Xi:Irritant;108-11-2Relevant articles and documents
Catalytic transfer hydrogenation of ketones catalyzed by orthometalated ruthenium(III) 2-(arylazo)phenolate complexes containing triphenylarsine
Venkatachalam, Galmari,Ramesh, Rengan
, p. 5215 - 5218 (2005)
Air-stable, mononuclear orthometalated ruthenium(III) 2-(arylazo)phenolate complexes of the general composition [RuX(AsPh3)2(L)] (X = Cl or Br; L = CNO donor of the 2-(arylazo)phenolate ligands) have been synthesized and characterized by IR, UV-vis, and EPR as well as by elemental analysis. One of the complexes [RuBr(AsPh3)2(azo-OMe)] was structurally characterized by X-ray analysis and was found to be an efficient catalyst for the transfer hydrogenation of ketones with excellent conversion in the presence of isopropanol at 80°C in 1 h.
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.
Hydroboration. 97. Synthesis of new exceptional chloroborane-Lewis base adducts for hydroboration. Dioxane-monochloroborane as a superior reagent for the selective hydroboration of terminal alkenes
Kanth,Brown
, p. 5359 - 5365 (2001)
Several less volatile oxygen-containing Lewis bases, such as tert-butyl methyl ether, dioxane, anisole, ethyl acetate, β-chloroethyl ether, and monoglyme, were examined as prospective mono- and dichloroborane carriers. Dioxane, ethyl acetate, and β-chloroethyl ether form relatively stable boron trichloride adducts, but the boron trichloride adduct of monoglyme is not very stable and must be used immediately. On the other hand, tert-butyl methyl ether and anisole fail to form stable boron trichloride adducts and the corresponding ether-cleaved products are obtained. Among the selected oxygen-containing Lewis bases, only dioxane forms stable and reactive mono- and dichloroborane adducts. Monoglyme and β-chloroethyl ether give stable dichloroborane adducts requiring excess of diborane. Convenient methods for the preparation of mono- and dichloroborane adducts of dioxane from dioxane-BCl3 and NaBH4 in the presence of catalytic amounts of tri- or tetraglyme were developed. The dioxane-monochloroborane adduct hydroborates representative olefins cleanly and rapidly. The corresponding alcohols were obtained in quantitative yields after oxidation. Also, the hydroboration of several terminal olefins with dioxane-monochloroborane were highly regioselective and the primary alcohols were obtained almost exclusively (>99.5%), after oxidation. Accordingly, dioxane-monochloroborane should serve as a reagent of choice for such hydroborations. The dioxane-dichloroborane adduct showed remarkable selectivity toward 2-substituted terminal olefins, such as 2-methyl-1-butene and β-pinene, when compared to simple terminal and hindered olefins, giving a unique tool for selective hydroborations. Dichloroborane adducts of monoglyme and β-chloroethyl ether also showed high reactivity, even at room temperature, toward simple unhindered olefins. However, hydroboration of hindered olefins is slow and requires either higher temperatures or the addition of 1 equiv of boron trichloride to liberate free dichloroborane, as in the case of the previously known dichloroborane adducts of methyl sulfide and diethyl ether.
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.
Stereoselective Oxidative Coupling and Asymmetric Hydride Reduction related to (-)-(S)-10,10'-Dihydroxy-9,9'-biphenanthryl
Yamamoto, Koji,Fukushima, Hitoshi,Nakazaki, Masao
, p. 1490 - 1491 (1984)
Oxidative coupling of 9-phenanthrol (1) with a (-)-(R)-1,2-diphenylethylamine-copper(II) complex yielded (-)-(S)-10,10'-dihydroxy-9,9'-biphenanthryl (2) (98percent optical purity); the chiral aluminium hydride reagent modified by (2) was found to exhibit enantioface selectivity towards a variety of prochiral carbonyl compounds.
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.
Syntheses of enantiopure aliphatic secondary alcohols and acetates by bioresolution with lipase B from candida antarctica
Ferreira, Hercules V.,Rocha, Lenilson C.,Severino, Richele P.,Porto, Andre L. M.
, p. 8955 - 8967,13 (2012)
The lipase B from Candida antarctica (Novozym 435, CALB) efficiently catalyzed the kinetic resolution of some aliphatic secondary alcohols: (±)-4-methylpentan- 2-ol (1), (±)-5-methylhexan-2-ol (3), (±)-octan-2-ol (4), (±)-heptan-3-ol (5) and (±)-oct-1- en-3-ol (6). The lipase showed excellent enantioselectivities in the transesterifications of racemic aliphatic secondary alcohols producing the enantiopure alcohols (>99% ee) and acetates (>99% ee) with good yields. Kinetic resolution of rac-alcohols was successfully achieved with CALB lipase using simple conditions, vinyl acetate as acylating agent, and hexane as non-polar solvent.
Heterogeneous catalytic conversions with hydrous SnO2
Waghoo, Gulzar,Jayaram,Joshi
, p. 513 - 520 (1999)
Hydrous Tin oxide (SnO2) was prepared by the action of conc. HNO3 on tin metal. It was found to catalyse transesterification, amidation and transferhydrogenation in the vapour phase significantly. There was no loss in activity for at least 50 runs of the reactions.
