106-86-5Relevant articles and documents
A simple and effective catalytic system for epoxidation of aliphatic terminal alkenes with manganese(II) as the catalyst
Ho, Kam-Piu,Wong, Wing-Leung,Lam, Kin-Ming,Lai, Cheuk-Piu,Chan, Tak Hang,Wong, Kwok-Yin
, p. 7988 - 7996 (2008)
A simple catalytic system that uses commercially available manganese(II) Perchlorate as the catalyst and peracetic acid as the oxidant is found to be very effective in the epoxidation of aliphatic terminal alkenes with high product selectivity at ambient temperature. Many terminal alkenes are epoxidised efficiently on a gram scale in less than an hour to give excellent yields of isolated product (>90%) of epoxides in high purity. Kinetic studies with some C9-alkenes show that the catalytic system is more efficient in epoxidising terminal alkenes than internal alkenes, which is contrary to most commonly known epoxidation systems. The reaction rate for epoxidation decreases in the order: 1-nonene>cis-3-nonene> trans-3-nonene. ESI-MS and EPR spectroscopic studies suggest that the active form of the catalyst is a high-valent oligonuclear manganese species, which probably functions as the oxygen atomtransfer agent in the epoxidation reaction.
Optimisation of alkene epoxidation catalysed by polymer supported Mo(VI) complexes and application of artificial neural network for the prediction of catalytic performances
Mohammed, Misbahu Ladan,Patel, Dipesh,Mbeleck, Rene,Niyogi, Debdarsan,Sherrington, David C.,Saha, Basudeb
, p. 142 - 152 (2013)
A greener and efficient alkene epoxidation process using heterogeneous molybdenum (Mo) based catalysts and tert-butyl hydroperoxide (TBHP) as an oxidant has been developed. A polybenzimidazole supported Mo(VI) complex, i.e. PBI.Mo and polystyrene 2-(aminomethyl) pyridine supported Mo(VI) complex, i.e. Ps.AMP.Mo catalysts have been successfully prepared and characterised. The catalytic activities of the polymer supported Mo(VI) catalysts have been tested for epoxidation of 1-hexene and 4-vinyl-1-cyclohexene in a jacketed stirred batch reactor. Batch experiments have been conducted to study the effect of different types of catalysts, catalyst loading, feed mole ratio (FMR) of alkene to TBHP and reaction temperature on the yield of epoxide for both alkenes, i.e. 1-hexene and 4-vinyl-1-cyclohexene. The long-term stability of PBI.Mo and Ps.AMP.Mo catalysts has been evaluated by recycling the catalyst several times for batch experiments using conditions that will form the basis of a continuous epoxidation process. The extent of Mo leaching from each polymer supported catalyst has been investigated by isolating any residue from reaction supernatant solutions after the removal of the heterogeneous catalyst and using the residue as potential catalyst for epoxidation. An artificial neural network (ANN) model has been employed to predict the catalytic performance of PBI.Mo and Ps.AMP.Mo catalysts for all batch experimental results. The ANN predicted values are in good agreement with the batch experimental results. The results obtained from batch experiments and ANN modelling provided useful information for conducting continuous epoxidation experiments in multi-functional reactors such as FlowSyn and reactive distillation column (RDC).
Hydrotalcite-catalyzed epoxidation of olefins using hydrogen peroxide and amide compounds
Yamaguchi, Kazuya,Ebitani, Kohki,Kaneda, Kiyotomi
, p. 2966 - 2968 (1999)
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Indictor,Brill
, p. 2074,2075 (1965)
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Efficient, regioselective epoxidation of dienes with hydrogen peroxide catalyzed by [γ-SiW10O34(H2O) 2]4-
Kamata, Keigo,Nakagawa, Yoshinao,Yamaguchi, Kazuya,Mizuno, Noritaka
, p. 224 - 228 (2004)
A divacant, lacunary, Keggin-type silicotungstate, [γ-SiW 10O34(H2O)2]4-, exhibits high catalytic performance for the epoxidation of various nonconjugated dienes using hydrogen peroxide under mild conditions, high regioselectivity to the more accessible double bonds, and high efficiency of hydrogen peroxide utilization. The high regioselectivity for the [γ-SiW10O34(H 2O)2]4--catalyzed epoxidation would be caused by the steric hindrance of the active site.
Epoxidation of allyl chloride to epichlorohydrin by a reversible supported catalyst with H2O2 under solvent-free conditions
Li, Jun,Zhao, Gongda,Gao, Shuang,Lv, Ying,Li, Jian,Xi, Zuwei
, p. 876 - 880 (2006)
Allyl chloride was epoxidized to epichlorohydrin with H2O 2 under solvent-free conditions in 94% selectivity using a new reversible supported catalyst, heteropolyphosphatotungstate/silanized silica gel. By the action of H2O2 the heteropolyphosphatotungstate dissolves from the carrier surface and forms an active homogeneous reagent. When all H2O2 is consumed, the reduced catalyst redeposits on the support carrier. The supported catalyst retains the character of a homogeneous catalyst during reaction but exhibits heterogeneous properties upon work-up. The solid-supported catalyst is easily isolated and can be reused. The reaction system for synthesis of epichlorohydrin therefore avoids the serious pollution issues known from the commercialized chlorohydrin methods. Some other olefins can also be epoxidized by this catalytic system under neat conditions.
Synthesis of epoxides catalyzed by a halide-free reaction-controlled phase-transfer catalytic system: [(CH3(CH2) 17)2N(CH3)2]3[PW 4O32]/H2O2/Dioxan/Olefin
Ding, Yong,Ma, Baochun,Tong, Dejie,Hua, Hui,Zhao, Wei
, p. 739 - 746 (2009)
The epoxidation of alkenes was successfully catalyzed by a recyclable catalytic system: [(CH3(CH2)17) 2N(CH3)2]3[PW4O 32]/H2O2/dioxan/olefin. This new catalytic system is not only capable of catalyzing homogeneous epoxidation of alkenes with a unique reaction-controlled phase-transfer character, but also avoids the use of chlorinated solvents. The reactions were conducted in a biphasic mixture of aqueous H2O2/dioxan, and many kinds of alkenes could be efficiently converted to the corresponding epoxides in high yields. Both new and used [(CH3(CH2)17)2N(CH 3)2]3[PW4O32] catalyst was characterized by 31P magic angle spin NMR, and IR. CSIRO 2009.
New aqua N-heterocyclic carbene Ru(II) complexes with two-electron process as selective epoxidation catalysts: An evaluation of geometrical and electronic effects
Dakkach, Mohamed,Atlamsani, Ahmed,Parella, Teodor,Fontrodona, Xavier,Romero, Isabel,Rodriguez, Montserrat
, p. 5077 - 5087 (2013)
New ruthenium complexes with general formula [RuII(T)(CN-Me)X] n+ (X = Cl- or H2O; T = 2,2′:6′, 2″-terpyridine, trpy, or N,N-bis(2-pyridyl)ethylamine, bpea; CN-Me = N-methyl-N′-2-pyridylimidazolium) have been prepared. The complexes obtained have been characterized in solution by spectroscopic (1D- and 2D-NMR and UV-vis) techniques, mass spectrometry, and elemental analysis. The chloro complexes have also been characterized by X-ray diffraction analysis. The redox properties of all the compounds were studied by CV revealing, for the reported Ru-OH2 complexes, bielectronic Ru(IV/II) redox processes throughout a wide pH range. The catalytic activity of aquo complexes was evaluated in the epoxidation of olefins using PhIO as oxidant, displaying in general good yields and high selectivities for the epoxide product. The influence of electronic and geometrical factors on the spectroscopic and electrochemical properties as well as on the catalytic activity is discussed.
Highly selective epoxidation of cycloaliphatic alkenes with aqueous hydrogen peroxide catalyzed by [PO4{WO(O2) 2}4]3-/imidazole
Kamata, Keigo,Sugahara, Kosei,Ishimoto, Ryo,Nojima, Susumu,Okazaki, Motoya,Matsumoto, Takaya,Mizuno, Noritaka
, p. 2327 - 2332 (2014)
In the presence of imidazole as an additive, a phosphorus-containing tetranuclear peroxotungstate, THA3[PO4{WO(O 2)2}4] (I, THA=tetra-n-hexylammonium), could act as an efficient catalyst for epoxidation of cycloaliphatic alkenes with 30% aqueous hydrogen peroxide (H2O2). Compound I showed higher catalytic activity and selectivity to epoxide than other tungstates. By using the I/imidazole system, various kinds of cycloaliphatic alkenes could be highly selectively converted into the acid-sensitive epoxides including industrially important diepoxides in high to excellent yields under the almost stoichiometric conditions. The 1H NMR spectroscopy showed that imidazole would work not only as a proton acceptor but also as a Lewis base to remarkably suppress the acid-catalyzed ring opening of epoxides.
A Ruthenium(II) Aqua Complex as Efficient Chemical and Photochemical Catalyst for Alkene and Alcohol Oxidation
Manrique, Ester,Fontrodona, Xavier,Rodríguez, Montserrat,Romero, Isabel
, p. 2124 - 2133 (2019)
Different synthetic routes have been developed to obtain the aqua complex trans-[RuII(trpy)(pypz-H)(OH2)](PF6)2, Ru6. This complex, together with the chlorido intermediate complexes cis- and trans-[RuIICl(pypz-H)(trpy)]+, Ru5a and Ru5b, have been fully characterized by analytical, spectroscopic, and electrochemical methods. Furthermore, the trans-Ru5b complex has been characterized in the solid state through single-crystal X-ray diffraction analysis. The aqua complex Ru6 was tested as catalyst in the photooxidation of alcohols in water and in the chemical oxidation of alkenes, displaying a good performance with high selectivity values in both catalytic processes.
A novel carbene ruthenium complex as reusable and selective two-electron catalyst for alkene epoxidation
Dakkach, Mohamed,Fontrodona, Xavier,Parella, Teodor,Atlamsani, Ahmed,Romero, Isabel,Rodriguez, Montserrat
, p. 231 - 238 (2011)
A new ruthenium aquo catalyst with the formula trans-[Ru(II)(CN-Me)(trpy) OH2](PF6)2 [where trpy=2,2a:6′,2″- terpyridine and CN-Me=3-methyl-1-(pyridin-2-yl)-imidazolylidene] has been prepared and thoroughly characterized by spectroscopic and electrochemical techniques. The complex has been tested in epoxidation catalysis both in dichloromethane and dichloromethane:ionic liquid media, displaying excellent performances and selectivities. Reuse of the catalyst in ionic liquid:solvent media has been explored for the first time in ruthenium-mediated epoxidation catalysis and its performance is fully maintained for up to ten runs.
A broad substrate-scope method for fast, efficient and selective hydrogen peroxide-epoxidation
Garcia-Bosch, Isaac,Ribas, Xavi,Costas, Miquel
, p. 348 - 352 (2009)
The efficient epoxidation of a broad range of olefins using hydrogen peroxide (H2O2) as the oxidant has been accomplished by a manganese catalyst that exhibits an uncommon chemoselectivity.
A stand-alone cobalt bis(dicarbollide) photoredox catalyst epoxidates alkenes in water at extremely low catalyst load
Guerrero, Isabel,Romero, Isabel,Teixidor, Francesc,Vi?as, Clara
supporting information, p. 10123 - 10131 (2021/12/27)
The cobalt bis(dicarbollide) complex, Na[3,3′-Co(η5-1,2-C2B9H11) (Na[1]), is an effective photoredox catalyst for the oxidation of alkenes to epoxides in water. Advantageous features of Na[1] include its lack of photoluminescence, high solubility and surfactant behavior in aqueous media, as well as the donor ability of the carborane ligand and high oxidizing power of the Co4+/3+ couple. These features differentiate it from the well-known and widely used photosensitizer tris (2,2′-bipyridine) ruthenium(ii) ([Ru(bpy)3]2+), which also participates in electron transfer through an outer sphere mechanism. A comparison of the catalytic performance of [Ru(bpy)3]2+ with Na[1] for alkene photo-oxidation is fully in favor of Na[1], as the former shows very low or null efficiency. With a catalyst loading of 0.1 mol% conversions between 65-97% have been obtained in short reaction times, 15 minutes, with moderate selectivity for the corresponding epoxide, due to the formation of side products as diols. But when the catalyst loading is reduced to 0.01 mol%, the selectivity for the corresponding epoxide increased considerably, being the only compound formed after 15 minutes of reaction (selectivity >99%). High TON values have been obtained (TON = 8500) for the epoxidation of aromatic and aliphatic alkenes in water. We have verified that Na[3,3′-Co(η5-1,2-C2B9H11)2] acts as a photocatalyst in both the epoxidation of alkenes and in their hydroxylation in aqueous medium with a higher rate for epoxidation than for hydroxylation. Preliminary photooxidation tests using methyl oleate as the substrate led to the selective epoxidation of the double bond. These results represent a promising starting point for the development of practical methods for the processing of unsaturated fatty acids, such as the valorisation of animal fat waste using this sustainable photoredox catalyst. This journal is
1,2-epoxy-4-vinylcyclohexane and preparation method thereof
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Paragraph 0027-0068, (2018/06/26)
The invention relates to 1,2-epoxy-4-vinylcyclohexane. 1,2-epoxy-4-vinylcyclohexane is prepared from the following raw materials in percentage by mass: 12%-14% of 4-vinyl-1-cyclohexene, 40%-45% of toluene, 17%-19% of acetic anhydride, 2%-4% of sodium acetate and 21%-23% of 35% hydrogen peroxide. The invention further relates to a preparation method of 1,2-epoxy-4-vinylcyclohexane. Prepared 1,2-epoxy-4-vinylcyclohexane has high yield and selectivity, and purity of a reaction product is improved; besides, 1,2-epoxy-4-vinylcyclohexane has low chlorine content and has no heavy metal residues, andgelation time of the product is short.
