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.
Organocatalytic epoxidation and allylic oxidation of alkenes by molecular oxygen
Orfanidou, Maria,Petsi, Marina,Zografos, Alexandros L.
supporting information, p. 9172 - 9178 (2021/11/30)
Pyrrole-proline diketopiperazine (DKP) acts as an efficient mediator for the reduction of dioxygen by Hantzsch ester under mild conditions to allow the aerobic metal-free epoxidation of electron-rich alkenes. Mechanistic crossovers are underlined, explaining the dual role of Hantzsch ester as a reductant/promoter of the DKP catalyst and a simultaneous competitor for the epoxidation of alkenes when HFIP is used as a solvent. Expansion of this protocol to the synthesis of allylic alcohols was achieved by adding a catalytic amount of selenium dioxide as an additive, revealing a superior method to the classical application of t-BuOOH as a selenium dioxide oxidant.
Selective cyclohexene oxidation with O2, H2O2and: Tert -butyl hydroperoxide over spray-flame synthesized LaCo1- x Fex O3nanoparticles
Alkan, Baris,Büker, Julia,Falk, Tobias,Fu, Qi,Muhler, Martin,Peng, Baoxiang,Schulwitz, Jonas,Schulz, Christof,Waffel, Daniel,Wiggers, Hartmut,Xia, Wei
, p. 5196 - 5206 (2020/08/19)
The elimination of waste and by-product generation and reduced dependence on hazardous chemicals are the key steps towards environmentally sustainable chemical transformations. Heterogeneously catalysed oxidation of cyclohexene with environmentally friendly oxidizing agents such as O2, H2O2 and tert-butyl hydroperoxide (TBHP) has great potential to replace existing processes using stoichiometric oxidants. A series of spray-flame synthesised nanoparticulate LaCo1-xFexO3 catalysts was employed for cyclohexene oxidation, and the comparative results showed that TBHP led to the highest initial activity and allylic selectivity, but O2 resulted in higher conversion for longer reaction times. Furthermore, the influence of Fe substitution was studied, which did not show any beneficial synergistic effects. LaCoO3 was found to be the optimum catalyst for cyclohexene oxidation with O2, following first-order reaction kinetics with an apparent activation energy of 57 kJ mol-1. The catalyst showed good reusability due to its highly stable particle size, morphology and perovskite structure. 7-Oxabicyclo[4.1.0]heptan-2-one was identified to be formed by the oxidation of 2-cyclohexene-1-one with 2-cyclohexene-1-hydroperoxide.
