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).
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.
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
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Barnard,Hargrave
, p. 476,480 (1951)
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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.
Structure and Catalytic Properties of Copper with ANKB-2 Ampholyte in the Reaction of Oxidation of Cyclohexene
Kokorin, A. I.,Berentzveig, V. V.
, p. 1537 - 1540 (1988)
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{[Co2(btec)(2,2′-bipy)2]·H 2O}n metal-organic framework: Structure and activity in the solvent-free oxidation of cyclohexene with oxygen
Hao, Jianmin,Li, Sijia,Han, Limin,Cheng, Lin,Suo, Quanling,Xiao, Yang,Jiao, Xiaoli,Feng, Xuemin,Bai, Weiwei,Song, Xiaofei
, p. 246 - 254 (2014)
A Co (II) metal-organic framework (MOF) {[Co2(btec)(2,2′- bipy)2]·H2O}n (H4btec: 1,2,4,5-benzenetetracarboxylic acid; 2,2′-bipy: 2,2′-bipyridine) was hydrothermally synthesized and characterized using X-ray crystallographic analysis, Fourier transform infrared spectroscopy, elemental analysis, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and N2 adsorption/desorption. Its catalytic performance was examined for the allylic oxidation of cyclohexene with oxygen under solvent-free conditions. It acted as a heterogeneous catalyst, which was deactivated in catalyst recycling and regenerated through treatment with a scCO2-expanded ethanol system. The inhibitive effect of H4btec and other ligands on cyclohexene oxidation was detected, presumed to be caused by hydrogen-bonding interaction between the H4btec and a 2-cyclohexene-1-hydroperoxide intermediate.
Catalytic Performance of Zr-Based Metal–Organic Frameworks Zr-abtc and MIP-200 in Selective Oxidations with H2O2
Maksimchuk, Nataliya V.,Ivanchikova, Irina D.,Cho, Kyung Ho,Zalomaeva, Olga V.,Evtushok, Vasiliy Yu.,Larionov, Kirill P.,Glazneva, Tatiana S.,Chang, Jong-San,Kholdeeva, Oxana A.
supporting information, p. 6985 - 6992 (2021/03/17)
The catalytic performance of Zr-abtc and MIP-200 metal–organic frameworks consisting of 8-connected Zr6 clusters and tetratopic linkers was investigated in H2O2-based selective oxidations and compared with that of 12-coordinated UiO-66 and UiO-67. Zr-abtc demonstrated advantages in both substrate conversion and product selectivity for epoxidation of electron-deficient C=C bonds in α,β-unsaturated ketones. The significant predominance of 1,2-epoxide in carvone epoxidation, coupled with high sulfone selectivity in thioether oxidation, points to a nucleophilic oxidation mechanism over Zr-abtc. The superior catalytic performance in the epoxidation of unsaturated ketones correlates with a larger amount of weak basic sites in Zr-abtc. Electrophilic activation of H2O2 can also be realized, as evidenced by the high activity of Zr-abtc in epoxidation of the electron-rich C=C bond in caryophyllene. XRD and FTIR studies confirmed the retention of the Zr-abtc structure after the catalysis. The low activity of MIP-200 in H2O2-based oxidations is most likely related to its specific hydrophilicity, which disfavors adsorption of organic substrates and H2O2.
Preparation method of allyl peroxide
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Paragraph 0046-0050, (2020/06/09)
The invention provides a preparation method of allyl peroxide, which comprises the step of reacting an allyl compound in a solvent under the action of nitrogen oxide, a metal catalyst and an oxidant to obtain the allyl peroxide. The method provided by the
