Xi:Irritant;108-11-2Relevant articles and documents
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Evans,R.J.D. et al.
, p. 552 - 556 (1974)
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The Catalytic Reduction of Aldehydes and Ketones with 2-Propanol over Silica-Supported Zirconium Catalyst
Inada, Kazushige,Shibagaki, Makoto,Nakanishi, Yukio,Matsushita, Hajime
, p. 1795 - 1798 (1993)
Reduction of aldehydes and ketones with 2-propanol proceeded efficiently over silica-supported zirconium catalyst, and the correspondimg alcohols were obtained in high yields.In the reduction of aldehyde, the acetalization did not occur and the side reaction, the aldol condensation, was inhibited.
Mont-K10 Supported Fe(II) Schiff-Base Complex as an Efficient Catalyst for Hydrogenation of Ketones
Sultana, Samim,Borah, Geetika,Gogoi, Pradip. K.
, p. 2142 - 2157 (2019)
Abstract: A new Fe(II) Schiff base complex anchored on mont-K10 (Fe@imine-mont-K10) was synthesized and extensively characterized by FTIR, powder X-ray diffraction, SEM–EDX, TEM, ESR, X-ray photoelectron spectroscopy (XPS), BET surface area measurement, solid state 29Si NMR and ICP-AES analysis. The catalytic activity of the complex was investigated for hydrogenation of ketones. The results indicated that it exhibited good catalytic activity for hydrogenation of aromatic as well as aliphatic ketones in i-PrOH/CH3CN (1:1) using Na-i-OPr as base at 80?°C resulting in moderate to excellent isolated yields (51–99%) of their corresponding products. The catalyst shows good reusability. Graphical Abstract: [Figure not available: see fulltext.].
Ruthenium(II) complexes containing quinone based ligands: Synthesis, characterization, catalytic applications and DNA interaction
Anitha,Manikandan,Endo,Hashimoto,Viswanathamurthi
, p. 174 - 180 (2012)
1,2-Naphthaquinone reacts with amines such as semicarbazide, isonicotinylhydrazide and thiosemicarbazide in high yield procedure with the formation of tridentate ligands HLn (n = 1-3). By reaction of ruthenium(II) starting complexes and quinone based ligands HLn (n = 1-3), a series of ruthenium complexes were synthesized and characterized by elemental and spectroscopic methods (FT-IR, electronic, 1H, 13C, 31P NMR and ESI-MS). The ligands were coordinated to ruthenium through quinone oxygen, imine nitrogen and enolate oxygen/thiolato sulfur. On the basis of spectral studies an octahedral geometry may be assigned for all the complexes. Further, the catalytic oxidation of primary, secondary alcohol and transfer hydrogenation of ketone was carried out. The DNA cleavage efficiency of new complexes has also been tested.
Ruthenium(III) chalconate complexes containing PPh3/AsPh3 and their use as catalysts
Muthukumar,Viswanathamurthi,Prabhakaran,Natarajan
, p. 3833 - 3848 (2010)
Ruthenium(III) complexes of the type [RuX(EPh3)(L)2] (X = Cl or Br; E = P or As; L = 2-hydroxychalcone) have been prepared by reacting [RuX3(EPh3)3] with 2-hydroxychalcones in benzene under reflux. The new complexes have been characterized by analytical and spectroscopic (infrared, electronic, electron paramagnetic resonance, and mass) methods. Redox potential studies of the complexes have been carried out to elucidate the electronic structure, geometry, and electrochemical features. On the basis of data obtained, an octahedral structure has been assigned for all the complexes. The new complexes exhibit catalytic activity for the oxidation of primary and secondary alcohols into their corresponding aldehydes and ketones in the presence of N-methylmorpholine-N-oxide as co-oxidant and they were also found to be efficient catalyst for the transfer hydrogenation of ketones.
Rhodium(I) complexes of β-diketonates and related ligands as hydrosilylation catalysts
Cullen, William R.,Wickenheiser, Eugene B.
, p. 141 - 154 (1989)
The complexes (O-O)Rh(CH2CH2)2 ((O-OH)=FcC(O)CH2C(O)CH3, PhC(O)CH2C(O)CH3, 1,2-(CH3CO)(OH)C6H4, 3-benzoyl-(+)-camphor) are catalysts for the hydrosilylation of PhMeCO with Ph2SiH2.The optical yield from the reaction catalyzed by the camphor derivative is too low to measure.Only low optical yields (max 8.7percent e.e.) are obtained from the same reaction by using similar in situ catalysts with ligands prepared from (+)-PhCH(Me)NH2.Bases such as H- and PhCH(Me)NH- catalyze the hydrosilylation reaction in the absence of rhodium salts, but only low optical yields are obtained.Ph2SiH2 reacts with 2-cyclohexen-1-one under these conditions and the mode of reaction depends on the reaction conditions.
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Huston,Tiefenthal
, p. 673,675,676 (1951)
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Enzymatic kinetic resolution of aliphatic sec-alcohols by LipG9, a metagenomic lipase
Bandeira, Pamela T.,Alnoch, Robson C.,De Oliveira, Alfredo R.M.,De Souza, Emanuel M.,De O.P., Fábio,Krieger, Nadia,Piovan, Leandro
, p. 58 - 63 (2016)
Bioprospection for new enantioselective enzymes for application in organic synthesis is a prominent area of investigation in biocatalysis. In this context, here we present the evaluation of an immobilized lipase isolated from a metagenomic library (LipG9) for the enzymatic kinetic resolution (EKR) of aliphatic sec-alcohols, which are still challenging substrates, since low enantioselectivity values are usually observed for these resolutions. LipG9 was successfully employed in EKR of aliphatic alcohols, which were resolved with satisfactory conversions (19-59%) and enantiomeric excesses for alcohols (26-88%) and esters (30-96%) by transesterification reactions, demonstrating that its performance is equal to or better than commercially available enzymes for the same reaction.
Transfer hydrogenation of ketones by ceria-supported Ni catalysts
Shimura, Katsuya,Shimizu, Ken-Ichi
, p. 2983 - 2985 (2012)
Ni-loaded CeO2, prepared by H2-reduction of NiO-loaded CeO2, was found to be an effective and recyclable catalyst for the transfer hydrogenation of aliphatic and aromatic ketones by 2-propanol to the corresponding alcohols under base free conditions with low catalyst loading (1-3 mol%).
SODIUM HYDROXIDE-ACTIVATED CATALYST OF COLLOIDAL NICKEL BORIDE FOR ATMOSPHERIC HYDROGENATION OF KETONES AND ALDEHYDES
Nakao, Yukimichi,Fujishige, Shoei
, p. 673 - 676 (1980)
Addition of sodium hydroxide to colloidal nickel boride in ethanol resulted in a marked enhancement of its catalytic activity for atmospheric hydrogenation of acetone at 30 deg C by a factor of more than 20.Other ketones and aldehydes with bulky substituents were smoothly hydrogenated by the activated colloidal catalyst.
Thexylchloroborane-Methyl Sulfide. A Selective Monohydroborating agent with Exceptional regioselectivity
Brown, Herbert C.,Sikorski, James A.,Kulkarni, Surendra U.,Lee, Hsiupu D.
, p. 4540 - 4542 (1980)
Thexylchloroborane, readily prepared from 2,3-dimethyl-2-butene and monochloroborane-methyl sulfide in dichloromethane solution, hydroborates representative alkenes with excellent regioselectivity to afford thexylalkylchloroboranes.
Montmorillonite supported (-)N-dodecyl-N-methyl ephedrenium borohydride: An efficient reducing agent
Sarkar,Rao
, p. 1247 - 1250 (1991)
The clay supported reagent reduces ketones under phase transfer conditions efficiently. A two fold activation of the carbonyl group - one by the Lewis acid sites on clay and the other by the β-hydroxy group of ephedreium moiety, ensures facile eductions -maintaining a fair degree of stereoselectivity in reducing some of the cyclic ketones. Asymmetric inductions of 1-9.7% were observed in case of some prochiral ketones.
Coordination behavior of ligand based on NNS and NNO donors with ruthenium(III) complexes and their catalytic and DNA interaction studies
Manikandan,Viswnathamurthi
, p. 864 - 870 (2012)
Reactions of 2-acetylpyridine-thiosemicarbazone HL1, 2-acetylpyridine-4-methyl-thiosemicarbazone HL2, 2-acetylpyridine-4- phenyl-thiosemicarbazone HL3 and 2-acetylpyridine-semicarbazone HL4 with ruthenium(III) precursor complexes were studied and the products were characterized by analytical and spectral (FT-IR, electronic, EPR and EI-MS) methods. The ligands coordinated with the ruthenium(III) ion via pyridine nitrogen, azomethine nitrogen and thiolate sulfur/enolate oxygen. An octahedral geometry has been proposed for all the complexes based on the studies. All the complexes are redox active and display an irreversible and quasireversible metal centered redox processes. Further, the catalytic activity of the new complexes has been investigated for the transfer hydrogenation of ketones in the presence of isopropanol/KOH and the Kumada-Corriu coupling of aryl halides with aryl Grignard reagents. The DNA cleavage efficiency of new complexes has also been tested.
Meerwein-Ponndorf-Verley Type Reduction of Ketones and Oppenauer Type Oxidation of Alcohols under the Influence of Cp2ZrH2
Ishii, Yasutaka,Nakano, Tatsuya,Inada, Akihiro,Kishigami, Yoshitaka,Sakurai, Katsunori,Ogawa, Masaya
, p. 240 - 242 (1986)
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Vigneron,Jacquet
, p. 939,944 (1976)
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A porous inorganic zirconyl pyrophosphate as an efficient catalyst for the catalytic transfer hydrogenation of ethyl levulinate to γ-valerolactone
Wang, Jianjia,Wang, Ruiying,Zi, Huimin,Wang, Haijun,Xia, Yongmei,Liu, Xiang
, p. 1370 - 1378 (2018)
Catalytic transfer hydrogenation (CTH) of ethyl levulinate (EL) to γ-valerolactone (GVL) is an alluring reaction in the field of biomass catalytic conversion, but it normally depends on the consumption of H2. In this study, we report a porous Zr-containing inorganic pyrophosphate catalyst (ZrOPP), which was used as a catalyst for CTH of EL to GVL in the presence of isopropanol and characterized using FT-IR, py-FTIR, TGA, XRD, BET, XPS, ICP-AES, SEM, TEM, NH3-TPD, and CO2-TPD. We achieved a high yield of 94% GVL at 433 K for 11 hr. Furthermore, the ZrOPP has the trait of easy separation and could be reused more than five times without distinct decrease in activity and selectivity. In addition, this catalyst could also be applied to other catalytic hydrogenation reactions, such as those of cyclohexanone, acetophenone, 2-heptanone etc. Its outstanding performance was mainly ascribed to the acid sites from the Zr element and basic sites from phosphate groups interspersing on the surface of the catalyst.
Carbon‐supported Raney nickel catalyst for acetone hydrogenation with high selectivity
Lu, Shuliang,Wu, Jiajia,Peng, Hui,Chen, Yong
, (2020)
Catalysts with high selectivity play key roles in green chemistry. In this work, a granular Raney Ni catalyst using carbon as support (Raney Ni/C) was developed by mixing phenolic resin with Ni-Al alloy, conducting carbonization at high temperature, and leaching with alkaline liquor. The as-prepared Raney Ni/C catalyst is suitable for use in fix-bed reactors. Moreover, it shows high activity and selectivity for catalytic acetone hydrogenation. For instance, at the reaction temperature of 120°C, the conversion of acetone can reach up to 99.9% and the main byproduct methyl isobutylcarbinol (MIBC) content can be diminished to 0.02 wt%. The Raney Ni/C may represent a new type of shaped Raney metal catalysts, which are important fix-bed catalysts in chemical industry.
The application of tunable tridendate P-based ligands for the Ru(II)-catalysed transfer hydrogenation of various ketones
Meri, Nermin,Durap, Feyyaz,Aydemir, Murat,Baysal, Akn
, p. 803 - 808 (2014)
Two novel versatile tridendate aminophosphine-phosphinite and phosphinite ligands were prepared and their trinuclear neutral ruthenium(II) dichloro complexes were found to be effective catalysts for the transfer hydrogenation of various ketones in excellent conversions up to 99% in the presence of 2-propanol/NaOH in 0.1M isopropanol solution. Particularly, [Ru3 (PPh2OC2H4)2N-PPh2 (η6-p-cymene)3Cl6] acts as an excellent catalyst giving the corresponding alcohols in excellent conversion up to 99% (turnover frequency ≤ 1176 h-1). A comparison of the catalytic properties of the complexes is also discussed briefly. Furthermore, the structures of these ligands and their corresponding complexes have also been clarified using a combination of multinuclear NMR spectroscopy, infrared spectroscopy and elemental analysis. 1H-13C HETCOR or 1H-1H COSY correlation experiments were used to confirm the spectral assignments.
Half?Sandwich (η6?p?Cymene) Ruthenium(II) complexes bearing 5?Amino?1?Methyl?3?Phenylpyrazole Schiff base ligands: Synthesis, structure and catalytic transfer hydrogenation of ketones
Ramesh, Madhan,Venkatachalam, Galmari
, p. 47 - 55 (2019)
New (η6?p?cymene) ruthenium(II) complexes containing Schiff base ligands of the general composition [RuCl(η6?p?cymene)(L1?3)] have been synthesized. The complexes were characterized by analytical and spectral (FT?IR, UV–Vis, 1H NMR and 13C NMR) methods. The molecular structure of the representative complex [RuCl(η6?p?cymene)(L3)] 6 was determined by single crystal X?ray diffraction studies, revealing a pseudo-octahedral piano stool geometry around ruthenium(II) ion. Further, one of the complexes 6 was screened for their efficiency as a catalyst in the transfer hydrogenation of various ketones to alcohols in the presence of KOH and 2?propanol showed an excellent conversion up to 99%. Under the optimized conditions, the influence of base, reaction temperature and substrate scope was also reported.
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Brown,Zweifel
, p. 4708,4709 (1960)
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Cycloruthenation of N-(naphthyl)salicylaldimine and related ligands: Utilization of the Ru-C bond in catalytic transfer hydrogenation
Dutta, Jayita,Richmond, Michael G.,Bhattacharya, Samaresh
, p. 4600 - 4610 (2014)
Upon reaction with [Ru(PPh3)2(CO)2Cl2], N-(naphthyl)-4-R-salicylaldimines (R = OCH3, H, Cl; H2L1-H2L3) and 2-hydroxy-N-(naphthyl)naphthaldimine (H2L4) readily undergo cycloruthenation by C-H bond activation at the peri position to afford complexes of the type [Ru(PPh3)2(L)(CO)] (L = L1-L4). The crystal structures of the [Ru(PPh3)2(L)(CO)] (L = L1, L2, L4) complexes were determined and the structure of [Ru(PPh3)2(L3)(CO)] optimized by DFT calculations. The thermodynamics for the reaction of [Ru(PPh3)2(CO)2Cl2] with H2L2 to give [Ru(PPh3)2(L2)(CO)] were determined. All the complexes show intense absorptions in the visible and UV regions, which have been analyzed by TDDFT calculations. Cyclic voltammetry of the four cycloruthenated complexes showed two oxidations within the range 0.50-1.35 V versus SCE and a reduction at around -1.75 V versus SCE. The [Ru(PPh3)2(L)(CO)] (L = L1-L4) complexes were found to efficiently catalyze the transfer hydrogenation of carbonyl compounds.
Synthesis method of antioxidant 6PPD to reduce side reactions
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Paragraph 0016; 0018-0019, (2022/03/02)
The present invention belongs to the field of fine chemical technology, relates to a method of continuous synthesis of adhesive antioxidant 6PPD. The patent of the present invention uses a precious metal catalyst to synthesize antioxidant 6PPD on a fixed bed, the precious metal catalyst is loaded into a fixed bed reaction device, nitrogen is filled with 0.1 ~ 0.5MPa pressure and replaces the entire high pressure reactor system, after the reaction system is replaced, the temperature rises, and the flow rate of hydrogen is 0.1 ~ 1L / min. Using 4-aminodiphenylamine and similar organic matter and methyl isobutyl methyl ketone and acetone as raw materials, the synthesis test of the antioxidant 6PPD using a precious metal catalyst was carried out. Compared with the existing precious metal kettle hydrogenation process, it has continuous operation, simple operation, avoids the catalyst loss caused by the use of powder catalyst due to filtration, and can reduce production costs; compared with the existing copper catalyst, due to the improvement of catalyst selectivity, NO MIBC dehydrogenation device can be added, saving energy consumption and having superiority.
Reduction of α,β-unsaturated carbonyl compounds and 1,3-diketones in aqueous media, using a raney ni-al alloy
Simion, Cristian,Mitoma, Yoshiharu,Katayama, Yumi,Simion, Alina Marieta
, p. 51 - 55 (2021/02/03)
The treatment of α,β-unsaturated carbonyl compounds and 1,3-diketones with Raney Ni-Al alloy in aqueous media yielded as major reaction products the corresponding saturated alcohols and/or the corresponding hydrocarbons, in a complete transformation of the starting material.
Primary Alcohols via Nickel Pentacarboxycyclopentadienyl Diamide Catalyzed Hydrosilylation of Terminal Epoxides
Lambert, Tristan H.,Steiniger, Keri A.
, p. 8013 - 8017 (2021/10/25)
The efficient and regioselective hydrosilylation of epoxides co-catalyzed by a pentacarboxycyclopentadienyl (PCCP) diamide nickel complex and Lewis acid is reported. This method allows for the reductive opening of terminal, monosubstituted epoxides to form unbranched, primary alcohols. A range of substrates including both terminal and nonterminal epoxides are shown to work, and a mechanistic rationale is provided. This work represents the first use of a PCCP derivative as a ligand for transition-metal catalysis.
