- Fine-Bubble-Slug-Flow Hydrogenation of Multiple Bonds and Phenols
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We describe a promising method for the continuous hydrogenation of alkenes or alkynes by using a newly developed fine-bubble generator. The fine-bubble-containing slug-flow system was up to 1.4 times more efficient than a conventional slug-flow method. When applied in the hydrogenation of phenols to the corresponding cyclohexanones, the fine bubble-slug-flow method suppressed over-reduction. As this method does not require the use of excess gas, it is expected to be widely applicable in improving the efficiency of gas-mediated flow reactions.
- Iio, Takuya,Nagai, Kohei,Kozuka, Tomoki,Sammi, Akhtar Mst,Sato, Kohei,Narumi, Tetsuo,Mase, Nobuyuki
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p. 1919 - 1924
(2020/11/09)
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- Direct conversion of carboxylic acids (Cn) to alkenes (C2n - 1) over titanium oxide in absence of noble metals
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Carbon-carbon bond formations and deoxygenation reactions are important for biomass up-grading. The classical ketonic decarboxylation of carboxylic acids provides symmetrical ketones with 2n + 1 carbon atoms and eliminates three oxygen atoms. Herein, this reaction is carried out with titanium oxide at 400°C, and an olefin with 2n + 1 carbon atoms is obtained instead of the ketone. For olefin formation hydrogen transfer reactions are required from suitable precursors to form aromatics and coke. Additional aldol condensation reactions increase further molecular weight in the product mixture. Hence, a combination of titanium oxide with a hydrodeoxygenation bed provides double amount of diesel fuel as the combination with zirconium oxide when reacting hexose-derived pentanoic acid.
- Oliver-Tomas, Borja,Renz, Michael,Corma, Avelino
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- Reductive dimerization and oligomerization of alcohols, ketones, and aldehydes to hydrocarbons on a promoted, fused iron catalyst
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A new reductive dimerization and oligomerization reaction of (C5 and C6) cycloalkanols and cycloalkanones, benzaldehyde, and benzyl alcohol to hydrocarbons containing as many, or more, carbon atoms as the reactant oxygenated compound on a promoted, fused iron catalyst proceeds at a temperature of 250-350°C, a hydrogen pressure of 0.1-1 MPa, a specific feed rate of oxygenated reagent of 80-320 g h-1kg-1Ct, and a hydrogen space velocity of 1 × 103 to 20 × 103 h-1. Possible reaction mechanisms have been considered.
- Glebov,Zaikin,Mikaya,Kliger
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p. 296 - 308
(2014/08/05)
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- The identification of 7-[(R)-2-((1S,2S)-2-benzyloxycyclopentylamino)-1- hydroxyethyl]-4-hydroxybenzothiazolone as an inhaled long-acting β2-adrenoceptor agonist
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The optimisation of two series of 4-hydroxybenzothiazolone derived β2-adrenoceptor agonists, bearing α-substituted cyclopentyl and β-phenethyl amino-substituents, as inhaled long-acting bronchodilators is described. Analogues were selected for synthesis using a lipophilicity based hypothesis to achieve the targeted rapid onset of action in combination with a long duration of action. The profiling of the two series led to identification of the α-substituted cyclopentyl analogue 2 as the optimal compound with a comparable profile to the inhaled once-daily long-acting β2-adrenoceptor agonist indacaterol. On the basis of these data 2 was promoted as the backup development candidate to indacaterol from the Novartis LABA project.
- Arnold, Nicola,Beattie, David,Bradley, Michelle,Brearley, Andrew,Brown, Lyndon,Charlton, Steven J.,Fairhurst, Robin A.,Farr, David,Fozard, John,Fullerton, Joe,Gosling, Martin,Hatto, Julia,Janus, Diana,Jones, Darryl,Jordan, Lynne,Lewis, Christine,Maas, Janet,McCarthy, Clive,Mercer, Mark,Oakman, Helen,Press, Neil,Profit, Rachel,Schuerch, Friedrich,Sykes, David,Taylor, Roger J.,Trifilieff, Alexandre,Tuffnell, Andrew
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p. 4341 - 4347
(2014/10/15)
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- Synthesis of renewable high-density fuels using cyclopentanone derived from lignocellulose
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By the combination of solvent-free aldol condensation and one-step hydrodeoxygenation under mild reaction conditions, a high-density (0.866 g mL-1) bicyclic C10 hydrocarbon was synthesized in high overall yield (up to 80%) using cyclopentanone derived from lignocellulose. The Royal Society of Chemistry 2014.
- Yang, Jinfan,Li, Ning,Li, Guangyi,Wang, Wentao,Wang, Aiqin,Wang, Xiaodong,Cong, Yu,Zhang, Tao
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supporting information
p. 2572 - 2574
(2014/03/21)
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- Self-coupling of secondary alcohols by Ni/CeO2 catalyst
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Supported nickel catalysts are studied for the liquid phase CC self-coupling of aliphatic secondary alcohols under additive free conditions in N2 atmosphere. Among various Ni catalysts, 1 or 3 wt% Ni/CeO 2 catalysts pre-reduced in H2 shows highest yield (94%) of a dimer product (a higher ketone) for the self-coupling of 1-octanol at 130 C, and the catalyst is reused. The catalysts are also effective for self-coupling of various secondary alcohols, providing the first heterogeneous catalytic system for the self-coupling of secondary alcohols under mild conditions. Effects of support material and oxidation state of Ni on the activity are studied and it is found that both CeO2 and metallic Ni are indispensable for the reaction. A possible reaction mechanism is proposed, in which ketones, formed by dehydrogenation of alcohol, undergone Aldol condensation to give α,β-unsaturated ketone which is finally hydrogenated by in situ formed NiH species.
- Shimura, Katsuya,Kon, Kenichi,Hakim Siddiki,Shimizu, Ken-Ichi
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p. 137 - 142
(2013/07/26)
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- New one-pot multistep process with multifunctional catalysts: Decreasing the e factor in the synthesis of fine chemicals
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The synthesis of a series of fine chemicals (4-(4-methoxyphenyl)-2- butanone, 4-(6,6-dimethylbicyclo[3,1,1]hept-2-en-2-yl)-2-butanone, and 2-cyclopentylcylopentanone) has been performed through a simple process that involves one-pot multi-step reactions (condensation-dehydration-reduction) using multifunctional base-acid-metal catalysts. The E factor for the specific process, as well as for the global process that includes the manufacturing of the reactants, has been calculated and compared with those obtained using conventional methods. In various cases, it is demonstrated that by means of process intensification with multifunctional solid catalysts, it is possible to decrease the E factor by one order of magnitude or more with respect to any of the manufacturing routes reported to date.
- Climent, Maria J.,Corma, Avelino,Iborra, Sara,Mifsud, Maria,Velty, Alexandra
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experimental part
p. 99 - 107
(2010/05/18)
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- Copper nanoparticles on hydrotalcite as a heterogeneous catalyst for oxidant-free dehydrogenation of alcohols
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We have developed a highly efficient heterogeneous catalytic system using hydrotalcite-supported Cu nanoparticles (Cu/HT) that can successfully promote the oxidant-free dehydrogenation of various alcohols under liquid-phase conditions. The Royal Society of Chemistry.
- Mitsudome, Takato,Mikami, Yusuke,Ebata, Kaori,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
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supporting information; experimental part
p. 4804 - 4806
(2009/03/12)
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- Catalytic oxidation of alkyl- and cycloalkylcyclanones into lactones
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Pilot-plant syntheses of alkyl and cycloalkylcyclanones and their subsequent liquid-phase oxidation into lactones are described. Characteristics of resulting intermediates and target products are reported.
- Abbasov,Alimardanov,Suleimanova
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p. 621 - 626
(2007/10/03)
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- Classical Organic Reactions in Pure Superheated Water
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At high temperatures and pressures, pure liquid water becomes a surprisingly effective medium for the reactions of organic compounds.It may function simultaneously as a convenient solvent, catalyst, and reagent for reactions which are typically acid- or base-catalyzed.Rapid and highly selective conversion are observed for the majority of the compounds in this study.
- Kuhlmann, Barbara,Arnett, Edward M.,Siskin, Michael
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p. 3098 - 3101
(2007/10/02)
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- Free-Radical Ring Expansion of Fused Cyclobutanones: Stereospecific Construction of 5,7-, 6,7-, 7,7-, 8,7-, and 5,8-Cis-Fused Bicyclic Systems
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A new method of appending seven- and eight-membered rings to cycloalkenes is described.Treatment of selected alkene precursors with an ω-bromoalkyl ketene or a keteniminium salt leads to haloalkyl cyclobutanone formation.Tri-n-butyltin hydride promoted ring expansion then yields the annulated product.Since the initial cyclobutanone is cis fused, the final product is also produced stereospecifically with a cis ring fusion.
- Dowd, Paul,Zhang, Wei
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p. 7163 - 7171
(2007/10/02)
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- Importance of Structure of α,β-Ethylenic Ketones during Their Reductive Coupling Promoted by the TiCl4-Mg Reagent
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In most cases, the reductive coupling of α,β-ethylenic ketones by the TiCl4-Mg reagent leads to 1,3,5-trienes and bisallylic pinacols.Some α,β-enones of s-cis configuration, such as (+)-pulegone, show a particular reactivity: formation of dihydro ketones in the presence of tert-butyl alcohol and reductive alkylation with allylic halides or benzyl bromide.Results are accordance with a polymeric structure for the native low-valent titanium species, and in the case of some s-cis-enones, they can be explained by the intervention of a oxametallacyclopentene.
- Pons, Jean-Marc,Santelli, Maurice
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p. 877 - 884
(2007/10/02)
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