- Alkylation of toluene with ethanol to para-ethyltoluene over MFI zeolites: Comparative study and kinetic modeling
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The production of para-ethyltoluene (p-ET) from the alkylation of toluene with ethanol was investigated over three MFI zeolites with varying SiO2/Al2O3 ratio (80, 280, and 2000). The ethylation reaction was conducted in a batch fluidized-bed reactor at a temperature range of 300-400 °C, reaction times of 5-20 s and molar feed ratio of toluene to ethanol at 1:1. Toluene conversion increased with temperature over all the MFI zeolites except for MFI-80, which showed a maximum conversion of 29% at 300°C. The product distribution exhibited ethyltoluenes as major product with a maximum yield of 26% over MFI-80. At 400°C, constant toluene conversion of 14% and 100% ethanol conversion, para-selectivity to p-ET was 100% over MFI-2000 compared with 27% and 48% over MFI-80 and MFI-280, respectively. The high para-selectivity over MFI-2000 is attributed to the combined effects of higher SiO2/Al2O3 ratio, very weak acid sites and larger crystal size (longer diffusion length). The experimental data were analyzed for each MFI zeolite and suitable reaction mechanism for toluene ethylation was proposed based on the Langmuir-Hinshelwood model. The activation energy for the formation of p-ET over MFI-280 and MFI-2000 is 30 kJ/mol and 65 kJ/mol, while the heat of adsorption of ethanol is 19 kJ/mol and 29 kJ/mol, respectively.
- Ogunbadejo, Babatunde A.,Osman, Mogahid S.,Arudra, Palani,Aitani, Abdullah M.,Al-Khattaf, Sulaiman S.
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- Effect of phosphorus content on physicochemical and catalytic properties of H-ultrasil in the reaction of toluene ethylation
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Physicochemical properties of H-ultrasil modified with phosphorus and effect of the modification on the toluene alkylation with ethanol were studied.
- Aliev,Akhmedov,Mamedov,Gakhramanov
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Read Online
- Effect of solvent in the hydrogenation of acetophenone catalyzed by Pd/S-DVB
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A solvent effect was found in the hydrogenation of acetophenone catalyzed by a new Pd/S-DVB catalyst, immobilized on a styrene (S)/divinylbenzene (DVB) copolymer containing phosphinic groups. The porous structure of the catalyst was characterized by a specific surface area of 94.7 m2g?1. The presence of Pd(ii) and Pd(0) in Pd/S-DVB was evidenced by XPS and TEM. Pd/S-DVB catalyzes the hydrogenation of acetophenone (APh) to 1-phenylethanol (PhE) and ethylbenzene (EtB). The highest conversion of APh was obtained in methanol (MeOH) and in 2-propanol (2-PrOH), while in water it was lower. The conversion of APh correlates well with the hydrogen-bond-acceptance (HBA) capacity of the solvent. However, in all binary mixtures of alcohol and water the APh conversion and the yield of products significantly decreased. The observed inhibiting effect can be explained by the microheterogeneity of these mixtures and the blocking of the catalyst surface restricting access of the substrates to the Pd centers.
- Bereta, Tomasz,Mieczyńska, Ewa,Ronka, Sylwia,Tylus, W?odzimierz,Trzeciak, Anna M.
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p. 5023 - 5028
(2021/03/26)
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- Highly selective hydrogenation of aromatic ketones to alcohols in water: effect of PdO and ZrO2
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Pd/ZrO2and PdO/ZrO2composites, containing Pd or PdO nanoparticles, were prepared using an original one-step methodology. These nanocomposites catalyze the hydrogenation of acetophenone (AP) at 1 bar and 10 bar of H2in an aqueous solution. Compared to unsupported Pd or PdO nanoparticles, a remarkable increase in their activity was achieved as a result of interaction with zirconia. An unsupported PdO hydrogenated AP mainly to ethylbenzene (EB), while excellent regioselectivity towards 1-phenylethanol (PE) was obtained with PdO/ZrO2and it was preserved during recycling. Similarly, regioselectivity to PE was higher with Pd/ZrO2compared to unsupported Pd NPs. PdO and zirconia resulted in high selectivity to alcohols in the hydrogenation of substituted acetophenones.
- Alsalahi, W.,Trzeciak, A. M.,Tylus, W.
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p. 10386 - 10393
(2021/08/09)
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- Ligand-enabled and magnesium-activated hydrogenation with earth-abundant cobalt catalysts
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Replacing expensive noble metals like Pt, Pd, Ir, Ru, and Rh with inexpensive earth-abundant metals like cobalt (Co) is attracting wider research interest in catalysis. Cobalt catalysts are now undergoing a renaissance in hydrogenation reactions. Herein, we describe a hydrogenation method for polycyclic aromatic hydrocarbons (PAHs) and olefins with a magnesium-activated earth-abundant Co catalyst. When diketimine was used as a ligand, simple and inexpensive metal salts of CoBr2in combination with magnesium showed high catalytic activity in the site-selective hydrogenation of challenging PAHs under mild conditions. Co-catalyzed hydrogenation enabled the reduction of two side aromatics of PAHs. A wide range of PAHs can be hydrogenated in a site-selective manner, which provides a cost-effective, clean, and selective strategy to prepare partially reduced polycyclic hydrocarbon motifs that are otherwise difficult to prepare by common methods. The use of well-defined diketimine-ligated Co complexes as precatalysts for selective hydrogenation of PAHs and olefins is also demonstrated.
- Han, Bo,Jiao, Hongmei,Ma, Haojie,Wang, Jijiang,Zhang, Miaomiao,Zhang, Yuqi
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p. 39934 - 39939
(2021/12/31)
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- Chemoselective Hydrogenation of Olefins Using a Nanostructured Nickel Catalyst
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The selective hydrogenation of functionalized olefins is of great importance in the chemical and pharmaceutical industry. Here, we report on a nanostructured nickel catalyst that enables the selective hydrogenation of purely aliphatic and functionalized olefins under mild conditions. The earth-abundant metal catalyst allows the selective hydrogenation of sterically protected olefins and further tolerates functional groups such as carbonyls, esters, ethers and nitriles. The characterization of our catalyst revealed the formation of surface oxidized metallic nickel nanoparticles stabilized by a N-doped carbon layer on the active carbon support.
- Klarner, Mara,Bieger, Sandra,Drechsler, Markus,Kempe, Rhett
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supporting information
p. 2157 - 2161
(2021/05/21)
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- Controlling the Lewis Acidity and Polymerizing Effectively Prevent Frustrated Lewis Pairs from Deactivation in the Hydrogenation of Terminal Alkynes
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Two strategies were reported to prevent the deactivation of Frustrated Lewis pairs (FLPs) in the hydrogenation of terminal alkynes: reducing the Lewis acidity and polymerizing the Lewis acid. A polymeric Lewis acid (P-BPh3) with high stability was designed and synthesized. Excellent conversion (up to 99%) and selectivity can be achieved in the hydrogenation of terminal alkynes catalyzed by P-BPh3. This catalytic system works quite well for different substrates. In addition, the P-BPh3 can be easily recycled.
- Geng, Jiao,Hu, Xingbang,Liu, Qiang,Wu, Youting,Yang, Liu,Yao, Chenfei
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p. 3685 - 3690
(2021/05/31)
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- Reductive Deamination with Hydrosilanes Catalyzed by B(C6F5)3
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The strong boron Lewis acid tris(pentafluorophenyl)borane B(C6F5)3 is known to catalyze the dehydrogenative coupling of certain amines and hydrosilanes at elevated temperatures. At higher temperature, the dehydrogenation pathway competes with cleavage of the C?N bond and defunctionalization is obtained. This can be turned into a useful methodology for the transition-metal-free reductive deamination of a broad range of amines as well as heterocumulenes such as an isocyanate and an isothiocyanate.
- Fang, Huaquan,Oestreich, Martin
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supporting information
p. 11394 - 11398
(2020/05/25)
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- Lewis-Pair-Mediated Selective Dimerization and Polymerization of Lignocellulose-Based β-Angelica Lactone into Biofuel and Acrylic Bioplastic
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This contribution reports an unprecedentedly efficient dimerization and the first successful polymerization of lignocellulose-based β-angelica lactone (β-AL) by utilizing a selective Lewis pair (LP) catalytic system, thereby establishing a versatile bio-refinery platform wherein two products, including a dimer for high-quality gasoline-like biofuel (C8–C9 branched alkanes, yield=87 %) and a heat- and solvent-resistant acrylic bioplastic (Mn up to 26.0 kg mol?1), can be synthesized from one feedstock by one catalytic system. The underlying reason for exquisite selectivity of the LP catalytic system toward dimerization and polymerization was explored mechanistically.
- Hong, Miao,Wang, Xiao-Jun
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supporting information
p. 2664 - 2668
(2020/01/24)
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- MICROCAPSULES AND PROCESSES FOR THEIR PREPARATION
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The present invention provides microcapsules encapsulating hydrophilic or hydrophobic active agents in an inorganic shell, processes for their preparation and compositions comprising them.
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Page/Page column 43-45
(2019/06/11)
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- Combined Photoredox/Enzymatic C?H Benzylic Hydroxylations
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Chemical transformations that install heteroatoms into C?H bonds are of significant interest because they streamline the construction of value-added small molecules. Direct C?H oxyfunctionalization, or the one step conversion of a C?H bond to a C?O bond, could be a highly enabling transformation due to the prevalence of the resulting enantioenriched alcohols in pharmaceuticals and natural products,. Here we report a single-flask photoredox/enzymatic process for direct C?H hydroxylation that proceeds with broad reactivity, chemoselectivity and enantioselectivity. This unified strategy advances general photoredox and enzymatic catalysis synergy and enables chemoenzymatic processes for powerful and selective oxidative transformations.
- Betori, Rick C.,May, Catherine M.,Scheidt, Karl A.
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supporting information
p. 16490 - 16494
(2019/11/03)
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- Bimetallic Co/Al nanoparticles in an ionic liquid: Synthesis and application in alkyne hydrogenation
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Herein, we report the microwave-induced decomposition of various organometallic cobalt and aluminum precursors in an ionic liquid (IL), 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIm]NTf2), resulting in Co/Al nanoalloys with different molar Co/Al ratios. The dual-source precursor system of dicobalt octacarbonyl (Co2(CO)8) and pentamethylcyclopentadienyl aluminum ([AlCp?]4) in [BMIm]NTf2 afforded CoAl nanoparticles (CoAl-NPs) with a molar Co/Al ratio of 1?:?1. Their size and size distribution were determined via transmission electron microscopy (TEM) to be an average diameter of 3.0 ± 0.5 nm. Furthermore, the dual-source precursor system of cobalt amidinate ([Co(iPr2-MeAMD)2]) and aluminum amidinate [Me2Al(iPr2-MeAMD)] in molar ratios of 1?:?1 and 3?:?1 resulted in CoAl-and Co3Al-NPs with an average diameter of 3 ± 1 and 2.0 ± 0.2 nm, respectively. All the obtained materials were characterized via TEM, energy dispersive X-ray spectroscopy (EDX), selected area electron diffraction (SAED), together with high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and (high-resolution) X-ray photoelectron spectroscopy ((HR-)XPS). Phase-pure Co/Al-NPs were not obtained since the concomitant formation of Co-NPs and Al2O3 occurred in this wet-chemical synthesis. The as-prepared Co/Al nanoalloys were evaluated as catalysts in the hydrogenation of phenylacetylene under mild conditions (2 bar H2, 30 °C in THF). In comparison to the monometallic Co-NPs, the Co/Al-NPs showed a significantly higher catalytic hydrogenation activity. The Co-and Co/Al-NPs were also active under harsher reaction conditions (80 bar H2, 80 °C) without the addition of the activating co-catalyst DIBAL-H.
- Schmolke, Laura,Gregori, Bernhard J.,Giesen, Beatriz,Schmitz, Alexa,Barthel, Juri,Staiger, Lena,Fischer, Roland A.,Jacobi Von Wangelin, Axel,Janiak, Christoph
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p. 16583 - 16594
(2019/11/11)
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- Room Temperature Chemoselective Deoxygenation of Aromatic Ketones and Aldehydes Promoted by a Tandem Pd/TiO2 + FeCl3 Catalyst
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A rapid and practical protocol for the chemoselective deoxygenation of various aromatic ketones and aldehydes was described, which used a tandem catalyst composed of heterogeneous Pd/TiO2 + homogeneous FeCl3 with the green hydrogen source, polymethylhydrosiloxane (PMHS). The developed catalytic system was robust and scalable, as exemplified by the deoxygenation of acetophenone, which was performed on a gram scale in an atmospheric environment utilizing only 0.4 mol % Pd/TiO2 + 10 mol % FeCl3 catalyst to give the corresponding ethylbenzene in 96% yield within 10 min at room temperature. Furthermore, the Pd/TiO2 catalyst was shown to be recyclable up to three times without an observable decrease in efficiency and it exhibited low metal leaching under the reaction conditions. Insights toward the reaction mechanism of Pd-catalyzed reductive deoxygenation for aromatic ketones and aldehydes were investigated through operando IR, NMR, and GC-MS techniques.
- Dong, Zhenhua,Yuan, Jinwei,Xiao, Yongmei,Mao, Pu,Wang, Wentao
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p. 11067 - 11073
(2018/09/12)
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- Distinct Catalytic Performance of Cobalt(I)- N -Heterocyclic Carbene Complexes in Promoting the Reaction of Alkene with Diphenylsilane: Selective 2,1-Hydrosilylation, 1,2-Hydrosilylation, and Hydrogenation of Alkene
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Selectivity control on the reaction of alkene with hydrosilane is a challenging task in the development of non-precious-metal-based hydrosilylation catalysts. While the traditional way of selectivity control relies on the use of different ligand type and/or different metals, we report herein that cobalt(I) complexes bearing different N-heterocyclic carbene ligands (NHCs) exhibit distinct selectivity in catalyzing the reaction of alkene with Ph2SiH2. [(IAd)(PPh3)CoCl] (IAd = 1,3-diadamantylimidazol-2-ylidene) is an efficient catalyst for anti-Markovnikov hydrosilylation of monosubstituted alkenes. [(IMes)2CoCl] (IMes = 1,3-dimesitylimidazol-2-ylidene) shows Markovnikov-addition selectivity in promoting the hydrosilylation of aryl-substituted alkenes. [(IMe2Me2)4Co][BPh4] (IMe2Me2 = 1,3-dimethyl-4,5-dimethylimidazol-2-ylidene) can catalyze hydrogenation of alkenes with Ph2SiH2 as the terminal hydrogen source. Mechanistic studies in combination with the knowledge on the steric nature of cobalt-NHC species suggest that (NHC)cobalt(I) silyl species and bis(NHC)cobalt(I) hydride species are the probable key intermediates for these hydrosilylation and hydrogenation reactions, respectively. The different steric nature of IAd versus IMes and the potential of IMes incurring π···π interaction with aryl-substituted alkenes are thought to be the causes of the observed 1,2- and 2,1-addition selectivity.
- Gao, Yafei,Wang, Lijun,Deng, Liang
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p. 9637 - 9646
(2018/10/02)
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- Decarboxylation of Lactones over Zn/ZSM-5: Elucidation of the Structure of the Active Site and Molecular Interactions
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Herein, we report the catalytic decarboxylation of γ-valerolactone (GVL) over Zn/ZSM-5 to butene, followed by aromatization at high yield with co-feeding of water. An evaluation of the catalytic performance after prolonged periods of time showed that a water molecule is essential to maintain the decarboxylation and aromatization activities and avoid rapid catalyst deactivation. Synchrotron X-ray powder diffraction and Rietveld refinement were then used to elucidate the structures of adsorbed GVL and immobilized Zn species in combination with EXAFS and NMR spectroscopy. A new route for the cooperative hydrolysis of GVL by framework Zn?OH and Br?nsted acidic sites to butene and then to aromatic compounds has thus been demonstrated. The structures and fundamental pathways for the nucleophilic attack of terminal Zn?OH sites are comparable to those of Zn-containing enzymes in biological systems.
- Ye, Lin,Song, Qi,Lo, Benedict T. W.,Zheng, Junlin,Kong, Dejing,Murray, Claire A.,Tang, Chiu C.,Tsang, S. C. Edman
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supporting information
p. 10711 - 10716
(2017/08/30)
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- Rhodium(i) diphenylphosphine complexes supported on porous organic polymers as efficient and recyclable catalysts for alkene hydrogenation
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This paper describes the synthesis and characterization of porous polymeric materials as a support for rhodium(i) cationic coordination compounds and their use as heterogeneous catalysts for alkene hydrogenation. The synthetic strategy was the insertion of a vinyl-moiety in a bis(2-chloroethyl)amine precursor to provide highly porous resins with an enriched modifiable surface. The precursors synthesized were N,N-bis(2-chloroethyl)prop-2-en-1-amine (Alk-POL) and N,N-bis(2-chloroethyl)acrylamide (Acy-POL). The resins were obtained through suspension polymerization of methyl acrylate and divinylbenzene as a co-polymer and cross-linker, respectively. The resin surfaces were functionalized with diphenylphosphine groups followed by Rh(i) metal deposition using [Rh(COD)2]BF4 (COD = 1,5-cyclooctadiene) as the catalyst precursor. The Rh-catalysts were characterized by different physicochemical techniques and assessed for their catalytic performances in the heterogeneous hydrogenation of styrene and its derivatives. It was found that the catalytic activities and selectivity of the heterogenized rhodium complex (Rh-Alk-POL and Rh-Acy-POL) in the hydrogenation reactions were comparable to its homogeneous analogue. Analysis of the spent homogeneous resin Rh-Alk-POL catalyst after the first reaction cycle showed the presence of metallic Rh nanoparticles arising from the reduction of the Rh complex. Extensive recycling and Rh leaching studies were carried out for the Rh-Acy-POL catalyst. Both the activity and selectivity could be maintained for at least seven reaction runs and without metal leaching during the reaction cycles. We have also studied the liquid-phase hydrogenation reaction of various styrene m-substituted derivatives. The Rh-Acy-POL catalyst exhibits excellent catalytic activity for hydrogenation of the substrates and only vinyl-group hydrogenation was detected. Finally, the presence of electron-donating/-withdrawing substituents at the meta-position resulted in different rates of vinyl group hydrogenation. This effect was quantified in terms of the Hammett relationship, in which the catalyst displayed a linear correlation between the Hammett substituent constant (σmeta) and the hydrogenation rate.
- Campos, Cristian H.,Belmar, Julio B.,Jeria, Solange E.,Urbano, Bruno F.,Torres, Cecilia C.,Alderete, Joel B.
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p. 3398 - 3407
(2017/01/24)
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- Alkene Metalates as Hydrogenation Catalysts
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First-row transition-metal complexes hold great potential as catalysts for hydrogenations and related reductive reactions. Homo- and heteroleptic arene/alkene metalates(1?) (M=Co, Fe) are a structurally distinct catalyst class with good activities in hydrogenations of alkenes and alkynes. The first syntheses of the heteroleptic cobaltates [K([18]crown-6)][Co(η4-cod)(η2-styrene)2] (5) and [K([18]crown-6)][Co(η4-dct)(η4-cod)] (6), and the homoleptic complex [K(thf)2][Co(η4-dct)2] (7; dct=dibenzo[a,e]cyclooctatetraene, cod=1,5-cyclooctadiene), are reported. For comparison, two cyclopentadienylferrates(1?) were synthesized according to literature procedures. The isolated and fully characterized monoanionic complexes were competent precatalysts in alkene hydrogenations under mild conditions (2 bar H2, r.t., THF). Mechanistic studies by NMR spectroscopy, ESI mass spectrometry, and poisoning experiments documented the operation of a homogeneous mechanism, which was initiated by facile redox-neutral π-ligand exchange with the substrates followed by H2 activation. The substrate scope of the investigated precatalysts was also extended to polar substrates (ketones and imines).
- Büschelberger, Philipp,G?rtner, Dominik,Reyes-Rodriguez, Efrain,Kreyenschmidt, Friedrich,Koszinowski, Konrad,Jacobi von Wangelin, Axel,Wolf, Robert
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p. 3139 - 3151
(2017/03/13)
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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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- Heterogeneous Catalytic Hydroarylation of Olefins at a Nanoscopic Aluminum Chlorofluoride
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We report on hydroarylation reactions of arenes with olefins under very mild conditions catalyzed heterogeneously by aluminum chlorofluoride (ACF; AlClxF3?x, x≈0.05–0.25). The reactions of benzene and toluene with ethylene or propylene proceed with high conversions to afford various alkylated arenes. For cyclohexene and 1-hexene, the reactions require higher temperatures and the conversions are lower. ACF also catalyzes the hydroarylation of 1,3,5-trifluorobenzene and pentafluorobenzene with ethylene and propylene. The alkylations of arenes with non-fluorinated olefins resemble typical Friedel–Crafts chemistry to give rise to Markovnikov regioselectivity. The reaction of CF3CH=CH2 with benzene proceeds with anti-Markovnikov regioselectivity to give the fluorinated olefin PhCHCH=CF2 and the alkylation product PhCH2CH2CF3 as products of C?F and C?H activation.
- Calvo, Beatriz,Wuttke, Jan,Braun, Thomas,Kemnitz, Erhard
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p. 1945 - 1950
(2016/07/06)
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- Method of producing ethyl toluene
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The invention relates to a method for producing ethyl toluene, mainly solves the problems in the prior art that the proportion of o-ethyltoluene, m-ethyltoluene and p-ethyltoluene in the product can not be accurately modulated, and the regeneration period
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Paragraph 0024; 0025
(2017/05/17)
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- Cu(II)/Cu(0)@UiO-66-NH2: Base metal@MOFs as heterogeneous catalysts for olefin oxidation and reduction
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Two copper-loaded MOF materials, namely Cu(ii)@Ui-O-66-NH2 (1) and Cu(0)@UiO-66-NH2 (2), are reported. They can, respectively, serve as highly efficient heterogeneous catalysts for olefin oxidation and hydrogenation under mild conditions. Complete styrene hydrogenation occurs in 15 min at ambient temperature with quantitative yield.
- Wang, Jian-Cheng,Hu, Yu-Hong,Chen, Gong-Jun,Dong, Yu-Bin
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p. 13116 - 13119
(2016/11/09)
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- Method for simultaneously synthesizing methyl-ethylbenzene and diethylbenzene by virtue of one-step method
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The invention relates to a method for simultaneously synthesizing methyl-ethylbenzene and diethylbenzene by virtue of a one-step method. Ethylene, benzene and methylbenzene are taken as raw materials to perform an alkylation reaction so as to synthesize methyl-ethylbenzene and diethylbenzene in one step. The method comprises a pretreatment stage, a reaction stage and an aftertreatment stage. In the method, one reaction system is adopted, and alkylation reaction and aftertreatment are sequentially performed so as to separate components, so that target products are obtained, and thus one-step simultaneous synthesis of methyl-ethylbenzene and diethylbenzene is realized; the problem that two independent devices are respectively used for production in a traditional production process is avoided, and the whole reaction process is convenient and rapid; the yields of different components can be effectively adjusted by adjusting different proportions of raw materials, and unreacted benzene and methylbenzene and the ethylbenzene generated in a reaction process are separated and recycled to serve as raw materials once again, so that the production cost is greatly saved, and meanwhile, the method can adapt to variations of the market to the greatest extent.
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Paragraph 0051-0065
(2016/12/22)
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- Continuous-flow hydrogenation of olefins and nitrobenzenes catalyzed by platinum nanoparticles dispersed in an amphiphilic polymer
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A method for the flow hydrogenation of olefins and nitrobenzenes in a continuous-flow reactor containing platinum nanoparticles dispersed on an amphiphilic polystyrene-poly(ethylene glycol) resin (ARP-Pt) was developed. The hydrogenation of olefins and nitrobenzenes was completed within 31 seconds in the continuous-flow system containing ARP-Pt, giving the corresponding hydrogenated products in up to 99% yield with good chemoselectivity. Moreover, long-term (63-70 h) continuous-flow hydrogenation of styrene and nitrobenzene produced more than ten grams of ethylbenzene and aniline, respectively, without significant loss of catalytic activity. The flow hydrogenation system provides an efficient and practical method for the chemoselective reduction of olefins and nitrobenzenes. This journal is
- Osako, Takao,Torii, Kaoru,Tazawa, Aya,Uozumi, Yasuhiro
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p. 45760 - 45766
(2015/06/08)
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- CATALYTIC CONVERSION OF ALCOHOLS HAVING AT LEAST THREE CARBON ATOMS TO HYDROCARBON BLENDSTOCK
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A method for producing a hydrocarbon blendstock, the method comprising contacting at least one saturated acyclic alcohol having at least three and up to ten carbon atoms with a metal-loaded zeolite catalyst at a temperature of at least 100°C and up to 550°C, wherein the metal is a positively-charged metal ion, and the metal-loaded zeolite catalyst is catalytically active for converting the alcohol to the hydrocarbon blendstock, wherein the method directly produces a hydrocarbon blendstock having less than 1 vol% ethylene and at least 35 vol% of hydrocarbon compounds containing at least eight carbon atoms.
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Paragraph 0062; 0063
(2015/01/16)
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- K-promoted Mo/Co- and Mo/Ni-catalyzed Fischer-Tropsch synthesis of aromatic hydrocarbons with and without a Cu water gas shift catalyst
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The catalyst systems Mo/Co/K/ZSM-5 and Mo/Ni/K/ZSM-5, alone and with the added copper-based water gas shift catalyst, were used for the conversion of two CO/H2 ratios in a batch reactor. GC analysis of the gas phase was used to determine CO conversion while GCMS and NMR studies were used to characterize the liquid products formed and liquid product selectivities. The liquids were hydrocarbons consisting mainly of alkyl substituted benzenes. Methyl substitution in the alkyl benzenes in the product liquid ranged from an average of 1.3 to 4.5 methyls per ring depending on reaction conditions and reactant gas mole ratios. The additional presence of the WGS catalyst significantly increased CO conversion in the reactions taking place at 280 °C from ~25% to ~90% while increasing selectivity toward higher average methyl substitution. Similar conversions and selectivities were observed with both a bio-syngas and a 50/50 mixture of H2 and CO.
- Wijayapala, Rangana,Yu, Fei,Pittman Jr., Charles U.,Mlsna, Todd E.
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- Maximum synergistic effect in the coupling conversion of bio-derived furans and methanol over ZSM-5 for enhancing aromatic production
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We firstly propose the coupling conversion of bio-derived furans and methanol over ZSM-5 for enhancing aromatic production. The coupling conversion of bio-derived furans and methanol was conducted in a continuous fixed bed reactor. 2-Methylfuran (MF) was used as a probe molecule to identify the possible reaction pathways. The effects of the methanol to MF molar ratio, reaction temperature and weight hourly space velocity (WHSV) on the product distribution from the coupling conversion of MF and methanol were investigated. The experimental results showed that the aromatic yield from the coupling conversion of MF and methanol is about 5.2 times higher than that of the catalytic fast pyrolysis of only MF. In addition, it can also enhance the yield of olefins, the selectivity of xylenes and reduce coke formation. These results indicate that there is a significant synergistic effect between MF and methanol. The synergistic effect could be attributed to the methanol-to-olefins reactions, the Diels-Alder reactions of furans with olefins, and the alkylation reaction of benzene/toluene with methanol occurring during the coupling conversion of MF and methanol. The reaction conditions for maximizing the synergistic effect were a methanol to MF molar ratio of 2 at 550 °C. Moreover, the comparative study of the coupling conversion of different bio-derived furans (MF, 2,5-dimethylfuran (DMF), furfural (FF) and furfuryl alcohol (FA)) and methanol were also considered in this study. The coupling conversion of DMF and methanol exhibited maximum yields of aromatics, olefins and a minimum yield of coke, suggesting that DMF is the best candidate of bio-derived furans for aromatic production in the coupling conversion of bio-derived furans and methanol. the Partner Organisations 2014.
- Zheng, Anqing,Zhao, Zengli,Chang, Sheng,Huang, Zhen,Zhao, Kun,Wu, Hongxiang,Wang, Xiaobo,He, Fang,Li, Haibin
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p. 2580 - 2586
(2014/05/06)
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- Comparison of microporous/mesoporous and microporous HZSM-5 as catalysts for Friedel-Crafts alkylation of toluene with ethene
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In this work we investigated the effect of mesopores in a standard zeolite used as a catalyst for Friedel-Crafts alkylation of toluene with ethene. A cationic polymer was used for templating mesopores in a microporous ZSM-5 framework. The mesopore-containing zeolite was compared with a regular zeolite with only micropores with respect to conversion, yield and selectivity. The two NaZSM-5 materials were prepared with the same Si/Al molar ratio and diffuse reflection infrared Fourier transform spectroscopy (DRIFT-FTIR) confirmed that the acidity of the ion-exchanged forms (HZSM-5) were identical. Scanning electron microscopy (SEM) and dynamic light scattering (DLS) were used to determine the particle size of the zeolites, which was similar for the two HZSM-5 materials and nitrogen sorption was used to determine the surface area and pore size distribution. X-ray diffraction (XRD) analysis displayed typical crystalline diffraction patterns for the ZSM-5 framework for both the microporous/mesoporous and the microporous ZSM-5 materials. The results from catalytic testing show an increase in the overall conversion of toluene for the zeolite that contains mesopores. Furthermore, a higher product yield (C 9) is obtained for this catalyst. The increase in yield and conversion is most likely due to the mesopores; however, incorporation of mesopores in the microporous ZSM-5 framework gives only minor effects on selectivity with respect to mono- vs. dialkylation, and ortho:meta:para ratio. Consequently, this work shows that the presence of mesopores in a microporous ZSM-5 framework is beneficial for the reaction in terms of conversion of starting material and reaction yield but does not markedly affect the product composition.
- Bohstroem, Zebastian,Haerelind, Hanna,Gevert, Boerje,Andersson, Sven-Ingvar,Holmberg, Krister
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p. 28786 - 28793
(2014/07/22)
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- Heteroatom-free arene-cobalt and arene-iron catalysts for hydrogenations
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75 years after the discovery of hydroformylation, cobalt catalysts are now undergoing a renaissance in hydrogenation reactions. We have evaluated arene metalates in which the low-valent metal species is - conceptually different from heteroatom-based ligands - stabilized by π coordination to hydrocarbons. Potassium bis(anthracene)cobaltate 1 and -ferrate 2 can be viewed as synthetic precursors of quasi-"naked" anionic metal species; their aggregation is effectively impeded by (labile) coordination to the various π acceptors present in the hydrogenation reactions of unsaturated molecules (alkenes, arenes, carbonyl compounds). Kinetic studies, NMR spectroscopy, and poisoning studies of alkene hydrogenations support the formation of a homogeneous catalyst derived from 1 which is stabilized by the coordination of alkenes. This catalyst concept complements the use of complexes with heteroatom donor ligands for reductive processes. Especially high selectivities were observed in the hydrogenation of various alkenes, ketones, and imines with bis(anthracene) cobaltate(-I) [K(dme)2{Co(C14H10)2}] under mild conditions (1-5 mol% cat., 1-10 bar H2, 20-60°C). Mechanistic studies indicate the operation in alkene hydrogenations of a homogeneous catalyst formed by initial ligand exchange and stabilized by the coordination of π-acidic alkenes or arenes.
- Gaertner, Dominik,Welther, Alice,Rad, Babak Rezaei,Wolf, Robert,Von Wangelin, Axel Jacobi
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supporting information
p. 3722 - 3726
(2014/04/17)
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- Photodriven Transfer Hydrogenation of Olefins
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An improved practical method for the photodriven diimide reduction of olefins was investigated. This catalyst-free procedure proceeds at ambient temperature, utilizes air as oxidant and a lower hydrazine loading, and produces inert nitrogen gas as the sole byproduct. Several functional groups were tolerated, and in some cases, the reaction was chemoselective. Challenging substrates such as cinnamate ester derivatives and trans-stilbene were reduced in excellent yields. The small amount of UVA rays emitted from a household compact fluorescent light bulb was proposed to enable the cis/trans isomerization of the diimide and to promote the loss of hydrogen from the diimide.
- Leow, Dasheng,Chen, Ying-Ho,Hung, Tzu-Hang,Su, Ying,Lin, Yi-Zhen
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supporting information
p. 7347 - 7352
(2016/02/18)
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- Immobilization of palladium catalyst on magnetically separable polyurea nanosupport
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This work describes a method for preparing magnetic polyurea nanoparticles (PU NPs) and their utilization as a catalyst support. The method is based on entrapment of hydrophilic magnetic nanoparticles within the polyurea matrix. The synthetic process of these magnetic polyurea nanoparticles is based on oil-in-oil nanoemulsification of an organic polar phase comprised of N,N-dimethylacetamide (DMAc), 2,6-diaminopyridine and ionic liquid modified magnetite nanoparticles (MNPs-IL), in heptane containing a suitable surfactant. This was followed by interfacial polycondensation reaction between an isocyanate monomer, polymethylenepolyphenyl isocyanate (PAPI 27), and the amine monomer producing magnetically separable polyurea nanoparticles. Subsequently, these particles were employed as a catalyst nanosupport. Two catalytic systems based on the encapsulation of Pd(OAc)2 within magnetic PU NPs or their adsorption on the surface of these particles were produced and subjected to hydrogenation reactions and selective hydrogenations of α,β-unsaturated compounds. Pd(OAc)2 adsorbed on the surface of the magnetic PU NPs demonstrated high catalytic activity and selectivity, which was superior to the conventional catalyst Pd/C or palladium nanoparticles supported directly on the surface of magnetite nanoparticles. The catalyst was easily recovered from the reaction mixture by applying an external magnetic field and recycled over five times without observing any significant loss in its catalytic efficiency. This journal is
- Natour, Suzana,Abu-Reziq, Raed
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p. 48299 - 48309
(2014/12/10)
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- Effect of triarylphosphane ligands on the rhodium-catalyzed hydrosilylation of alkene
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A series of triarylphosphanes (1a, 2a, 3a, 4a, 5a, 6a, 7a, 8a, 9a, 10a, 11a) have been synthesized. An X-ray crystal structure analysis of (2-bromophenyl)diphenylphosphane (1a) unambiguously confirmed the constitution of the functionalized phosphane. The hydrosilylation reaction of styrene with triethoxysilane catalyzed with RhCl3/triarylphosphane was studied. In comparison with the classic Wilkinson's catalyst, rhodium complexes with functionalized triarylphosphane ligands are characterized by a very high catalytic effectiveness for the hydrosilylation of alkene. Among these catalysts tested, RhCl3/diphenyl(2-(trimethylsilyl)phenyl)phosphane (8a) exhibited excellent catalytic properties. Using this silicon-containing phosphane ligand for the rhodium-catalyzed hydrosilylation of styrene, both higher conversion of alkene and higher β-adduct selectivity were obtained than with Wilkinson's catalyst.
- Xue, Mei,Li, Jiayun,Peng, Jiajian,Bai, Ying,Zhang, Guodong,Xiao, Wenjun,Lai, Guoqiao
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p. 120 - 126
(2014/02/14)
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- Rhenium-mediated dehydrogenative silylation and highly regioselective hydrosilylation of nitrile substituted olefins
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The rhenium (I) complex [Re(CH3CN)3Br 2(NO)] catalyzes the homogeneous hydrosilylation of a variety of substituted acrylonitriles, which were converted into the corresponding silyl-substituted alkanes with high regioselectivity of up to 94%. The products were analyzed by 1H NMR and GC-MS. A rhenium specific mechanism is proposed for the hydrosilylation of olefins.
- Dong, Hailin,Jiang, Yanfeng,Berke, Heinz
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- Highly efficient iron(0) nanoparticle-catalyzed hydrogenation in water in flow
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Highly efficient catalytic hydrogenations are achieved by using amphiphilic polymer-stabilized Fe(0) nanoparticle (Fe NP) catalysts in ethanol or water in a flow reactor. Alkenes, alkynes, aromatic imines and aldehydes were hydrogenated nearly quantitatively in most cases. Aliphatic amines and aldehydes, ketone, ester, arene, nitro, and aryl halide functionalities are not affected, which provides an interesting chemoselectivity. The Fe NPs used in this system are stabilized and protected by an amphiphilic polymer resin, providing a unique system that combines long-term stability and high activity. The NPs were characterized by TEM of microtomed resin, which established that iron remains in the zero-valent form despite exposure to water and oxygen. The amphiphilic resin-supported Fe(0) nanoparticles in water and in flow provide a novel, robust, cheap and environmentally benign catalyst system for chemoselective hydrogenations.
- Hudson, Reuben,Hamasaka, Go,Osako, Takao,Yamada, Yoichi M. A.,Li, Chao-Jun,Uozumi, Yasuhiro,Moores, Audrey
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p. 2141 - 2148
(2013/09/24)
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- Iron-catalysed alkene hydrogenation and reductive cross-coupling using a bench-stable iron(II) pre-catalyst
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Operationally simple, iron-catalysed hydrogenation and reductive cross-coupling protocols have been developed using a bench-stable iron(ii) pre-catalyst. The hydrogenation of 18 alkenes (50-99%) and reductive cross-coupling of vinyl halides with aryl- and alkyl Grignard reagents (8 examples, 18-99%) is reported using 3 mol% pre-catalyst and hydrogen as stoichiometric reductant (1-50 bar).
- Frank, Dominik J.,Guiet, Lea,Kaeslin, Alexander,Murphy, Elliot,Thomas, Stephen P.
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p. 25698 - 25701
(2013/12/04)
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- ZEOLITIC CATALYTIC CONVERSION OF ALCOHOLS TO HYDROCARBONS
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A method for converting an alcohol to a hydrocarbon, the method comprising contacting said alcohol with a metal-loaded zeolite catalyst at a temperature of at least 100°C and up to 550°C, wherein said alcohol can be produced by a fermentation process, said metal is a positively-charged metal ion, and said metal-loaded zeolite catalyst is catalytically active for converting said alcohol to said hydrocarbon.
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Page/Page column 19
(2013/02/28)
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- Effect of extra-framework Al formed by successive steaming and acid leaching of zeolite MCM-22 on its structure and catalytic performance
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Dealuminated MCM-22 samples have been prepared by a two-step dealumination procedure. Detailed assessment of the properties of the materials obtained at each one of the successive stages, i.e. steaming (at 500 °C, 700 °C and 800 °C) and acid reflux (HCl and oxalic), has been made by XRD, N 2 adsorption-desorption, m-xylene adsorption, 27Al MAS NMR and FT-IR of pyridine adsorption. It was found that steaming generates extra-framework aluminum (EFAl) species and the majority of them cannot be extracted by the consecutive acid leaching. These extra-lattice entities block the zeolite micropores which makes the remaining Broensted acid sites isolated and inefficient. It is shown that the presence of such species vastly affects the catalytic performance of zeolite MCM-22 in the reaction of m-xylene conversion. The consequences are reduced adsorption capacity and catalytic activity, modified reaction products distribution, enhanced p-xylene selectivity, as well as altered mode of coke formation and composition of the coke precursors.
- Mihályi,Kollár,Király,Karoly,Mavrodinova
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scheme or table
p. 76 - 86
(2012/05/04)
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- A mild and efficient rhenium-catalyzed transfer hydrogenation of terminal olefins using alcoholysis of amine-borane adducts as a reducing system
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[ReBr2(NO)(CH3CN)(PTA)2] (PTA = 1, 3, 5-triaza-7-phosphaadamantane) catalyzes the alcoholysis of ammonia-borane and amine-boranes and the catalytic transfer hydrogenations of various terminal olefins. Excellent yields were achieved at 70 °C in isopropanol using tBuOK as a co-catalyst affording TOF values up to 396 h-1.
- Dong, Hailin,Berke, Heinz
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experimental part
p. 1803 - 1808
(2011/06/19)
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- Aromatization of isobutene using H-ZSM-5/Oxide composite catalysts
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Aromatization of isobutene was investigated using zeolite H-ZSM-5 (Si/Al = 30) as well as physical mixtures of H-ZSM-5 with metal oxides (Ga 2O3, ZnO and CuO). The study was aimed at determining the effect on the selectivity to aroma
- Al-Otaibi, Naif M.,Hutching, Graham
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experimental part
p. 191 - 195
(2011/01/03)
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- Side chain ethylation of toluene with ethanol over hydrotalcite-like compounds
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Calcined Mg, Ni, Cu, Co, and Zn hydrotalcites (CHTs) tested for their catalytic performance in the side chain ethylation of toluene with ethanol at 300, 350, 400, and 450°C. The major products were propylbenzene, β-methylstyrene, ortho-, para-, and meta-ethyltoluene. MgAl-CHTs gave side chain alkylated propylbenzene, while over Co, Ni, Cu, and Zn-CHTs, side chain as well as nuclear alkylated products and ethyltoluene were observed.
- Manivannan,Pandurangan
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scheme or table
p. 56 - 62
(2010/07/09)
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- Regioselective arene functionalization: Simple substitution of carboxylate by alkyl groups
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Arenes with various alkyl side-chains were synthesized in high yields and excellent regioselectivities. Starting from toluic and naphthoic acids, the carboxylate group was conveniently substituted by alkyl halides by Birch reduction and subsequent decarbonylation. The method is characterized by inexpensive starting materials and reagents, and methylation of arenes was realized. Besides simple alkyl substituents, the scope of arene functionalization was extended by benzyl, fluoro, amino, and ester groups. We were able to control the alkylation of 1-naphthoic acid during Birch reduction by the addition of tert-butanol. This allowed the regioselective synthesis of mono and bis-substituted naphthalenes from the same starting material.
- Krueger, Tobias,Vorndran, Katja,Linker, Torsten
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experimental part
p. 12082 - 12091
(2010/05/17)
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- Intermolecular hydroarylation of unactivated olefins catalyzed by homogeneous platinum complexes
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Designing catalysts: The five-coordinate platinum(IV) complex A and the platinum(II) trans complex B act as precatalysts for the hydroarylation of unactivated olefins. The catalytic cycle features an aryl-olefin insertion at PtII and a C-H bond activation of the arene solvent as key steps. The Pt II cis complex C has been observed in hydroarylation reactions of ethylene with benzene.
- Luedtke, Avery T.,Goldberg, Karen I.
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supporting information; experimental part
p. 7694 - 7696
(2009/04/11)
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- Catalytic ring-attachment isomerization and dealkylation of diethylbenzenes over halide clusters of group 5 and group 6 transition metals
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A molybdenum halide cluster, (H3O)2[(Mo 6Cl8)Cl6]·6H2O, possessing an octahedral metal framework was used as a catalyst in a gas flow reactor under 1 atm of hydrogen. On reaction of p-diethylbenzene, dehydrogenation to ethylstyrene proceeded selectively at 300°C. At 400°C, mutual interconversion of o-, m-, and p-diethylbenzenes proceeded selectively. The ethyl group migrated by an intramolecular 1,2-shift mechanism without yielding disproportionation products. Niobium and tungsten chloride clusters with the same metal framework were also active catalysts for the isomerization of p-diethylbenzene. All the reactions resulted in appreciable yields of dealkylation products. The catalytic activity for isomerization can be ascribed to acid sites on the cluster surface, and the catalytic activity for dealkylation, to the metallic nature of the framework metal.
- Kamiguchi, Satoshi,Kondo, Kunihiko,Kodomari, Mitsuo,Chihara, Teiji
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- Reduction of carbonyl groups to the corresponding methylenes with Ni-Al alloy in water
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The reduction of carbonyl compounds 1a-h using Ni-Al alloy in water under reflux proceeded to give the corresponding methylene compounds 2a-h within 2 h in 89.0-99.8% relative yields.
- Ishimoto, Keiko,Mitoma, Yoshiharu,Nagashima, Satoko,Tashiro, Hideki,Prakash, G. K. Surya,Olah, George A.,Tashiro, Masashi
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p. 514 - 515
(2007/10/03)
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- Simple two-step ipso substitution of aromatic carboxylic acids by alkyl halides
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Methyl-substituted arenes can be synthesized with high regioselectivity in only two steps through formal exchange of an aromatic carboxylic acid function with an alkyl substituent. The results obtained with toluic acid illustrate that good to very good yields can be obtained from inexpensive reagents (see scheme).
- Vorndran, Katja,Linker, Torsten
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p. 2489 - 2491
(2007/10/03)
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- Mesoporous aluminophosphate and silicoaluminophosphate molecular sieves: Room temperature synthesis, characterization and catalytic performance
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Mesoporous aluminophosphate (AIPO) and silicon substituted aluminophosphate molecular sieves (SAPO) have been synthesized using ordered array of cetyltrimethylammonium bromide as structure-directing agent at room temperature. The characteristics of these new materials are ascertained by low angle XRD, TGA, FT-IR, SEM and DRIFT spectra. Vapour phase ethylation of toluene has been attempted over these molecular sieves as a probe reaction. The principal product is p-ethyltoluene in this reaction. This study also indicates more free uncondensed -OH groups in pure AIPO.
- Rajesh,Palanichamy,Kazansky,Murugesan
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p. 1262 - 1268
(2007/10/03)
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- Ethylation of toluene over aluminophosphate based molecular sieves in the vapour phase
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Ethylation of toluene with ethanol has been examined over MnAPO-46, NAPO-46 and ZAPO-46 catalysts at 300, 350, 400 and 450 °C. The products obtained are benzene, styrene, m-ethyltoluene and diethyl ether. Toluene conversion is maximum at 350 °C. Formation
- Cheralathan,Kannan,Palanichamy,Murugesan
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p. 921 - 927
(2007/10/03)
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- The first rhodium-catalyzed anti-markovnikov hydroamination: Studies on hydroamination and oxidative amination of aromatic olefins
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The first transition-metal-catalyzed regiospecific anti-Markovnikov hydroamination of aromatic olefins is reported. Styrene and substituted styrenes react with secondary aliphatic amines, especially morpholine and Narylpiperazines, in the presence of cationic rhodium complexes to give 2- aminoethenylbenzene and 2-aminoethylbenzene derivatives. Cationic [Rh(cod)2]+BF4- and various phosphines (l:2-mixture) were employed as in situ catalysts. According to labeling experiments, there is no evidence that the hydroamination is a consecutive hydrogenation of a previously formed enamine. Hydroamination with simple secondary amines, for example piperidine, can also be achieved by the use of a higher olefin concentration and higher reaction temperatures than those given in previously published reaction procedures. Kinetic investigations of the major reaction pathway reveal that the reaction rate of the oxidative amination and the hydroamination is dependent on the styrene and on the catalyst concentration, and independent of the amine concentration. Experiments that employed deuterium-labeled amines (N-D) provided evidence that the mechanism involves an amine- activating pathway. The substituents on the styrene, the phosphine ligand, and the solvent influence the yield of the aminations and the enamine:alkylamine ratio.
- Beller,Trauthwein,Eichberger,Breindl,Herwig,Mueller,Thiel
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p. 1306 - 1319
(2007/10/03)
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- THE EFFECT OF EXTRA-FRAMEWORK ALUMINUM IN DEALUMINATED ZSM-5 ZEOLITES ON THE TRANSFORMATION OF AROMATIC HYDROCARBONS
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H-ZSM-5 zeolite was dealuminated by steaming under ''mild'' and ''severe'' conditions at 675 and 975 K for 71.5 and 0.5 h, respectively.It resulted to a comparable number of Al atoms released from the zeolite framework, although of their different nature.
- Cejka, Jiri,Vondrova, Alena,Wichterlova, Blanka,Jerschkewitz, Hans G.,Lischke, Guenter,Schreier, Ellen
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p. 412 - 420
(2007/10/02)
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