1074-43-7Relevant academic research and scientific papers
Room temperature iron catalyzed transfer hydrogenation usingn-butanol and poly(methylhydrosiloxane)
Coles, Nathan T.,Linford-Wood, Thomas G.,Webster, Ruth L.
supporting information, p. 2703 - 2709 (2021/04/21)
Reduction of carbon-carbon double bonds is reported using a three-coordinate iron(ii) β-diketiminate pre-catalyst. The reaction is believed to proceedviaa formal transfer hydrogenation using poly(methylhydrosiloxane), PMHS, as the hydride donor and a bio-alcohol as the proton source. The reaction proceeds well usingn-butanol and ethanol, withn-butanol being used for substrate scoping studies. Allyl arene substrates, styrenes and aliphatic substrates all undergo reduction at room temperature. Unfortunately, clean transfer of a deuterium atom usingd-alcohol does not take place, indicating a complex catalytic mechanism. However, changing the deuterium source tod-aniline gives close to complete regioselectivity for mono-deuteration of the terminal position of the double bond. Finally, we demonstrate that efficient dehydrocoupling of alcohol and PMHS can be undertaken using the same pre-catalyst, giving high yields of H2within 30 minutes at room temperature.
Insight into forced hydrogen re-arrangement and altered reaction pathways in a protocol for CO2 catalytic processing of oleic acid into C8-C15 alkanes
Xing, Shiyou,Lv, Pengmei,Yuan, Haoran,Yang, Lingmei,Wang, Zhongming,Yuan, Zhenhong,Chen, Yong
supporting information, p. 4157 - 4168 (2017/09/07)
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.
Catalytic Synthesis of “Super” Linear Alkenyl Arenes Using an Easily Prepared Rh(I) Catalyst
Webster-Gardiner, Michael S.,Chen, Junqi,Vaughan, Benjamin A.,McKeown, Bradley A.,Schinski, William,Gunnoe, T. Brent
, p. 5474 - 5480 (2017/04/27)
Linear alkyl benzenes (LAB) are global chemicals that are produced by acid-catalyzed reactions that involve the formation of carbocationic intermediates. One outcome of the acid-based catalysis is that 1-phenylalkanes cannot be produced. Herein, it is reported that [Rh(μ-OAc)(η2-C2H4)2]2 catalyzes production of 1-phenyl substituted alkene products via oxidative arene vinylation. Since C C bonds can be used for many chemical transformations, the formation of unsaturated products provides a potential advantage over current processes that produce saturated alkyl arenes. Conditions that provide up to a 10:1 linear:branched ratio have been achieved, and catalytic turnovers >1470 have been demonstrated. In addition, electron-deficient and electron-rich substituted benzenes are successfully alkylated. The Rh catalysis provides ortho:meta:para selectivity that is opposite to traditional acid-based catalysis.
A new approach for bio-jet fuel generation from palm oil and limonene in the absence of hydrogen
Zhang, Jingjing,Zhao, Chen
, p. 17249 - 17252 (2015/12/08)
The traditional methodology includes a carbon-chain shortening strategy to produce bio-jet fuel from lipids via a two-stage process with hydrogen. Here, we propose a new solution using a carbon-chain filling strategy to convert C10 terpene and lipids to jet fuel ranged hydrocarbons with aromatic hydrocarbon ingredients in the absence of hydrogen.
Design and performance of supported Lewis acid catalysts derived from metal contaminated biomass for Friedel-Crafts alkylation and acylation
Losfeld, Guillaume,Escande, Vincent,Vidal De La Blache, Paul,L'Huillier, Laurent,Grison, Claude
experimental part, p. 111 - 116 (2012/09/08)
The main goal of this work was to prove the interest of metal hyperaccumulator plants in supported Lewis acid catalysis. Friedel-Crafts alkylation and acylation reveal the great catalytic activity of different plant extracts. This approach is a green solution with chemical benefits including high yield, excellent regioselectivity, small amounts of catalyst, mild conditions and concrete perspectives towards the depletion of mineral resources. The results also constitute an incentive for the development of phytoextraction programs on metal-bearing soils.
Intermolecular hydroarylation of unactivated olefins catalyzed by homogeneous platinum complexes
Luedtke, Avery T.,Goldberg, Karen I.
supporting information; experimental part, p. 7694 - 7696 (2009/04/11)
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.
Catalytic ring-attachment isomerization and dealkylation of diethylbenzenes over halide clusters of group 5 and group 6 transition metals
Kamiguchi, Satoshi,Kondo, Kunihiko,Kodomari, Mitsuo,Chihara, Teiji
, p. 54 - 63 (2007/10/03)
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.
DETERMINATION OF COMPOSITION OF REACTION MIXTURES FROM ALKYLATION OF TOLUENE ON PHOSPHORUS-MODIFIED H-ZSM-5 ZEOLITE
Mravec, Dusan,Herain, Jiri,Holotik, Stefan
, p. 1832 - 1839 (2007/10/02)
Determination of analytical composition of reaction mixtures formed by alkylation of toluene with ethylene on a phosphorus-modified H-ZSM-5 zeolite was made by capillary high resolution gas chromatography.Identification of individual components on these reaction mixtures was performed by GC-MS method, using the samples obtained at 320 and 400 deg C on H-ZSM-5 catalyst (modul 43.6) modified with 3.4 wt.percent phosphorus at toluene to ethylene molar ratio 4.5:1 and the catalyst loading expressed as weight hour space velocity WHSV (for toluene) = 6.9 h-1.The reaction mixtures contained a total 86 hydrocarbons.It was confirmed that in addition to the main alkylation reaction, there proceeds also ethylene oligomerization with subsequent cyclization and aromatization, disproportionation, alkylation and cyclization reactions of alkylaromatic hydrocarbons to give alkylnaphthalines and alkylindanes.
Competitive concerted and stepwise addition of free arylium ions to propane in the gas phase
Angelini, Giancarlo,Sparapani, Cinzia,Speranza, Maurizio
, p. 1393 - 1400 (2007/10/02)
Labelled tolylium ions from the decay of ring-multitritiated toluene have been allowed to react with propane in the gas phase, at pressures ranging from 20 to 744 Torr, yielding isomeric propyltoluenes as the major addition products. The relative composition of the n- versus iso-propyltoluenes (σp:σs 3.2-4.7) is found to depend appreciably upon the total pressure of the system and the presence of added bases (NH 3 or CH3OH). Pressure and base effects on the isomeric distribution of both n- and iso-propyltoluenes are also investigated. The results are consistent with a reaction pattern involving preliminary formation of an electrostatic adduct, wherein fast hydride-ion transfer from a secondary C-H bond of C3H8 to the arylium ion takes place. The same mechanism does not seem operative when the first interaction occurs between the tolylium ions and a primary C-H bond of the substrate. The behaviour of isomeric tolylium ions towards propane is discussed and compared with related studies involving unsubstituted phenylium ions. A mechanistic model is proposed for both reactions, which accounts for the apparent discrepancy between the indiscriminate affinity of arylium ions for any kind of substrate and their 'abnormally' high site selectivities.
Aromatic Substitution in the Gas Phase. A Comparative Study of the Alkylation of Benzene and Toluene with C3H7+ Ions from the Protonation of Cyclopropane and Propene
Attina, Marina,Cacace, Fulvio,Giacomello, Pierluigi
, p. 4768 - 4772 (2007/10/02)
Gas-phase alkylaton of benzene and toluene has been used as a probe to sample the isomeric population of C3H7+ ions obtained from the protonation of cyclopropane and of propene, respectively, with H3+ ions in H2 gas at pressures from 50 to 720 torr.The reagent from cyclopropane promotes extensive (over 40percent) n-propylation, in addition to isopropylation of the arenes, on contrast to the reagent from propene that yields only traces of n-propylated products.The n-propylating reagent is identified as protonated cyclopropane, whose lifetime must exceed 10-7 s in the gaseous systems investigated.The mechanism and the selectivity of the gas-phase alkylation are discussed and compared to relevant mass spectrometric and kinetic results.
