106-86-5Relevant academic research and scientific papers
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.
A bulky bis-pocket manganese(V)-oxo corrole complex: Observation of oxygen atom transfer between triply bonded MnV≡O and alkene
Liu, Hai-Yang,Yam, Fei,Xie, Yu-Tao,Li, Xiao-Yuan,Chang, Chi K.
, p. 12890 - 12891 (2009)
(Graph Presented) The highly bulky bis-pocket corrole 5,10,15-tris(2,4,6- triphenylphenyl)corrole (H3TTPPC) has been synthesized. Resonance Raman spectroscopy revealed a triply bonded Mn≡O moiety in its manganese(V)-oxo complex. Direct oxygen atom transfer from (TTPPC)Mn≡O to styrene was confirmed by an 18O-labeling experiment. The (TTPPC)MnIII complex also exhibits significant shape selectivity in the catalytic epoxidation of nonconjugated dienes.
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).
Tris(pyrazolyl)methane molybdenum tricarbonyl complexes as catalyst precursors for olefin epoxidation
Gomes, Ana C.,Neves, Patrícia,Figueiredo, Sónia,Fernandes, José A.,Valente, Anabela A.,Almeida Paz, Filipe A.,Pillinger, Martyn,Lopes, André D.,Gon?alves, Isabel S.
, p. 64 - 76 (2013)
The molybdenum tricarbonyl complexes [Mo(CO)3(HC(3,5-Me 2pz)3)] (1) and [Mo(CO)3(HC(pz)3)] (2) (HC(3,5-Me2pz)3 = tris(3,5-dimethyl-1-pyrazolyl) methane, HC(pz)3 = tris(1-pyrazolyl)methane) were obtained in good yields by the microwave-assisted reaction of Mo(CO)6 with the respective organic ligand. Complete oxidative decarbonylation of 1 and 2 was achieved by reaction with excess tert-butylhydroperoxide (TBHP) in 1,2-dichloroethane at 55 °C. For complex 1, the (μ2-oxo) bis[dioxomolybdenum(VI)] hexamolybdate of composition [{MoO2(HC(3,5- Me2pz)3)}2(μ2-O)][Mo 6O19] (3) was obtained in good yield, and its structure was determined by single crystal X-ray diffraction. The compound (4) obtained by oxidative decarbonylation of 2 was not unambiguously identified, but may be chemically analogous to 3. Compounds 1-4 were examined for the first time as homogeneous (pre)catalysts for the epoxidation of olefins with TBHP, using different types of cosolvents at 55 °C. During the catalytic reactions 1 and 2 transform in situ into 3 and 4, respectively, and the latter two are fairly stable catalysts. Catalytic tests and characterization studies of the recovered catalysts were carried out in an attempt to understand the kinetic differences observed between the compounds prepared in situ during the catalytic reaction and those prepared prior to the catalytic reaction, from the same precursor complex.
A Recoverable Ruthenium Aqua Complex Supported on Silica Particles: An Efficient Epoxidation Catalyst
Ferrer, íngrid,Fontrodona, Xavier,Roig, Anna,Rodríguez, Montserrat,Romero, Isabel
, p. 4096 - 4107 (2017)
The preparation and characterization of complexes with a phosphonated terpyridine (trpy) ligand (trpy-P-Et) and a bidentate pyridylpyrazole (pypz-Me) ligand, with formula [RuII(trpy-P-Et)(pypz-Me)X]n+ (2: X=Cl, n=1; 3: X=H2O, n=2), is described, together with the anchoring of 3 on two types of supports: mesoporous silica particles (SP) and silica-coated magnetic particles (MSP). Aqua complex 3 is easily obtained by heating 2 in refluxing water and exhibits a two-electron RuIV/II redox process. It was anchored on SP and MSP supports by two different synthetic strategies, yielding the heterogeneous systems SP@3 and MSP@3, which were fully characterized by IR and UV/Vis spectroscopy, SEM, cyclic voltammetry, and differential pulse voltammetry. Catalytic olefin epoxidation was tested with molecular complex 3 and its SP@3 and MSP@3 heterogeneous counterparts, including reuse of the heterogeneous systems. The MSP@3 material can be easily recovered by a magnet, which facilitates its reusability.
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 OLEFINS BY HYDROGEN PEROXIDE IN THE PRESENCE OF TETRACHLOROACETONE
Stark, Charles J.
, p. 2089 - 2092 (1981)
1,1,3,3-Tetrachloroacetone, an inexpensive, commercially available material, has been shown to be effective in mediating the hydrogen peroxide oxidation of a variety of olefins to epoxides.The chloroacetone is readily recovered for re-use.
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.
Stereospecific and regioselective catalytic epoxidation of alkenes by a novel ruthenium(II) complex under aerobic conditions
Kesavan, Venkitasamy,Chandrasekaran, Srinivasan
, p. 3115 - 3116 (1997)
Epoxidation of alkenes by molecular oxygen is effected in high yields by catalysis of RuCl2(biox)2 using isobutyraldehyde as the co-reductant: the reaction is stereospecific and regioselective.
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.
