydroxymethylation processes and oxidative dehydroformylation methods, which are beneficially conducted in the presence of a sacrificial acceptor of H2 gas, such as N,N-dimethylacrylamide.
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Paragraph 0056
(2019/09/06)
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- Iron-catalyzed AlkylAlkyl negishi coupling of organoaluminum reagents
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The first iron-catalyzed cross-coupling reaction of alkyl halides with alkylaluminum reagents (alkylalkyl Negishi coupling) is developed using an iron/bisphosphine catalyst system. The reaction shows high functional group tolerance: various primary alkyl halides possessing a non-protected indole, carboxyl, or hydroxy group are coupled with primary alkylaluminum reagents in good yields. Potassium fluoride plays a key role to promote the reaction by generating an aluminate species, which facilitates the transmetalation between the organoaluminum and the iron catalyst.
- Agata, Ryosuke,Kawamura, Shintaro,Isozaki, Katsuhiro,Nakamura, Masaharu
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supporting information
p. 238 - 241
(2019/03/13)
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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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- 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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- CATALYST FOR ONE CARBON-REDUCTION REACTION, AND METHOD FOR PRODUCING ONE CARBON-REDUCTION COMPOUND USING THE SAME
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PROBLEM TO BE SOLVED: To provide a method for producing selectively a one carbon-reduction compound, using a compound having a primary hydroxy group, a carboxyl group, or an alkoxycarbonyl group, or a lactone compound, as a substrate. SOLUTION: A method of obtaining a one carbon-reduction compound includes the reaction of a compound as a substrate represented by formula (1-1) or (1-2) or (1-3) with hydrogen in the presence of a catalyst in which a metal selected from Ru, Rh, Pd, Ir, and Pt is supported on a support selected from CeO2, hydroxyapatite, ZrO2, TiO2, hydrotalcite, SiO2, MgO, and Al2O3 (R1-R3 independently represent H, a substituted/unsubstituted monovalent hydrocarbon group, or a monovalent group in which two or more hydrocarbon groups are bound together through a linking group; R1-R3 may form a ring with adjacent carbon; L is a substituted/unsubstituted divalent hydrocarbon group or the like; and n is an integer of 0 or greater). SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0060; 0070; 0071
(2018/07/28)
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- Tandem Catalysis: Transforming Alcohols to Alkenes by Oxidative Dehydroxymethylation
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We report a Rh-catalyst for accessing olefins from primary alcohols by a C-C bond cleavage that results in dehomologation. This functional group interconversion proceeds by an oxidation-dehydroformylation enabled by N,N-dimethylacrylamide as a sacrificial acceptor of hydrogen gas. Alcohols with diverse functionality and structure undergo oxidative dehydroxymethylation to access the corresponding olefins. Our catalyst protocol enables a two-step semisynthesis of (+)-yohimbenone and dehomologation of feedstock olefins.
- Wu, Xuesong,Cruz, Faben A.,Lu, Alexander,Dong, Vy M.
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supporting information
p. 10126 - 10130
(2018/08/23)
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- Palladium-metalated porous organic polymers as recyclable catalysts for chemoselective decarbonylation of aldehydes
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A novel palladium nanoparticle (NP)-metalated porous organic ligand (Pd NPs/POL-xantphos) has been prepared for the chemoselective decarbonylation of aldehydes. This heterogenous catalyst not only has excellent catalytic activity and chemoselectivity, but also holds high activity after 10 runs of reuse. The effective usage of this method is demonstrated through the synthesis of biofuels such as furfuryl alcohol (FFA) via the highly chemoselective decarbonylation of biomass-derived 5-hydroxy-methylfurfural (HMF) with a TON up to 1540. More importantly, 9-fluorenone could be obtained in one step through the decarbonylation of 2-bromobenzaldehyde by using this heterogeneous catalyst.
- Li, Wen-Hao,Li, Cun-Yao,Li, Yan,Tang, Hai-Tao,Wang, Heng-Shan,Pan, Ying-Ming,Ding, Yun-Jie
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supporting information
p. 8446 - 8449
(2018/08/28)
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- PROCESS FOR THE DECARBOXYLATIVE KETONIZATION OF FATTY ACIDS OR FATTY ACID DERIVATIVES
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The present invention is directed to a process for synthesizing an internal ketone K1 by decarboxylative ketonization reaction of a fatty acid, a fatty acid derivative or a mixture thereof in a liquid phase with a metal compound as catalyst in a reaction medium, said process being characterized in that a ketone K2 at liquid state, which is identical or similar to the ketone K1, is introduced into the reaction medium. The so-synthesized internal ketone K1 can be used for the preparation of a variety of end compounds, including surfactants having a twin-tail structure or a Gemini structure.
- -
-
Paragraph 00523-00525
(2018/03/09)
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- Hydrodeoxygenation of Sorbitol into Bio-Alkanes and -Alcohols Over Phosphated Ruthenium Molybdenum Catalysts
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Biofuels such as renewable alkanes and higher alcohols have drawn considerable interests for the use in internal combustion engines. Especially, higher alcohols could be used as a blending agent for diesel fuels. Herein, carbon supported phosphated ruthenium-molybdenum (RuMoP) catalysts were employed in continuous trickle-bed reactor for converting sorbitol into renewable alkanes and higher alcohols. The results showed that RuMoP on an active carbon (AC) support presented a complete sorbitol conversion and high yields of alkanes and alcohols in gasoline and diesel range. Subsequently, carbon nanotube (CNT) supported RuMoP was prepared and studied in detail for comparison. RuMoP/CNT presented a low C?C bond cracking property in sorbitol conversion and high selectivity of C6 products in gas-phase (C6 alkane, 74.7 %) and oil-phase (C6 alkane and alcohols, 87.8 %). Finally, detailed characterizations (N2-adsorption, XRD, HRTEM, XPS, NH3-TPD, Py-IR spectrums, etc.) were performed over relevant catalysts (RuMoP/C and RuMoP/CNT) for correlating their catalytic and physicochemical properties.
- Weng, Yujing,Wang, Tiejun,Wang, Chenguang,Liu, Qiying,Zhang, Yulong,Duan, Peigao,Wang, Longlong,Yin, Hongxing,Liu, Shijun,Ma, Longlong
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p. 5046 - 5052
(2018/10/26)
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- Rhodium-Catalyzed Intermolecular Carbonylative [2 + 2 + 1] Cycloaddition of Alkynes Using Alcohol as the Carbon Monoxide Source for the Formation of Cyclopentenones
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A highly regioselective rhodium-catalyzed intermolecular carbonylative [2 + 2 + 1] cycloaddition of alkynes using alcohol as a CO surrogate to access 4-methylene-2-cyclopenten-1-ones has been developed. In this transformation, the alcohol performs multiple roles, including generating the Rh-H intermediate, functioning as the CO source, and assisting in the isomerization of the alkyne. Alkynes can act as both the olefin and the alkyne partner in the cyclopentenone core.
- Kim, Ju Hyun,Song, Taemoon,Chung, Young Keun
-
supporting information
p. 1248 - 1251
(2017/03/14)
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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.
- -
-
Paragraph 0059-0065
(2017/03/21)
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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)
-
- 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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- 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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- Effect of functional groups in organic chlorides on radical reduction with hydrostannane under microwave irradiation
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The effect of functional groups on the activation of molecules by microwave irradiation in the reduction of organic chlorides by Bu3SnH was investigated. The reactivity of a substrate with a hydroxy group increased under microwave heating conditions in comparison with conventional heating.
- Nishimoto, Yoshihiro,Yazawa, Satoshi,Kiyokawa, Kensuke,Kajiki, Takahito,Tsukahara, Yasunori,Yamauchi, Tomohisa,Wada, Yuji,Baba, Akio,Yasuda, Makoto
-
supporting information
p. 1116 - 1118
(2017/08/07)
-
- 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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- 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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- 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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- Scope and Mechanistic Analysis for Chemoselective Hydrogenolysis of Carbonyl Compounds Catalyzed by a Cationic Ruthenium Hydride Complex with a Tunable Phenol Ligand
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A cationic ruthenium hydride complex, [(C6H6)(PCy3)(CO)RuH]+BF4- (1), with a phenol ligand was found to exhibit high catalytic activity for the hydrogenolysis of carbonyl compounds to yield the corresponding aliphatic products. The catalytic method showed exceptionally high chemoselectivity toward the carbonyl reduction over alkene hydrogenation. Kinetic and spectroscopic studies revealed a strong electronic influence of the phenol ligand on the catalyst activity. The Hammett plot of the hydrogenolysis of 4-methoxyacetophenone displayed two opposite linear slopes for the catalytic system 1/p-X-C6H4OH (ρ = -3.3 for X = OMe, t-Bu, Et, and Me; ρ = +1.5 for X = F, Cl, and CF3). A normal deuterium isotope effect was observed for the hydrogenolysis reaction catalyzed by 1/p-X-C6H4OH with an electron-releasing group (kH/kD = 1.7-2.5; X = OMe, Et), whereas an inverse isotope effect was measured for 1/p-X-C6H4OH with an electron-withdrawing group (kH/kD = 0.6-0.7; X = Cl, CF3). The empirical rate law was determined from the hydrogenolysis of 4-methoxyacetophenone: rate = kobsd[Ru][ketone][H2]-1 for the reaction catalyzed by 1/p-OMe-C6H4OH, and rate = kobsd[Ru][ketone][H2]0 for the reaction catalyzed by 1/p-CF3-C6H4OH. Catalytically relevant dinuclear ruthenium hydride and hydroxo complexes were synthesized, and their structures were established by X-ray crystallography. Two distinct mechanistic pathways are presented for the hydrogenolysis reaction on the basis of these kinetic and spectroscopic data. (Chemical Equation Presented).
- Kalutharage, Nishantha,Yi, Chae S.
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supporting information
p. 11105 - 11114
(2015/09/15)
-
- Hydrogenation of arenes, nitroarenes, and alkenes catalyzed by rhodium nanoparticles supported on natural nanozeolite clinoptilolite
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Abstract Nanozeolite clinoptilolite supported rhodium nanoparticles (Rh/NZ-CP) has been prepared and characterized by a variety of techniques, including XRD, BET, TEM, EDX, ICP-OES and XPS analysis. This nanomaterial contains 2 wt% Rh in the range of 5-20 nm metallic nanoparticles distributed on nanozeolite. The catalytic performance of Rh/NZ-CP was evaluated by the hydrogenation of arenes, nitroarenes, and alkenes under moderate reaction conditions. The prepared nanocatalyst can be facilely recovered and reused many times without significant decrease in activity and selectivity. The high catalytic activity, thermal stability and reusability, simple recovery and eco-friendly nature make present catalyst as a unique catalytic system, which is particularly attractive in green chemistry.
- Baghbanian, Seyed Meysam,Farhang, Maryam,Vahdat, Seyed Mohammad,Tajbakhsh, Mahmood
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p. 128 - 136
(2015/07/15)
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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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- BIOREFINING COMPOUNDS AND ORGANOCATALYTIC UPGRADING METHODS
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The invention provides new methods for the direct umpolung self-condensation of 5-hydroxymethylfurfural (HMF) by organocatalysis, thereby upgrading the readily available substrate into 5,5'-di(hydroxymethyl) furoin (DHMF). While many efficient catalyst systems have been developed for conversion of plant biomass resources into HMF, the invention now provides methods to convert such nonfood biomass directly into DHMF by a simple process as described herein. The invention also provides highly effective new methods for upgrading other biomass furaldehydes and related compound to liquid fuels. The methods include the organocatalytic self-condensation (umpolung) of biomass furaldehydes into (C8-C12)furoin intermediates, followed by hydrogenation, etherification or esterification into oxygenated biodiesel, or hydrodeoxygenation by metal-acid tandem catalysis into premium hydrocarbon fuels.
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Page/Page column 37; 38; 42; 43
(2014/01/18)
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- PROCESS FOR MAKING LINEAR LONG CHAIN ALKANES USING RENEWABLE FEEDSTOCKS
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A hydrodeoxygenation process for producing a linear alkane from a feedstock comprising a saturated or unsaturated C10-18 oxygenate that comprises an ester group, carboxylic acid group, carbonyl group and/or alcohol group is disclosed. The process comprises contacting the feedstock with a catalyst comprising (i) about 0.1% to 10% by weight of a metal selected from Group IB or VIII of the Periodic Table, and (ii) about 0.5% to 15% by weight of tungsten, rhenium, molybdenum, vanadium, manganese, zinc, chromium, germanium, tin, titanium, gold, and/or zirconium, at a temperature between about 150° C. to 250° C. and a hydrogen gas pressure of at least 300 psig. By contacting the feedstock with the catalyst under these temperature and pressure conditions, the C10-18 oxygenate is hydrodeoxygenated to a linear alkane that has the same carbon chain length as the C10-18 oxygenate.
- -
-
Paragraph 0119-0124
(2014/04/03)
-
- PROCESS FOR MAKING LINEAR LONG-CHAIN ALKANES FROM RENEWABLE FEEDSTOCKS USING CATALYSTS COMPRISING HETEROPOLYACIDS
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A hydrodeoxygenation process for producing a linear alkane from a feedstock comprising a saturated or unsaturated C10-18 oxygenate that comprises an ester group, carboxylic acid group, carbonyl group and/or alcohol group is disclosed. This process comprises contacting the feedstock with (i) a catalyst comprising about 0.1 % to about 10% by weight of a metal selected from Group IB, VIB, or VIII of the Periodic Table, and (ii) a heteropolyacid or heteropolyacid salt, at a temperature between about 150 °C to about 250 °C and a hydrogen gas pressure of at least about 300 psig. By contacting the feedstock with the catalyst and heteropolyacid or heteropolyacid salt under these temperature and pressure conditions, the C10-18 oxygenate is hydrodeoxygenated to a linear alkane that has the same carbon chain length as the C10-18 oxygenate.
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-
Page/Page column 37; 39
(2014/10/15)
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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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- Integrated catalytic process for biomass conversion and upgrading to C 12 furoin and alkane fuel
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Report herein is an integrated catalytic process for conversion and upgrading of biomass feedstocks into 5,5′-dihydroxymethyl furoin (DHMF), through self-coupling of 5-hydroxymethyl furfural (HMF) via organocatalysis, and subsequently into n-C12H26 alkane fuel via metal-acid tandem catalysis. The first step of the process involves semicontinuous organocatalytic conversion of biomass (fructose, in particular) to the high-purity HMF. N-Heterocyclic carbenes (NHCs) are found to catalyze glucose-to-fructose isomerization, and the relatively inexpensive thiazolium chloride [TM]Cl, a Vitamin B1 analog, catalyzes fructose dehydration to HMF of good purity (>99% by HPLC), achieving a constant HMF yield of 72% over 10 semicontinuous extraction batch runs. Crystallization of the crude HMF from toluene yields the spectroscopically and analytically pure HMF as needle crystals. The second step of the process is the NHC-catalyzed coupling of C 6 HMF produced by the semicontinuous process to C12 DHMF; the most effective organic NHC catalyst produces DHMF in 93% or 91% isolated yield with an NHC loading of 0.70 mol % or 0.10 mol % at 60°C for 3 h under solvent-free conditions. The third step of the process converts C12 DHMF to linear alkanes via hydrodeoxygenation. With a bifunctional catalyst system consisting of Pd/C + acetic acid + La(OTf)3 at 250°C and 300 psi H2 for 16 h, DHMF has been transformed to liquid hydrocarbon fuel (78% alkanes), with a 64% selectivity to n-C12H26 and an overall C/H/O % ratio of 84/11/5.0.
- Liu, Dajiang,Chen, Eugene Y.-X.
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p. 1302 - 1310
(2014/05/20)
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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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- Simple, chemoselective hydrogenation with thermodynamic stereocontrol
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Few methods permit the hydrogenation of alkenes to a thermodynamically favored configuration when steric effects dictate the alternative trajectory of hydrogen delivery. Dissolving metal reduction achieves this control, but with extremely low functional group tolerance. Here we demonstrate a catalytic hydrogenation of alkenes that affords the thermodynamic alkane products with remarkably broad functional group compatibility and rapid reaction rates at standard temperature and pressure.
- Iwasaki, Kotaro,Wan, Kanny K.,Oppedisano, Alberto,Crossley, Steven W. M.,Shenvi, Ryan A.
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supporting information
p. 1300 - 1303
(2014/02/14)
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- Rhodium-catalyzed tandem isomerization/hydroformylation of the bio-sourced 10-undecenenitrile: Selective and productive catalysts for production of polyamide-12 precursor
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The hydroformylation of 10-undecenenitrile (1) - a substrate readily prepared from renewable castor oil - in the presence of rhodium-phosphane catalysts systems is reported. The corresponding linear aldehyde (2) can be prepared in high yields and regioselectivities with a (dicarbonyl)rhodium acetoacetonate-biphephos [Rh(acac)(CO)2-biphephos] catalyst. The hydroformylation process is accompanied by isomerization of 1 into internal isomers of undecenenitrile (1-int); yet, it is shown that the Rh-biphephos catalyst effectively isomerizes back 1-int into 1, eventually allowing high conversions of 1/1-int into 2. Recycling of the catalyst by vacuum distillation under a controlled atmosphere was demonstrated over 4-5 runs, leading to high productivities up to 230,000 mol (2)×mol (Rh)-1 and 5,750 mol (2)×mol (biphephos)-1. Attempted recycling of the catalyst using a thermomorphic multicomponent solvent (TMS) phase-separation procedure proved ineffective because the final product 2 and the Rh-biphephos catalyst were always found in the same polar phase. Auto-oxidation of the linear aldehyde 2 into the fatty 10-cyano-2-methyldecanoic acid (5) proceeds readily upon exposure to air at room temperature, opening a new effective entry toward polyamide-12. Copyright
- Ternel, Jeremy,Couturier, Jean-Luc,Dubois, Jean-Luc,Carpentier, Jean-Francois
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p. 3191 - 3204
(2013/12/04)
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- Synthesis of (2-alkylthiothiazolin-5-yl)methyl dodecanoates via tandem radical reaction
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A series of (2-alkylthiothiazolin-5-yl)methyl dodecanoates was synthesized from various alkyl N-allylcarbamodithioates and dilauroyl peroxide via a tandem radical hydrogen-abstraction-cyclization-substitution/combination reaction with a 5-exo-trig radical cyclization as a key step. The current route is the first, convenient, and efficient synthesis of (2-alkylthiothiazolin-5-yl)methanol derivatives. The Royal Society of Chemistry.
- Kakaei, Saeed,Xu, Jiaxi
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p. 5481 - 5490
(2013/08/28)
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- Nickel-catalyzed decyanation of inert carbon-cyano bonds
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Nickel catalyzed decyanation of aryl and aliphatic cyanides with hydrosilane as the hydride source has been developed. This method is easy to handle, scalable and can be carried out without a glove box. The method has been applied in the cyanide directed functionalization reaction and α-substitution of benzyl cyanide.
- Patra, Tuhin,Agasti, Soumitra,Akanksha,Maiti, Debabrata
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supporting information
p. 69 - 71
(2013/02/21)
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- METHOD TO CONVERT FERMENTATION MIXTURE INTO FUELS
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The present disclosure provides methods to produce ketones suitable for use as fuels and lubricants by catalytic conversion of an acetone-butanol-ethanol (ABE) fermentation product mixture that can be derived from biomass.
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Page/Page column 78-79
(2013/02/27)
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