4845-05-0Relevant articles and documents
A General Route to Dioxabicycloalkanes
Bloodworth, A. J.,Eggelte, Henny J.
, p. 865 - 866 (1982)
6,7-Dioxabicyclooctane has been prepared from its cis-8-bromo derivative by reduction with tributyltin hydride generated in situ from bis(tributyltin) oxide and polymethylhydrogen siloxane; analogous reactions have afforded 7,8-diozabicyclon
Mixed-Metal Strategy on Metal-Organic Frameworks (MOFs) for Functionalities Expansion: Co Substitution Induces Aerobic Oxidation of Cyclohexene over Inactive Ni-MOF-74
Sun, Dengrong,Sun, Fangxiang,Deng, Xiaoyu,Li, Zhaohui
, p. 8639 - 8643 (2015)
Different amounts of Co-substituted Ni-MOF-74 have been prepared via a post-synthetic metal exchange. Inductively coupled plasma mass spectrometry, powder X-ray diffraction (XRD), N2 adsorption/desorption, and extended X-ray absorption fine structure (EXAFS) analyses indicated the successful metathesis between Co and Ni in Ni-MOF-74 to form the solid-solution-like mixed-metal Co/Ni-MOF-74. It was found that introduction of active Co into the Ni-MOF-74 framework enabled the inert Ni-MOF-74 to show activity for cyclohexene oxidation. Since Co was favorably substituted at positions more accessible to the substrate, the mixed-metal Co/Ni-MOF-74 showed superior catalytic performance, compared with pure Co-MOF-74 containing a similar amount of Co. This study provides a facile method to develop solid-solution-like MOFs for heterogeneous catalysis and highlights the great potential of this mixed-metal strategy in the development of MOFs with specific endowed functionalities. (Chemical Equation Presented).
Facile Synthesis of CuO–Ni/Al Composites for Catalytic Oxidation of Cyclohexene
Ma, Ang,Cheng, YangYang,Bai, Yijia,Hao, Jianmin,Chu, Fumin,Han, Limin,Zhou, Huacong
, p. 1337 - 1344 (2019)
CuO–Ni/Al composites were synthesized by electroless deposition and thermal oxidation and characterized by inductively coupled plasma optical emission spectrometry, X-ray powder diffraction, scanning electron microscopy and X-ray photoelectron spectroscopy. Their performances as the heterogeneous catalysts for the solvent-free allylic oxidation of cyclohexene by oxygen were determined. It was found that the CuO contents and the amount of adsorbed oxygen species on the composites could significantly affect their catalytic performances in cyclohexene oxidation. The highest catalytic activity was achieved over CuO–Ni/Al-3 containing 18.5?wt% CuO with the highest amount of adsorbed oxygen species, which resulted in the maximum cyclohexene conversion of 39.1% and the total selectivity of 85.5% to 2-cyclohexene-1-ol, 2-cyclohexene-1-one, 2-cyclohexene-1-hydroperoxide and cyclohexene oxide. In addition, the catalyst was successfully recycled with no significant catalytic activity loss after three cycles. Graphical Abstract: [Figure not available: see fulltext.].
Selective Hydroperoxygenation of Olefins Realized by a Coinage Multimetallic 1-Nanometer Catalyst
Kambe, Tetsuya,Moriai, Tatsuya,Tanabe, Makoto,Tsukamoto, Takamasa,Yamamoto, Kimihisa
, p. 23051 - 23055 (2020)
The science of particles on a sub-nanometer (ca. 1 nm) scale has attracted worldwide attention. However, it has remained unexplored because of the technical difficulty in the precise synthesis of sub-nanoparticles (SNPs). We recently developed the “atom-hybridization method (AHM)” for the precise synthesis of SNPs by using a suitably designed macromolecule as a template. We have now investigated the chemical reactivity of alloy SNPs obtained by the AHM. Focusing on the coinage metal elements, we systematically evaluated the oxidation reaction of an olefin catalyzed by these SNPs. The SNPs showed high catalytic performance even under milder conditions than those used with conventional catalysts. Additionally, the hybridization of multiple elements enhanced the turnover frequency and the selectivity for the formation of the hydroperoxide derivative. We discuss the unique quantum-sized catalysts providing generally unstable hydroperoxides from the viewpoint of the miniaturization and hybridization of materials.
Perfluorocarbons as novel reaction media for photooxidation reactions
Chambers, Richard D.,Sandford, Graham,Shah, Aneela
, p. 1861 - 1866 (1996)
Perfluorocarbons are excellent alternatives to chlorinated solvents as non-toxic, non-ozone-depleting, inert reaction media for photooxidation reactions. Essentially quantitative yields of peroxide products are obtained and the perfluorocarbon solvents ar
Establishing a Au nanoparticle size effect in the oxidation of cyclohexene using gradually changing Au catalysts
Donoeva, Baira G.,Ovoshchnikov, Daniil S.,Golovko, Vladimir B.
, p. 2986 - 2991 (2013)
The effect of the size of gold nanoparticles on their catalytic activity in aerobic oxidation of cyclohexene was established using supported gold nanoparticles that gradually undergo a change in size during the catalytic reaction. Two triphenylphosphine-s
The N-Hydroxyphthalimide catalyzed oxidation of cyclohexene to cyclohexenyl hydroperoxide: Reasons for deactivation and stability of the catalyst
Kuznetsova,Kuznetsova,Yakovina,Babushkin,Bal'zhinimaev
, p. 84 - 88 (2018)
Selective oxidation of cyclohexene to cyclohexenyl hydroperoxide catalyzed by N-hydroxyphthalimide (NHPI) was studied. Kinetic observations and 13C and 1H NMR spectroscopy showed that accumulation of cyclohexenyl hydroperoxide was ac
L-Proline derived mimics of the non-haem iron active site catalyse allylic oxidation in acetonitrile solutions
Dungan, Victoria J.,Poon, Belinda M.-L.,Barrett, Elizabeth S.,Rutledge, Peter J.
, p. 1236 - 1238 (2013)
Non-haem iron complexes are important reagents for the oxidative functionalisation of C-H bonds. Peptidomimetic ligands derived from l-proline, pyridine-2,6-dimethanol and pyridine-2,6-dicarboxylic acid have been combined with iron(II) triflate and hydrogen peroxide in acetonitrile. The resulting complexes convert cyclohexene into the allylic oxidation products, 2-cyclohexen-1-ol, 2-cyclohexen-1-one and 2-cyclohexenyl hydroperoxide in high turnover yields. A mechanism for product formation is proposed, in which the hydroperoxy radical (HOO) is the active oxidant.
A study of photooxygenation of cycloalkenes under 2,4,6-triphenylpyrylium tetrafluoroborate sensitization
Sridhar, Madabhushi,Kumar, Butty Ashok
, p. 461 - 462 (1998)
2,4,6-Triphenylpyrylium tetrafluoroborate sensitized oxygenation of cycloalkenes to allylic hydroperoxides is described. This reaction appears to involve unusual electron transfer mechanism in the formation of observed products.
Synthesis of Cu Single Atoms Supported on Mesoporous Graphitic Carbon Nitride and Their Application in Liquid-Phase Aerobic Oxidation of Cyclohexene
Büker, Julia,Bitzer, Johannes,Huang, Xiubing,Kleist, Wolfgang,Muhler, Martin,Peng, Baoxiang
, p. 7863 - 7875 (2021)
Different loadings of Cu single atoms were anchored on a graphitic carbon nitride (g-C3N4) matrix using a two-step thermal synthesis method and applied in liquid-phase cyclohexene oxidation under mild conditions using molecular O2 as the oxidizing agent. The oxidation state of Cu was determined to be Cu+, which is in linear coordination with two neighboring nitrogen atoms at a distance of 1.9 ?. The catalyst with 0.9 wt % Cu pyrolyzed at 380 °C was found to exhibit the best catalytic performance with the highest conversion up to 82% with an allylic selectivity of 55%. It also showed high reusability over four catalytic runs without any detectable Cu leaching. Cyclohexene oxidation followed first-order kinetics with an apparent activation energy of 66.2 kJ mol-1. The addition of hydroquinone as a radical scavenger confirmed that cyclohexene oxidation proceeds via a radical mechanism. Time-resolved in situ attenuated total reflection infrared (ATR-IR) spectroscopy was carried out to qualitatively monitor the cyclohexene oxidation pathways. The comparison with the homogeneous analogue Cu(I) iodide indirectly verified the linearly N-coordinated single Cu(I) species to be the active sites for cyclohexene oxidation.
