108-82-7Relevant articles and documents
Cationic ruthenium(II)–NHC pincer complexes: Synthesis, characterisation and catalytic activity for transfer hydrogenation of ketones
Yadav, Dibya,Misra, Shilpi,Kumar, Dheeraj,Singh, Suryabhan,Singh, Amrendra K.
, (2021)
Cationic ruthenium pincer complexes, [Ru(CNC)(CO)(PPh3)Cl]X (CNC = 2,6-bis(1-methylimidazol-2-ylidene)-pyridine, X = Cl? [1a], PF6? [1b]), [Ru(CNC)(PPh3)2Cl]X (X = Cl? [2a], PF6? [2b]) and [Ru(CNC)(PPh3)2(H)]X (X = Cl? [3a], PF6? [3b]) with triphenylphosphine, CO and halides as coligands have been synthesised and characterised by 1H, 13C, 31P NMR, mass and single-crystal X-ray crystallography. The application of Ru complexes in the transfer hydrogenation of a wide range of ketones with 2-propanol as the hydrogen source is explored. The in situ transformations observed during the synthesis help understand and suggest a plausible mechanism via the hydride complex 3b. All complexes appear to be efficient catalyst precursors for transfer hydrogenation of ketones.
Greener synthesis of pristane by flow dehydrative hydrogenation of allylic alcohol using a packed-bed reactor charged by pd/c as a single catalyst
Fukuyama, Takahide,Furuta, Akihiro,Hirobe, Yuki,Hyodo, Mamoru,Kasakado, Takayoshi,Ryu, Ilhyong
, (2021/10/05)
Our previous work established a continuous-flow synthesis of pristane, which is a saturated branched alkane obtained from a Basking Shark. The dehydration of an allylic alcohol that is the key to a tetraene was carried out using a packed-bed reactor charged by an acid–silica catalyst (HO-SAS) and flow hydrogenation using molecular hydrogen via a Pd/C catalyst followed. The present work relies on the additional propensity of Pd/C to serve as an acid catalyst, which allows us to perform a flow synthesis of pristane from the aforementioned key allylic alcohol in the presence of molecular hydrogen using Pd/C as a single catalyst, which is applied to both dehydration and hydrogenation. The present one-column-two-reaction-flow system could eliminate the use of an acid catalyst such as HO-SAS and lead to a significant simplification of the production process.
Multiple Halogenation of Aliphatic C?H Bonds within the Hofmann–L?ffler Manifold
Del Castillo, Estefanía,Martínez, Mario D.,Bosnidou, Alexandra E.,Duhamel, Thomas,O'Broin, Calvin Q.,Zhang, Hongwei,Escudero-Adán, Eduardo C.,Martínez-Belmonte, Marta,Mu?iz, Kilian
supporting information, p. 17225 - 17229 (2018/11/10)
An innovative approach to position-selective polyhalogenation of aliphatic hydrocarbon bonds is presented. The reaction proceeded within the Hofmann-L?ffler manifold with amidyl radicals as the sole mediators to induce selective 1,5- and 1,6-hydrogen-atom transfer followed by halogenation. Multiple halogenation events of up to four innate C?H bond functionalizations were accomplished. The broad applicability of this new entry into polyhalogenation and the resulting synthetic possibilities were demonstrated for a total of 27 different examples including mixed halogenations.
Synthesis of Acetone-Derived C6, C9, and C12Carbon Scaffolds for Chemical and Fuel Applications
Moore, Cameron M.,Jenkins, Rhodri W.,Janicke, Michael T.,Kubic, William L.,Polikarpov, Evgueni,Semelsberger, Troy A.,Sutton, Andrew D.
, p. 3382 - 3386 (2016/12/27)
A simple, inexpensive catalyst system (Amberlyst 15 and Ni/SiO2–Al2O3) is described for the upgrading of acetone to a range of chemicals and potential fuels. Stepwise hydrodeoxygenation of the produced ketones can yield branched alcohols, alkenes, and alkanes. An analysis of these products is provided, which demonstrates that this approach can provide a product profile of valuable bioproducts and potential biofuels.
PRODUCTION METHOD OF DIISOBUTYL CARBINOL BY HYDROGENATION OF DIISOBUTYL KETONE
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Paragraph 0022, (2016/12/22)
PROBLEM TO BE SOLVED: To provide a production method for producing efficiently diisobutyl carbinol having a small content of a ketone body, which is suitable for producing hydrogen peroxide by an anthraquinone method by hydrogenation of diisobutyl ketone. SOLUTION: A production method of diisobutyl carbinol has following steps 1 and 2. Step 1: diisobutyl ketone is hydrogenated at a temperature of 130°C-200°C and at a pressure of 0.1 MPa or higher in the presence of a catalyst containing one or more kinds of metal atoms selected from among copper, zinc, chromium, palladium, rhodium, ruthenium and platinum. Step 2: after finish of step 1, the temperature is lowered to 120°C or lower, while keeping the pressure at 0.1 MPa or higher. COPYRIGHT: (C)2015,JPO&INPIT
Hydrogenation of ketones over bifunctional Pt-heteropoly acid catalyst in the gas phase
Alharbi,Kozhevnikova,Kozhevnikov
, p. 457 - 462 (2015/10/05)
Gas-phase hydrogenation of a wide range of ketones to alkanes, including hydrogenation of aliphatic ketones and acetophenone, was investigated using bifunctional metal-acid catalysis. The catalysts were comprised of a metal (Pt, Ru, Ni, and Cu) supported on acidic caesium salt of tungstophosphoric heteropoly acid Cs2.5H0.5PW12O40 (CsPW). The reaction occurred via a sequence of steps involving hydrogenation of ketone to alcohol on metal sites followed by dehydration of alcohol to alkene on acid sites and finally hydrogenation of alkene to alkane on metal sites. Catalyst activity decreased in the order: Pt > Ru >> Ni > Cu. Pt/CsPW showed the highest catalytic activity, giving almost 100% alkane yield at 100 °C and 1 bar pressure. Evidence is provided that the reaction with Pt/CsPW at 100 °C is limited by ketone-to-alcohol hydrogenation, whereas at lower temperatures (≤60 °C) by alcohol dehydration yielding alcohol as themain product. The catalyst comprised of a physical mixture of Pt/C + CsPW was found to be highly efficientas well, which indicates that the reaction is not limited by migration of intermediates between metal andacid sites in the bifunctional catalyst.
Dramatic promotion of copper-alumina catalysts by sodium for acetone trimerisation
Ligner, Emanuelle,Meunier, Frederic,Travert, Arnaud,Maury, Sylvie,Cadran, Nicolas
, p. 2480 - 2483 (2014/07/22)
Na-promoted Cu-Al materials are efficient multifunctional catalysts for the direct conversion of gas phase acetone to diisobutyl ketone (DIBK) with unprecedented yields (up to 31%). The Na content is a major parameter determining the stability and the catalytic performance of these materials.
Variations on an NHC theme: Which features enhance catalytic transfer hydrogenation with ruthenium complexes?
Depasquale, Joseph,Kumar, Mukesh,Zeller, Matthias,Papish, Elizabeth T.
, p. 966 - 979 (2013/04/23)
N-heterocyclic carbene (NHC) based ruthenium complexes were studied as catalysts for the transfer hydrogenation of ketones. Variations in the catalyst structure were investigated for their impact on hydrogenation and catalyst stability. Catalyst attributes included bis- or mono-NHC ligands, pendant ether groups in some cases, and arene ligands of varied bulk and donor strength. Ruthenium complexes were synthesized and fully characterized, including complexes with a monodentate NHC ligand containing a tethered ether N substituent (ImEt,CH2CH2OEtRuCl2(η6-arene); arene = benzene (4), p-cymene (5), hexamethylbenzene (6)), a complex with a monodentate NHC ligand with solely alkyl N substituents (Im Et,PentylRuCl2(η6-p-cymene) (8)), and a complex with a bis-NHC ligand ([RuCl(methylenebis(ImEt) 2)(η6-p-cymene)]PF6 (7)) (Im = imidazole-derived NHC; superscripts indicate N substituents). X-ray crystal structures were obtained for 4, 5, 7, and 8. All of the ruthenium complexes were tested and found to be active transfer hydrogenation catalysts for the reduction of acetophenone to 1-phenylethanol in basic 2-propanol. Precatalyst 4, which contains a tethered ether group and benzene ligand, was found to be the most active catalyst. Variable-temperature 1H NMR studies of complexes 4-6 show that arene lability increases in the order C 6Me6 -1 and 845, respectively, for ketone reduction with catalyst 4.
Rhodium and iridium nanoparticles entrapped in aluminum oxyhydroxide nanofibers: Catalysts for hydrogenations of arenes and ketones at room temperature with hydrogen balloon
Park, In Soo,Kwon, Min Serk,Kang, Kyung Yeon,Lee, Jae Sung,Park, Jaiwook
, p. 2039 - 2047 (2008/09/17)
The recyclable metal nanoparticle catalysts, rhodium in aluminum oxyhydroxide [Rh/ AlO(OH)] and iridium in aluminum oxyhydroxide [Ir/A1O(OH)], were simply prepared from readily available reagents. The catalysts showed high activities in the hydrogenation of various arenes and ketones under mild conditions. Selective hydrogenation was possible for bicyclic and tricyclic arenes in high yields. The catalysts were active at room temperature even with a hydrogen balloon. Also, the catalysts showed high turnover frequency (TOF) values under solventless conditions at 75 °C under 4 atm hydrogen pressure: ca. 1700h 1 in the hydrogenation of benzene. Furthermore, Rh/A1O(OH) can be reused forat least 10 times without activity loss. The catalysts were characterized by the transmission electron microscopy (TEM), powder X-ray diffraction (XRD), inductively coupled plasma (ICP), energy dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption and hydrogen chemisorption experiments. The sizes of rhodium and iridium particles were estimated to be 3-4 nm and 2-3 nm, respectively. Aluminum oxyhydroxide nanofibers of these catalysts have surface areas of 500-600 m2 g -1.
