Simulation of the reaction front propagation during co oxidation on Pt (100) under unsteady-state conditions

Acid tetrabutylammonium salts of Ti(IV)-monosubstituted heteropolytungstate, PW₁₁TiO₄₀ ⁵⁻, show high catalytic acitivity in the oxidation of methyl phenyl sulfide with hydrogen peroxide, while the corresponding tetrabutylammonium salts containing no protons are poor catalysts for this reaction.     

Bromination Products of 2‐Substituted 5,7‐Dimethoxy‐4‐Naphthols

Bromination in acetic acid is favored at C‐8 in 5,7‐dimethoxy‐4‐naphthol when the C‐2 substituent is methyl carboxylate, whereas C‐1 is favored when the C‐2 substituent is either acetoxymethylene or methyl.     

Experimental survey of the kinetics of acene Diels–Alder reactions

Second‐order rate constants were gathered for solution Diels–Alder reactions of substituted and unsubstituted acenes, with the intention of ascertaining ideal diene–dienophile combinations. Particular focus was placed on the larger ring systems namely tetracene, pentacene, and rubrene. The rate constants between the acenes ranged roughly six orders of magnitude, from the slowest reacting diene, rubrene, to the fastest diene, pentacene. The utilized dienophiles covered a large range of reactivity from 2,3‐dichloromaleic anhydride to tetracyanoethylene. To aid in the interpretation of acene reactivity, constants were compared to the extensive body of Diels–Alder literature with well‐studied dienes such as anthracene and trans‐1‐methoxy‐1,3‐butadiene serving as points of reference. Complex reaction kinetics for the addition of MeTAD and rubrene was found: initial fast consumption generated an intermediate, followed by dramatically slower product formation. The kinetic data creates a foundation for the analysis of prior and future reactions between organic semiconductor acene materials with volatized dienophiles, a surface functionalization technique for enhancing these electronic materials. Copyright © 2015 John Wiley & Sons, Ltd.     

α-Al2O3的性质对负载钯催化剂催化CO偶联反应的影响

 以不同来源的 α-Al2O3 为载体制备了用于催化CO偶联制草酸二甲酯反应的Pd/α-Al2O3 催化剂,利用X射线衍射、 N2吸附和X射线能谱等手段对载体进行了表征. 结果表明,催化剂活性与载体的比表面积没有必然联系,但依赖于载体孔容及孔径的分布范围. 同时 α-Al2O3 的纯度和杂质种类对催化剂活性也有影响,少量钠氧化物和 γ-Al2O3 的存在会大大降低催化剂的活性. 此外,利用CO化学吸附法分析了催化剂活性组分的分布情况. 结果表明,催化剂表面活性金属Pd的分散度达到3.94%以上时,分散度的进一步增大对CO偶联反应没有明显影响.     

Application of multifunctional initiation system in block copolymerization of ethylene oxide and methyl methacrylate

A block copolymer composed of hydrophilic and crystallinic polyethylene oxide and hydrophobic and non-crystallinic polymethyl methacrylate (PMMA) was prepared by sequential initiation of alkoxy-anion and charge transfer complex using p-aminophenol as parent compound. The structure of copolymer was characterized by GPC, IR, 1H NMR and DSC in detail. The propagation of PMMA chain is dependent on the molecular weight and concentration of the first block PEO and also the polarity of solvents. The reasons are discussed.     

A twofold interpenetrating three‐dimensional CdII coordination framework: poly[[μ2‐1,3‐bis(2‐methyl‐1H‐imidazol‐1‐yl)benzene](μ3‐5‐nitrobenzene‐1,3‐dicarboxylato)cadmium(II)]

A twofold interpenetrating three‐dimensional Cd^II coordination framework, [Cd(C₈H₃NO₆)(C₁₄H₁₄N₄)]_n, has been prepared and characterized by IR spectroscopy, elemental analysis, thermal analysis and single‐crystal X‐ray diffraction. The asymmetric unit consists of a divalent Cd^II atom, one 1,3‐bis(2‐methyl‐1H‐imidazol‐1‐yl)benzene (1,3‐BMIB) ligand and one fully deprotonated 5‐nitrobenzene‐1,3‐dicarboxylate (NO₂‐BDC²⁻) ligand. The coordination sphere of the Cd^II atom consists of five O‐donor atoms from three different NO₂‐BDC²⁻ ligands and two imidazole N‐donor atoms from two different 1,3‐BMIB ligands, forming a distorted {CdN₂O₅} pentagonal bipyramid. The NO₂‐BDC ligand links three Cd^II atoms via a μ₁‐η¹:η¹ chelating mode and a μ₂‐η²:η¹ bridging mode. The title compound is a twofold interpenetrating 3,5‐connected network with the {4².6⁵.8³}{4².6} topology. In addition, the compound exhibits fluorescence emissions in the solid state at room temperature.     

杂芳基硼化合物的合成

利用２－溴噻吩、镁屑、硼酸三正丁酯或三氟化硼乙醚室温下一锅反应分别合成了一噻吩基、二噻吩基硼酸,三噻吩基硼烷及其衍生物．利用５－甲基－２－呋喃基锂、２－苯并呋喃基锂与硼酸三正丁酯或三氟化硼乙醚低温下反应合成了几种含呋喃基硼化合物．利用烃基格氏试剂与噻吩基硼酸正丁酯低温下反应合成噻吩基烃基硼酸衍生物     

离子液体(1-甲基-3-羧甲基咪唑)钴配合物的合成和晶体结构

由离子液体1-甲基-3-羧甲基咪唑硫酸氢盐([C6H9N2O2][HSO4])和氯化钴合成了一种新的配合物[Co(H2O)4(C6H8N2O2)2]Cl2.2H2O;采用单晶X射线衍射方法测定了配合物的晶体结构.结果表明,所合成的配合物C12H28Cl2CoN4O10属于三斜晶系,空间群P-1,a=0.66753(5)nm,b=0.91751(6)nm,c=1.80604(13)nm,α=85.618(5)°,β=83.385(5)°,γ=83.443(5)°,V=1.08934(13)nm3,Z=2,Mr=520.23,F(000)=538,Dc=1.580g.cm-3,μ(Mo-Kα)=1.088mm-1,R1=0.0861,wR2=0.2878.单晶X射线分析结果表明,在所合成的配合物中,每个1-甲基-3-羧甲基咪唑除羧基外其它原子均位于同一平面,咪唑环带正电荷,而羧基氢原子消失;即整个1-甲基-3-羧甲基咪唑分子不带电荷.总体而言,配合物的内界[Co(H2O)4(C6H8N2O2)2]2+带两个正电荷,外界游离的两个氯离子起平衡电荷作用.     

Characterization and Activity of MnO/γ‐Al2O3 for Hydrogenation of Methyl Benzoate to Benzaldehyde

The activities of a MnO/γ‐Al₂O₃ catalyst for the selective reduction of methyl benzoate to benzaldehyde have been studied in a continuous flow reactor. Characterization of the catalyst has been conducted by XRD, XPS, NH₃‐TPD and TPD‐IR. XRD and XPS results revealed that the steady state catalyst is mainly MnO₂/γ‐AlO₃ before reduction and MnO/γ‐Al₂O₃ after reduction. Monolayer dispersion capacity obtained by XPS method is about w (Mn)11.3% TPD‐IR results revealed that there are only L acidic centers on the catalytic surface. NH₃‐TPD determinations have verified that the catalyst with a certain number of moderate strength acidic sites is advantageous to hydrogenation of methyl benzoate to benzaldehyde.