873-94-9Relevant articles and documents
Could the energy cost of using supercritical fluids be mitigated by using CO2 from carbon capture and storage (CCS)?
Stevens, James G.,Gomez, Pilar,Bourne, Richard A.,Drage, Trevor C.,George, Michael W.,Poliakoff, Martyn
, p. 2727 - 2733 (2011)
This article explores the possibility of utilising supercritical CO 2 obtained from carbon capture and storage (CCS) as a solvent and examines the hydrogenation of isophorone to 3,3,5-trimethylcyclohexanone using supercritical CO2 with added N2, CO or H2O to emulate the contaminants expected in CO2 from CCS. None of the impurities appear to cause insuperable problems in the hydrogenation of isophorone when present at concentrations likely to be found in CO2 from CCS. N2 introduces modest changes in phase behaviour at some pressures, while CO and H2O reduce the activity of the catalyst. However, the activity can be largely regained by increasing the reaction temperature.
Water-soluble dendritic architectures with carbohydrate shells for the templation and stabilization of catalytically active metal nanoparticles
Kraemer, Michael,Perignon, Nelly,Haag, Rainer,Marty, Jean-Daniel,Thomann, Ralf,Viguerie, Nancy Lauth-De,Mingotaud, Christophe
, p. 8308 - 8315 (2005)
Hyperbranched poly(ethylenimine) (PEI) with amino groups or carbohydrate terminal groups have been used as support materials for metal nanoparticles (i.e., Cu, Ag, Au, and Pt) in water. Various parameters have been optimized, such as pH, concentration of the polymer in solution, and [metal ions]/ [polymer] ratio in order to obtain stable metal nanoparticles with a narrow size distribution. TEM measurements revealed that particles with a diameter as low as 1.4 nm were obtained. An increase of stability was obtained after functionalization of PEI with glycidol, gluconolactone, or lactobionic acid. In the case of Pt the catalytical activity of the corresponding nanoparticles was evidenced.
Study on the selective hydrogenation of isophorone
Xu, Lei,Sun, Shaoyin,Zhang, Xing,Gao, Haofei,Wang, Wei
, p. 4465 - 4471 (2021/02/03)
3,3,5-Trimethylcyclohexanone (TMCH) is an important pharmaceutical intermediate and organic solvent, which has important industrial significance. The selective hydrogenation of isophorone was studied over noble metal (Pd/C, Pt/C, Ir/C, Ru/C, Pd/SiO2, Pt/SiO2, Ir/SiO2, Ru/SiO2), and non-noble metal (RANEY Ni, RANEY Co, RANEY Cu, RANEY Fe, Ni/SiO2, Co/SiO2, Cu/SiO2, Fe/SiO2) catalysts and using solvent-free and solvent based synthesis. The results show that the solvent has an important effect on the selectivity of TMCH. The selective hydrogenation of isophorone to TMCH can be influenced by the tetrahydrofuran solvent. The conversion of isophorone is 100%, and the yield of 3,3,5-trimethylcyclohexanone is 98.1% under RANEY Ni and THF. The method was applied to the selective hydrogenation of isopropylidene acetone, benzylidene acetone and 6-methyl-5-ene-2-heptanone. The structures of the hydrogenation product target (4-methylpentan-2-one, 4-benzylbutan-2-one and 6-methyl-heptane-2-one) were characterized using 1H-NMR and 13C-NMR. The yields of 4-methylpentan-2-one, 4-benzylbutan-2-one and 6-methyl-heptane-2-one were 97.2%, 98.5% and 98.2%, respectively. The production cost can be reduced by using RANEY metal instead of noble metal palladium. This method has good application prospects. This journal is
Gas phase transfer hydrogenation of α, β- unsaturated carbonyl compounds into saturated carbonyl compounds over supported Cu catalysts
K, Saidulu Reddy,Enumula, Siva Sankar,Koppadi, Kumara Swamy,Rao Kamaraju, Seetha Rama,Burri, David Raju
, (2019/11/28)
This work aims to produce hydrocinnamaldehyde via selective C[dbnd]C bond hydrogenation of cinnamaldehyde via transfer hydrogenation catalyzed by supported Cu catalysts. The catalytic activity and characterization results demonstrated that conversion of cinnamaldehyde and selectivity to hydrocinnamaldehyde is an integrated result of active Cu metal surface area and nature of support material. In the case of Cu/SiO2 catalysts, the rate of formation of hydrocinnamaldehyde was linearly dependent on the active Cu metal surface area. A maximum rate of formation of hydrocinnamaldehyde 167.82 μmol.g?1.s-1 was obtained at an active Cu metal surface area of 6.1 m2.gcat-1 over 20 wt. % Cu/SiO2 catalyst. While in the case of other supported Cu catalysts (Cu/MgO, Cu/ZrO2 and Cu/γ-Al2O3) along with the active Cu metal surface area, the surface acidity and basicity governed the selectivity of hydrocinnamaldehyde. The rate of formation of hydrocinnamaldehyde followed the trend Cu/SiO2 >Cu/Al2O3 >Cu/MgO > Cu/ZrO2. Unlike Cu/SiO2 catalyst, the competitive adsorption of C[dbnd]C and CO[dbnd] bonds over these (Al2O3, MgO and ZrO2) supported Cu catalysts altered the selectivity of hydrocinnamaldehyde. Cu/SiO2 catalyst was superior in selective C[dbnd]C hydrogenation of α, β-unsaturated carbonyl compounds via transfer hydrogenation. Cyclohexenone, isophorone and crotonaldehyde were selectively converted into their saturated carbonyl compounds.
Cucurbit[5]uril-mediated electrochemical hydrogenation of α,β-unsaturated ketones
Sales, Ayrlane,de Oliveira e Castro, Isabela Andrade,de Menezes, Frederico Duarte,Selva, Thiago Matheus Guimar?es,Vilar, Márcio
, p. 295 - 305 (2019/09/03)
The potential of cucurbit[5]uril to be used as inverse phase transfer catalyst in electrocatalytic hydrogenation of α,β-unsaturated ketones is illustrated. The interaction behavior among isophorone and cucurbit[5]uril was also investigated using cyclic voltammetry and UV/vis absorption spectroscopy. The results concerning to both techniques revealed an enhancement in the intensity of the absorption peak and also in the current cathodic peak of isophorone in presence of cucurbit[5]uril. This achievement is related to the increase of the isophorone solubility in the medium being an indicative of a host-guest complex formation. The electrochemical hydrogenation of isophorone using cucurbit[5]uril was more efficient than others well-stablish methodologies. Regarding to (R)-(+)-pulegone and (S)-(+)-carvone, the use of cucurbit[5]uril leads to an increase of 17% and 9%, on average, respectively, in the yields when compared to the control reaction. The efficiency of selective C=O bond hydrogenation of 1-acetyl-1-cyclohexene was evaluated. The presence of cucurbit[5]uril increased by 12% the hydrogenations yields of 1-acetyl-1-cyclohexene when compared to the control reaction. In this sense, these results open up an opportunity to carry out electrocatalytic reactions within the cucurbit[5]uril environment.
Iron-Catalyzed Chemoselective Reduction of α,β-Unsaturated Ketones
Lator, Alexis,Gaillard, Sylvain,Poater, Albert,Renaud, Jean-Luc
supporting information, p. 5770 - 5774 (2018/03/26)
An iron-catalyzed chemo- and diastereoselective reduction of α,β-unsaturated ketones into the corresponding saturated ketones in mild reaction conditions is reported herein. DFT calculations and experimental work underline that transfer hydride reduction is a more facile process than hydrogenation, unveiling the fundamental role of the base.
Ammonium Tungstate as an Effective Catalyst for Selective Oxidation of Alcohols to Aldehydes or Ketones with Hydrogen Peroxide under Water - A Synergy of Graphene Oxide
Fu, Huihui,Hu, Chuanfeng,Huang, Zhida,Zhou, Jianhao,Peng, Xinhua
supporting information, p. 447 - 451 (2017/11/27)
Ammonium tungstate was found to be a facile and efficient catalyst for selective oxidation of alcohols to the corresponding carbonyl compounds with hydrogen peroxide as oxidant. Heterogeneous graphene oxide as acid effectively intensified the transformations and resulted in excellent yields. The use of water as solvent rendered the reactions promising both economically and environmentally.
Wilkinson-Type Immobilized Catalyst on Diamond Nanoparticles for Alkene Reduction
Queffélec, Clémence,Schlindwein, Simon H.,Gudat, Dietrich,Silvestre, Virginie,Rodriguez-Zubiri, Mireia,Fayon, Franck,Bujoli, Bruno,Wang, Qi,Boukherroub, Rabah,Szunerits, Sabine
, p. 432 - 439 (2017/02/15)
The immobilization of heterogeneous catalysts on solid support materials is an important task of current catalytic and materials science research. We report here the development of a diamond nanoparticles-based Wilkinson's type catalyst for the reduction of olefins to saturated hydrocarbons. The strategy is based on the formation of rhodium(I)-modified nanodiamonds (NDs–Rh) using a surface-immobilized catechol phosphane ligand, to which rhodium metal centers can be coordinated. The resulting material was characterized by solid-state NMR spectroscopy, X-ray photoelectron spectroscopy, thermogravimetry, and TEM before testing the catalytic efficiency of the catalyst. Excellent hydrogenation efficiency with yields in the range of 85–99 % could be obtained with these new NDs–Rh catalysts, which showed in addition good recyclability without loss of activity.
P-Chirogenic Xantphos Ligands and Related Ether Diphosphines: Synthesis and Application in Rhodium-Catalyzed Asymmetric Hydrogenation
Holz, Jens,Rumpel, Katharina,Spannenberg, Anke,Paciello, Rocco,Jiao, Haijun,B?rner, Armin
, p. 6162 - 6169 (2017/09/15)
A series of P-chirogenic Xantphos ligands and related diaryl ether diphosphines have been synthesized by a modification of the well-established Jugé method. The approach consists of the in situ deboranation of the chiral ephedrine-based phosphinite before the P-C coupling takes place. The stereochemical integrity of the stereocenters of the diphosphines during synthesis, long-time storage, and catalytic application was evaluated. In the rhodium-catalyzed asymmetric hydrogenation of isophorone as a model substrate for industrially relevant prostereogenic enones with some of the diphosphines, almost complete conversion, high chemoselectivity, and 96% ee were achieved.
The selective hydrogenation of the isophorone is 3, 3, 5 - trimethyl cyclohexanone method (by machine translation)
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Paragraph 0018; 0022-0024; 0025-0027; 0028-0030; 0031-0034, (2017/08/27)
The selective hydrogenation of the isophorone is 3, 3, 5 - trimethyl cyclohexanone, isophorone and water will be added after mixing the hydrogen gas after the nano-Pd catalyst, isophorone with hydrogen gas in the reaction under the constant temperature of the cooling after a certain period of time, oil-water phase separation, the oil phase obtained in the 3, 3, 5 - trimethyl cyclohexanone, wherein: nano Pd catalyst preparation method is as follows: with the molten state of the palladium acetate PEG reaction of black are a solid. (by machine translation)
