502-41-0Relevant academic research and scientific papers
Kinetics of Peroxyradical Attack at Cyclic Hydrocarbons: Ring-Strain Effects on H-Abstraction
Harnisch, Ralf,Lauterbach, Gerlinde,Pritzkow, Wilhelm
, p. 60 - 62 (1995)
Relative autoxidation rates were determined for the cycloalkanes C7 to C12, the methyl cycloalkanes C6 to C9 and the ethyl cycloalkanes C5 to C9 (ring size in each case) by competitive oxidation of the cycloparaffins with cumene.In the case of the methyl and ethyl cycloalkanes the reactivities of the tertiary C-H bonds coould be calculated from the amounts of tertiary alcohols formed after LiAlH4 reduction of the oxidates.As expected, the C-H reactivities are especially low in six-membered cycloparaffins and especially high in five-, seven- and eight-membered cycloparaffins.The C-H reactivity of cyclododecane lies in the same order of magnitude as the reactivities of secondary C-H bonds of normal paraffins.
Meerwein-Ponndorf-Verley reduction of cycloalkanones over magnesium-aluminium oxide
Aramendía, María A.,Borau, Victoriano,Jiménez, César,Marinas, José M.,Ruiz, José R.,Urbano, Francisco J.
, p. 1122 - 1125 (2002)
MgO-Al2O3 obtained from layered double hydroxide has been studied as a catalyst in the Meerwein-Ponndorf-Verley (MPV) reduction of cycloalkanones and substituted cyclohexanones in the liquid phase. Conversions for cycloalkanones always exceeded 95% and the selectivity was 100% within thefirst 10h of reaction. In the MPV reduction of 4-tert-butylcyclohexanone to 4-tert-butylcyclohexanol a high stereoselectivity (cis:trans ratio > 12) was obtained. This stereoselectivity is explained by the transition-state selectivity imposed by the adsorption complex. For the reduction of cyclohexanone, a recycling test showed that the catalyst can be reused up to four times without losing more than 10% catalytic activity.
Synthesis of luminescent rhodium(III) cyclometalated complex by sp2(C)–S bond activation: Application as catalyst in transfer hydrogenation of ketones and live cell imaging
Roy, Puspendu,Sarkar, Deblina,Ghosh, Paramita,Manna, Chandan Kumar,Murmu, Nabendu,Mondal, Tapan Kumar
, (2020)
A new fluorescent Rh(III) cyclometalated complex, [Rh(PPh3)2(L)Cl] (1) is synthesized via sp2(C)–S bond activation of a thioether containing azo-phenol ligand (L-SCH2CH3). The pseudo octahedral geometry around rhodium is confirmed by single crystal X-ray diffraction method. Cyclic voltammogram of the complex exhibits a quasi-reversible oxidation couple with E1/2 of 0.74 V (ΔE = 100 mV) along with a quasi-reversible reduction couple (E1/2 = ?1.18 V, ΔE = 130 mV) in acetonitrile. The complex exhibits low energy emission band at 682 nm with emission quantum yield (? = 0.103) upon excitation at 583 nm. Cytotoxicity of the complex is studied by MTT method with human breast cancer cell lines and IC50 value is found to 18.5 μM. In presence of the complex (10 μM) a bright red fluorescence image of MCF-7 cell lines is observed under fluorescence microscope. Moreover, the complex acts as effective catalyst towards transfer hydrogenation of ketones.
Extending the family of quinolone antibacterials to new copper derivatives: self-assembly, structural and topological features, catalytic and biological activity
Xerras, Panagiotis,Bacharidou, Anna-Maria,Kalogiannis, Stavros,Perdih, Franc,Kirillova, Marina V.,Kirillov, Alexander M.,Turel, Iztok,Psomas, George
, p. 19644 - 19658 (2018)
A new series of copper(ii) compounds, [Cu(pef)2(MeOH)] (1), [Cu(pef)(bipyam)Cl] (2), [Cu(pef)(phen)Cl] (3) and [Cu(pef)(bipy)Cl] (4), bearing the quinolone family member pefloxacin (Hpef) were self-assembled in the presence (optional) of N,N′-donor heterocyclic ligands such as 2,2′-bipyridylamine (bipyam), 1,10-phenanthroline (phen), or 2,2′-bipyridine (bipy). The products were fully characterized, including single-crystal X-ray diffraction analysis of 2-4. The structures are extended into 1D (2), 2D (3), or 3D (4) networks via multiple H-bonds between the monocopper(ii) units and guest water and/or methanol molecules; the latter are arranged into different types of water and hybrid water-methanol clusters. The resulting H-bonded networks were classified from a topological viewpoint, revealing diverse topologies that also include an undocumented type. Compounds 2-4 also act as homogeneous catalysts in a model oxidation reaction, namely the mild oxidation of C6-C8 cycloalkanes by H2O2 at 50 °C to give cyclic alcohols and ketones. The effects of various reaction parameters (substrate scope, temperature, and loadings of catalyst, cycloalkane, and oxidant) and selectivity features were investigated. Besides, products 1-4 also show remarkable antibacterial activity against four different microorganisms (Escherichia coli, Xanthomonas campestris, Staphylococcus aureus and Bacillus subtilis), which is superior to that of free Hpef. The interaction of the Cu(ii) compounds with calf-thymus DNA was studied suggesting intercalation as the most possible binding mode. Furthermore, the interaction of the obtained copper(ii) derivatives with human/bovine serum albumin was investigated by fluorescence emission spectroscopy and the corresponding albumin-binding constants were established. This study widens a limited family of transition metal pefloxacin derivatives.
Oxidoreduction between Cycloalkanols and Cycloalkanones in the Cultured Cells of Nicotiana tabacum. Correlation of the Reaction Rate with the 13C NMR Chemical Shift of the Carbonyl Carbon
Suga, Takayuki,Izumi, Shunsuke,Hirata, Toshifumi
, p. 2053 - 2056 (1986)
The enzyme system responsible for the oxidoreduction between cycloalkanols and their corresponding cycloalkanones in the cultured cells of Nicotiana tabacum was found to be alcohol dehydrogenase which is similar to the dehydrogenase from tea seeds and horse liver.The rate constants and the equilibrium constants of the oxidoreduction between the cycloalkanols and their corresponding cycloalkanones with this enzyme system were well correlated with the 13C NMR chemical shift of the carbonyl carbon of the oxidation products, i.e., the cycloalkanones.
Aluminum metal-organic framework as a new host for preparation of encapsulated metal complex catalysts
Chen, Yanfeng,Fan, Binbin,Lu, Ningyue,Li, Ruifeng
, p. 91 - 95 (2015)
A facile strategy for encapsulation of metal complex guests into MOFs was proposed. This strategy involves pre-adsorbing metal salt on MOF, and then coordinating the metal ions with the organic ligand, as exemplified by encapsulation of tris(1,10-phenanthroline) Cu(II) complexes (CuPhen) in MIL-100(Al) (denoted as CuPhen/MIL). CuPhen encapsulated in MIL-100(Al) showed higher catalytic activity than the neat CuPhen and CuPhen encapsulated in zeolite-Y. The prepared CuPhen/MIL catalyst was stable and could be reused at least three times without significant loss in activity. This work is beneficial for the host-guest chemistry study and the development of new heterogeneous catalysts.
Mild oxidative C?H functionalization of alkanes and alcohols using a magnetic core-shell Fe3O4@mSiO2@Cu4 nanocatalyst
Kirillova, Marina V.,Santos, Carla I.M.,Wu, Wenyu,Tang, Yu,Kirillov, Alexander M.
, p. 343 - 349 (2017)
A new hybrid Fe3O4@mSiO2@Cu4 material was constructed by loading a bio-inspired tetracopper(II) coordination compound [Cu4(μ4-O){N(CH2CH2O)3}4(BOH)4][BF4]2 (Cu4) onto the Fe3O4@mSiO2 core-shell nanoparticles (NPs) composed of a magnetite (Fe3O4) core and mesoporous silica (mSiO2) shell with perpendicularly aligned channels. The obtained Fe3O4@mSiO2@Cu4 magnetic nanoparticles were characterized by transmission electron microscopy (TEM), FT-IR spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), and field-dependent magnetization. This hybrid material acts as a magnetically recoverable C?H functionalization nanocatalyst, namely for the mild oxidation, by t-butyl hydroperoxide at 50–70?°C in acetonitrile medium, of cycloalkanes (cyclopentane, cyclohexane, cycloheptane, and cyclooctane) to the corresponding alcohols and ketones (with up to ～15% yields based on cycloalkane; TON 335). A related oxidation process using cyclohexanol as a more reactive substrate leads to the formation of cyclohexanone in up to ～25% yield (TON 570). The Fe3O4@mSiO2@Cu4 nanocatalyst can be recycled five times without an appreciable loss of activity. The bond-, regio-, and stereoselectivity parameters were investigated in the oxidation of different alkane substrates (n-hexane, n-heptane, n-octane, methylcyclohexane, adamantane, cis- and trans-1,2-demethylcyclohexane), and the obtained results were compared with the homogeneous systems based on the Cu4 catalyst. In particular, the high bond selectivity parameters detected in the oxidation of methylcyclohexane (1°:2°:3° of 1:8:142) and adamantane (2°:3° of 1:21) catalyzed by Fe3O4@mSiO2@Cu4 suggest that the reactions possibly occur in hydrophobic pockets of the nanocatalyst.
Synthesis of new rhodium(III) complex by benzylic C[sbnd]S bond cleavage of thioether containing NNS donor Schiff base ligand: Investigation of catalytic activity towards transfer hydrogenation of ketones
Biswas, Sujan,Das, Akash,Kumar Manna, Chandan,Kumar Mondal, Tapan,Naskar, Rahul
, (2020/11/04)
A new rhodium(III)-triphenylphosphine mixed ligand complex, [Rh(PPh3)(L)Cl2] (1) is synthesized by benzylic C[sbnd]S bond cleavage of L-CH2Ph ligand (where, L-CH2Ph = 2-(benzylthio)-N-(pyridin-2-ylmethylene)aniline). The complex is thoroughly characterized by several spectroscopic techniques. Geometry of the complex is confirmed by single crystal X-ray crystallography. Electronic structure, redox properties, absorption and emission properties of the complex were studied. DFT and TDDFT calculations were carried out to interpret the electronic structure and absorption properties of the complex respectively. The synthesized Rh(III) complex was tested as catalyst towards transfer hydrogenation reaction of ketones in iPrOH and an excellent catalytic conversion was observed under mild conditions.
Ruthenium complexes of phosphine-amide based ligands as efficient catalysts for transfer hydrogenation reactions
Yadav, Samanta,Vijayan, Paranthaman,Yadav, Sunil,Gupta, Rajeev
, p. 3269 - 3279 (2021/03/16)
This work presents three mononuclear Ru(ii) complexes of tridentate phosphine-carboxamide based ligands providing a NNP coordination environment. The octahedral Ru(ii) ion shows additional coordination with co-ligands; CO, Cl and CH3OH. All three Ru(ii) complexes were thoroughly characterized including their crystal structures. These Ru(ii) complexes were utilized as catalysts for the transfer hydrogenation of assorted carbonyl compounds, including some challenging biologically relevant substrates, using isopropanol as the hydrogen source. The binding studies illustrated the coordination of the isopropoxide ion by replacing a Ru-ligated chloride ion followed by the generation of the Ru-H intermediate that was isolated and characterized and was found to be involved in the catalysis.
Pincerlike molybdenum complex and preparation method thereof, catalytic composition and application thereof, and alcohol preparation method
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Paragraph 0134-0140, (2021/08/11)
The invention discloses a clamp-type molybdenum complex, a preparation method, a corresponding catalyst composition and application. The method comprises the steps: obtaining 9 molybdenum complexes with different structures through coordination reaction of 2-(substituent ethyl)-(5, 6, 7, 8-tetrahydroquinolyl) amine and a corresponding carbonyl molybdenum metal precursor; and catalyzing a ketone compound transfer hydrogenation reaction through a molybdenum complex to generate 40 alcohol compounds. The preparation method of the molybdenum complex is simple, high in yield and good in stability. For a transfer hydrogenation reaction of ketone, the molybdenum-based catalytic system has high catalytic activity and small molybdenum loading capacity, is used for production of aromatic and aliphatic alcohols, and has the advantages of simple method, small environmental pollution and high yield.
