Synthesis and catalytic activity of binuclear Mn(III,III)–BINOL complexes for epoxidation of olefins

The novel binuclear complexes [Mn₂^{(III, III)}(BINOL)₃L₂]2H₂O, where, L = 2, 2′‐bipyridine (Bpy) or 1,10‐phenanthroline (Phen) and BINOL = 1, 1′‐bi‐2‐naphthol were synthesized and characterized by elemental analyses, magnetic susceptibility and various spectral methods. The catalytic activity of these complexes was studied for the epoxidation reaction of unfunctionalized olefins like styrene, 1‐hexene, 1‐octene and 1‐decene. The products thus obtained were analyzed by GC. The epoxidation reactions were carried out, in the presence of catalyst with different oxidants, to study the effect of the nature of the oxidant on the reactions. The different oxidants used were the peroxide oxygen donor (e.g. TBHP and H₂O₂), mono oxygen donor (e.g. PhIO) and dioxygen donor (e.g. molecular O₂). TBHP was found to be the best oxidant for the epoxidation reaction. To study the effect of the solvent on the epoxidation, the reactions were carried out in different media, such as a polar media (e.g. with CH₃OH as solvent), non‐polar media (e.g. with CH₂Cl₂ and C₆H₆ as solvents) and coordinating solvent (e.g. CH₃CN). The maximum epoxide formation was observed in CH₂Cl₂ medium. The epoxidation reactions with optically active BINOL catalysts under optimum established conditions were carried out to examine the enantioselectivity of the catalysts. The complexes were, however, found not to be enantioselective. Copyright © 2006 John Wiley & Sons, Ltd.     

Use of solvents in the low-pressure plasma oxidation of olefins

The oxidation ofn-octene has been studied in mixtures with dimethylbutane, 1,4-dimethylcyclohexane, ethylcyclohexane, and dibutyl ether. Except for dimethylbutane, total yields increase on addition of a solvent, and the fraction of epoxide among the products is higher than in reactions with neat octene.     

Nickel Boride Catalysts in Organic Synthesis (IV). The Effect of Water Washing on P-2 Nickel Boride Catalyst

Water washing of P-2 nickel boride brings about a new catalyst designated as P-2W nickel boride. This P-2W catalyst is more reactive than P-1 or P-2 in the hydrogenation of cyclohexanone and nitrobenzene. The P-2W, however, is less selective than P-2 in the hydrogenation of cyclic olefins.     

Catechol‐Functionalized Polyolefins

The incorporation of comonomers during ethylene polymerization can efficiently modulate important material properties of the polyolefins. Utilizing bioresourced comonomers for the generation of high‐performance polyolefin materials is attractive from a sustainability point of view. In this contribution, bioresourced eugenol and related comonomers were incorporated into polyolefins through palladium‐catalyzed copolymerization and terpolymerization reactions. Importantly, high‐molecular‐weight catechol‐functionalized polyolefins can be generated. The introduction of different metal ions induces efficient interactions with the incorporated catechol groups, leading to enhanced mechanical properties and self‐healing properties. Moreover, the catechol functionality can greatly improve other properties such as surface properties, adhesion properties, and compatibilizing properties. The catechol‐functionalized polyolefin was demonstrated as a versatile platform polymer for accessing various materials with dramatically different properties.     

氮气吹扫和费托合成的脉冲过程以提高α-烯烃的选择性

费托合成可以将煤炭或者生物质气化得到的合成气转化为α-烯烃等重要的化工产品。研究将费托合成和氮气吹扫操作组合成一脉冲过程,在稳定的操作状态下保证费托合成和氮气吹扫交替进行。在传统的费托合成条件下(反应气速为2 000 h^-1,温度为497 K, 压力为 2.0 MPa, 氢碳体积比为2.0)考察了Fe-Co催化剂在脉冲过程中费托合成的活性和选择性。结果表明,N₂吹扫温度和压力分别为517 K和0.2 MPa下的费托合成的C₃烯烷比是未脉冲的相同反应条件下的九倍左右。同时,反应过程中CH₄的选择性和CO的转化率有所下降。在此基础上,通过间歇反应在固定床反应器中进行该脉冲过程,实验结果表明,利用脉冲操作在费托反应中可以获得更高的烯烃选择性。     

Catalytic Asymmetric Bromination of Unfunctionalized Olefins with H2O as a Nucleophile

The dimeric cinchona alkaloid (DHQD)₂PHAL is used to catalyze an effective asymmetric bromohydroxylation of unfunctionalized olefins with H₂O as nucleophile an N‐bromobenzamide as a bromine source. A variety of optically active bromohydrins are formed with up to 88 % ee.     

A comparative study on the catalytic performance of heme and non‐heme catalysts: Metal porphyrins versus metal Schiff bases

Catalytic activity and oxidative stability of a series of iron and manganese porphyrins with 2‐chlorophenyl, phenyl and 4‐methoxyphenyl at the meso positions and metallosalens (Mn‐ and Fe‐salens) including N,N′‐bis(salicylidene)ethylenediamine, N,N′‐bis(5‐ chlorosalicylidene)ethylenediamine and N,N′‐bis(2,4‐dihydroxysalicylidene)ethylenediamine for the oxidation of olefins with tetra‐n‐butylammonium periodate (TBAP) and tetra‐n‐butyl‐ammonium Oxone (TBAO) have been investigated and compared. Although the metalloporphyrins showed an increased catalytic activity relative to the Schiff base complexes, the former provided no significant catalytic advantage over the latter. Also, a comparable or slightly higher oxidative stability was observed for the Schiff base complexes under the reaction conditions. Furthermore, in spite of large difference between the oxidizing ability of TBAO and TBAP, similar patterns were observed for the order of catalytic activity and oxidative stability of the used heme and non‐heme catalysts. The introduction of a methyl group at the ɑ position of styrene led to an increase in its reactivity, indicating the dominance of electronic effects over the steric ones in these catalytic systems.     

Hydroformylation of methyl-3-pentenoate over a phosphite ligand modified Rh/SiO2 catalyst

A phosphite ligand modified Rh/SiO2 catalyst has been developed for hydroformylation of internal olefins to linear aldehydes, which showed high activity and regioselectivity and could be separated easily by filtration after reaction in an autoclave. Effects of reaction temperature and syngas pressure on the performances of the catalyst in the reaction were also investigated.