286-99-7Relevant articles and documents
Fe-doped H3PMo12O40 immobilized on covalent organic frameworks (Fe/PMA@COFs): A heterogeneous catalyst for the epoxidation of cyclooctene with H2O2
Yu, Dandan,Gao, Wenxiu,Xing, Shuyu,Lian, Lili,Zhang, Hao,Wang, Xiyue,Lou, Dawei
, p. 4884 - 4891 (2019)
Covalent organic frameworks (COFs) have arisen as one kind of devisable porous organic polymer that has attracted immense attention in catalytic applications. In this work, we prepared cost-effective imine-based COFs (COF-300, COF-LZU1 and CIN-1) via a reaction kettle operated in place of a traditional sealed Pyrex tube. Then, phosphomolybdic acid (PMA) and iron ions were immobilized on the COF supports by impregnation; the resulting frameworks were denoted as Fe/PMA@COFs (Fe/PMA@COF-LZU1, Fe/PMA@CIN-1 and Fe/PMA@COF-300). A series of characterization results demonstrated that the PMA and iron ions were uniformly dispersed on the surface/cavities of the COFs. The catalytic properties of the obtained Fe/PMA@COFs were investigated in the epoxidation of cyclooctene with H2O2 as the oxidant. The experimental results show that the Fe/PMA@CIN-1 composite can act as an efficient heterogeneous catalyst for the epoxidation of cyclooctene. The intramolecular charge transfer between the COFs and the dual sites (PMA and Fe ions), the spatial structure and the nitrogen content of the COFs played critical roles in dispersing and stabilizing the active species, which are closely connected with the activity and stability of the catalysts. A novel efficient heterogeneous catalyst for the epoxidation of olefins via a simple and cost-effective process is provided, and this experiment demonstrates the notable application prospects of the covalent organic skeleton as a catalyst support.
Highly efficient and selective oxidation of various substrates under mild conditions using a lanthanum-containing polyoxometalate as catalyst
Zhao, Shen,Jia, Yueqing,Song, Yu-Fei
, p. 188 - 194 (2013)
A lanthanum-containing polyoxometalate (POM) of DA11[La(PW 11O39)2] (denoted as DA-La(PW 11)2; DA = Decyltrimethylammonium cation) is highly efficient and selective for oxidation of various substrates including alkenes, alkenols, sulfides, silane and alcohol with only one equiv. H2O 2 as oxidant at 25 °C, and the POM catalyst can be easily recovered and reused for ten times without obvious decrease of catalytic activity and the yields for catalyst recovery are all above 95%. The epoxidation of cis-cyclooctene proceeds efficiently in 98% yield with only 0.08 mol% of DA-La(PW11)2, and the turnover number (TON) can reach as high as 1200 at 25 °C.
Catalytic epoxidation of cyclic alkenes with air over CoOx/zeolite heterogeneous catalysts
Ma,Lu,Wei,Zhao,Zhan,Zhou,Xia
, p. 98 - 102 (2015)
The supported CoOx/zeolites have been prepared and applied for the epoxidation of cyclic alkenes with air. The catalysts are characterized by powder X-ray diffraction (XRD), ultraviolet-visible spectroscopy (UV-vis) and scanning electron microscope (SEM). Among these CoOx/zeolite catalysts, 2.4% CoOx/Y exhibits the best catalytic activity for the epoxidation of cis-cyclooctene with 61.2 mol% conversion and 98.8 mol% selectivity of epoxide. Some factors such as the kind of zeolites, the oxidants, the solvents, the Co contents, the reaction temperature and time play important roles in controlling the epoxidation. The recyclable stability of the 2.4% CoOx/Y catalyst is confirmed.
Selective Catalytic Olefin Epoxidation with MnII-Exchanged MOF-5
Stubbs, Amanda W.,Braglia, Luca,Borfecchia, Elisa,Meyer, Randall J.,Román-Leshkov, Yuriy,Lamberti, Carlo,Dincǎ, Mircea
, p. 596 - 601 (2018)
Partial substitution of ZnII by MnII in Zn4O(terephthalate)3 (MOF-5) leads to a distorted all-oxygen ligand field supporting a single MnII site, whose structure was confirmed by Mn K-edge X-ray absorption spectroscopy. The MnII ion at the MOF-5 node engages in redox chemistry with a variety of oxidants. With tBuSO2PhIO, it produces a putative MnIV-oxo intermediate, which upon further reaction with adventitious hydrogen is trapped as a MnIII-OH species. Most intriguingly, the intermediacy of the high-spin MnIV-oxo species is likely responsible for catalytic activity of the MnII-MOF-5 precatalyst, which in the presence of tBuSO2PhIO catalyzes oxygen atom transfer reactivity to form epoxides from cyclic alkenes with >99% selectivity. These results demonstrate that MOF secondary building units serve as competent platforms for accessing terminal high-valent metal-oxo species that consequently engage in catalytic oxygen atom transfer chemistry owing to the relatively weak ligand fields provided by the SBU.
Epoxidation of alkenes through oxygen activation over a bifunctional CuO/Al2O3 catalyst
Scotti, Nicola,Ravasio, Nicoletta,Zaccheria, Federica,Psaro, Rinaldo,Evangelisti, Claudio
, p. 1957 - 1959 (2013)
The epoxidation of alkenes was carried out over a CuO/Al2O 3 catalyst using cumene as an oxygen carrier, through a one-pot reaction, giving high conversion and selectivity with different substrates. Trans-β-methylstyrene gave the corresponding epoxide in 95% yield after 3 h. The Royal Society of Chemistry 2013.
Epoxidation of cycloolefins with hydrogen peroxide in the presence of heteropoly acids combined with phase transfer catalyst
Timofeeva,Pai,Tolstikov,Kustova,Selivanova,Berdnikova,Brylyakov,Shangina,Utkin
, p. 480 - 486 (2003)
Oxidation of cycloolefins (cyclohexene, cyclooctene, and cyclododecene) with a 30% solution of hydrogen peroxide at 65°C in the presence of heteropoly acids (HPA) H3PW12-xMoxO 40 (x = 0-12), which are precursors of active peroxo complexes, and phase transfer catalysts Q+Cl-, where Q+ is the quaternary ammonium cation containing C4-C18 alkyl groups or [C5H5NC16H33] +, was studied. The catalytic activity decreases in the HPA series: H3PW12O40 > H3PW 9Mo3O40 > H3PW6Mo 6O40 > H3PW3Mo9O 40 > H3PMo12O40. The state of the H3PW12O40-H2O2 system was studied using UV, IR, and 31P NMR spectroscopies with variation of the [H2O2]:[HPA] ratio from 2 to 200 during cyclohexene epoxidation. Despite different catalytic precursors, the reaction proceeds through the same peroxo complex.
Lipase catalysed oxidations in a sugar-derived natural deep eutectic solvent
Vagnoni, Martina,Samorì, Chiara,Pirini, Daniele,Vasquez De Paz, Maria Katrina,Gidey, Dawit Gebremichael,Galletti, Paola
, (2021/05/06)
Chemoenzymatic oxidations involving the CAL-B/H2O2 system was developed in a sugar derived Natural Deep Eutectic Solvent (NaDES) composed by a mixture of glucose, fructose and sucrose. Good to excellent conversions of substrates like cyclooctene, limonene, oleic acid and stilbene to their corresponding epoxides, cyclohexanone to its corresponding lactone and 2-phenylacetophenone to its corresponding ester, demonstrate the viability of the sugar NaDES as a reaction medium for epoxidation and Baeyer-Villiger oxidation.
Fast-synthesis and catalytic property of heterogeneous Co-MOF catalysts for the epoxidation of α-pinene with air
Zhang, Haifu,He, Jie,Lu, Xinhuan,Yang, Lu,Wang, Chenlong,Yue, Fanfan,Zhou, Dan,Xia, Qinghua
, p. 17413 - 17421 (2020/11/02)
In the past decades, many methods have been developed for synthesizing MOFs, including solvothermal synthesis, mechanical synthesis, electrochemical synthesis, and microwave synthesis. Based on the existing research, a method is proposed for synthesizing Co-MOF by rapidly rotating hydrothermal crystallization, which largely shortens the crystallization time of Co-MOF. When the rotation speed was 150 rpm, only 2 h of crystallization time was needed to synthesize Co-MOF-150-2 with high crystallinity and stability. The optimal Co-MOF-150-2 manifested remarkable activity and selectivity for the epoxidation of α-pinene under mild conditions. The catalytic conversion of α-pinene reached the highest over the Co-MOF-150-2 catalyst, in which the conversion of α-pinene was 99.5% and the yield of 2,3-epoxypinane was 95.7%. The Co-MOF materials synthesized by the rotary method also had excellent stability and highly catalytic activity in recycling experiments. This journal is
Highly selective and efficient olefin epoxidation with pure inorganic-ligand supported iron catalysts
Zhou, Zhuohong,Dai, Guoyong,Ru, Shi,Yu, Han,Wei, Yongge
supporting information, p. 14201 - 14205 (2019/10/02)
Over the past two decades, there have been major developments in the transition iron-catalyzed selective oxidation of alkenes to epoxides; a common structure found in drug, isolated natural products, and fine chemicals. Many of these approaches have enabled highly efficient and selective epoxidation of alkenes via the design of specialized ligands, which facilitates to control the activity and selectivity of the reactions catalyzed by iron atom. Herein, we report the development of the olefin epoxidation with inorganic-ligand supported iron-catalysts using 30% H2O2 as an oxidant, and the mechanism is similar to iron-porphyrin type. With the catalyst 1, (NH4)3[FeMo6O18(OH)6], various aromatic and aliphatic alkenes were successfully transformed into the corresponding epoxides with excellent yields as well as chemo- and stereo-selectivity. This catalytic system possesses the advantages of being able to avoid the use of expensive, toxic, air/moisture sensitive and commercially unavailable organic ligands. The generality of this methodology is simple to operate and exhibits high catalytic activity as well as excellent stability, which gives it the potential to be used on an industrial scale, and maybe opens a way for the catalytic oxidation reaction via inorganic-ligand coordinated iron catalysis.
Modular Polyoxometalate–Layered Double Hydroxides as Efficient Heterogeneous Sulfoxidation and Epoxidation Catalysts
Li, Tengfei,Zhang, Wei,Chen, Wei,Miras, Haralampos N.,Song, Yu-Fei
, p. 188 - 197 (2017/11/28)
The selective sulfoxidation of sulfides and the epoxidation of olefins are two types of important organic reactions, and the corresponding products of sulfoxides, sulfones and epoxides are used widely as raw materials in industrial processes. The fabrication of one efficient catalyst for both reactions remains a challenging task. We report the preparation of a highly efficient heterogeneous catalyst Mg3Al-ILs-La(PW11)2 using an exfoliation/assembly approach. The catalyst was characterised by FT-IR spectroscopy, XRD, thermogravimetric and differential thermal analysis, BET measurements, X-ray photoelectron spectroscopy, 29Si cross-polarisation magic-angle spinning NMR spectroscopy, 27Al magic-angle spinning NMR spectroscopy, SEM, high-resolution TEM, and energy-dispersive X-ray spectroscopy. The designed catalyst showed a high efficiency and selectivity for the sulfoxidation of sulfides and the epoxidation of olefins under mild conditions at a production rate of 208 and 31 mmol g?1 h?1, respectively. Moreover, Mg3Al-ILs-La(PW11)2 can be recycled and re-used at least five times without a clear decrease of its catalytic activity. The scaled-up experiments revealed that the catalyst retained its efficiency and robustness, which demonstrates the great potential of the catalyst for industrial applications.
