Synthesis,Structure and DFT Calculations of a Novel Copper(Ⅱ)Complex Based on Tert-butyl 2-[N-(tert-butyloxycarbonylmethyl)-2-picolyamino]acetate

A novel copper（Ⅱ） complex with tert-butyl 2-[N-（tert-butyloxycarbonylmethyl）-2-picolyamino]acetate（ampy） was synthesized and structurally characterized by elemental analysis, FT-IR spectrum, electrospray ionization-mass spectrometry, UV-vis spectrum and single-crystal X-ray diffraction, respectively. A mononuclear copper（II） complex with ampy, [Cu（ampy）Cl2]（1）, was formed irrespective of the metal-to-ligand molar ratios（[Cu2＋]：[ampy] = 0.5：1, 1：1, and 2：1） as a single product. Complex 1 crystallizes in the orthorhombic system, space group Pbca with a = 12.343（2）, b = 18.928（3）, c = 20.058（4） A, V = 4686.1（14） A3, Z = 8, Dc = 1.3349（4） g/cm3, F（000） = 1920, S = 1.016, R = 0.0693 and w R = 0.1721 for 3151 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the central copper（II） ion is bound by pyridyl N, tertiary amine N and carbonyl O atoms of the quadridentate ampy as well as two Cl anions, constructing a slightly distorted octahedral geometry. Complex 1 further constructs a stable 3D supramolecular architecture by intermolecular C–H…Cl hydrogen bonds. In addition, the molecular geometry was calculated by density functional theory（DFT/B3LYP） method with the basis sets（6-31＋G（d,p） for H, C, N, O and Cl atoms, and LANL2 DZ for Cu atom, respectively）. The calculated results show that the optimized geometrical parameters are in good agreement with the experimental data. Natural bond orbital（NBO） analysis and frontier molecular orbitals（FMOs） analysis were investigated at the same level.

SYNTHESIS OF 3,7-DIMETHYL-2-TRIDECANYL ACETATE--Active Component of Sex Pheromone of Pine Sawfly Diprion pini

The total synthesis of 3,7 dimethyl 2 tridecanyl acetate,the active component of the sex pheromone of diprion pini,was investigated in this paper.The two key synthins blocks,2 methyl octan 1 yl lithium and 3,4 dimethyl γ butyrolactone,were obtained from diethyl malonate and 2,3 epoxybutane.2 Methyl octan 1 yl lithium reacted with 3,4 dimethyl γ butyrolactone to yield the ketoalcohol and then followed by Huang Minlong reduction to afford 3,7 dimethyl 2 tridecanol,acylated with acetic anhydide to give 3,7 dimethyl 2 tridecanyl acetate.

In_2O_3-modified Cu/SiO_2 as an active and stable catalyst for the hydrogenation of methyl acetate to ethanol

A series of indium oxide‐modified Cu/SiO2catalysts were synthesized and used to produce ethanol via methyl acetate hydrogenation.In‐Cu/SiO2catalyst containing1.0wt%In2O3exhibited the best catalytic activity and stability.The physicochemical properties of the synthesized catalysts were investigated using several characterization methods and the results showed that introducing suitable indium to Cu/SiO2increased the copper dispersion,diminished the copper crystallite size,and enriched the surface Cu+concentration.Furthermore,the Cu/SiO2catalyst gradually deactivated during the stability test,which was mainly attributed to copper sintering and the valence change in surface copper species.In contrast,indium addition can inhibit the thermal transmigration and accumulation of copper nanoparticles to stabilize the catalyst.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

Vapor Pressure Measurement and Correlation of 2-Methyl-Butanol Acetate Containing Calcium Chloride

The CaCl2 solubility in 2-methyl-butanol acetate and the vapor pressure of 2-methyl-butanol acetate containing CaCl2 were measured in the range of 90-135°C and from very low salt concentration to saturation.The experimental data were correlated with two equations,a modified Antoine equation with the dissolved salt taken into account and a nonrandom two liquid-electrolyte（e-NRTL）model.Both models are in good agreement with the experimental data.This study provides essential physical data for further investigation of vapor-liquid equilibrium system containing salt.

Synthesis and Crystal Structure Analysis of 2-(3,5-Di-tert-butyl-2-hydroxyphenyl)-2-(3,4- dimethylphenyl) Acetic Acid Dimethylamine Salt

A new compound 2-（3,5-di-tert-butyl-2-hydroxyphenyl）-2-（3,4-dimethylphenyl） acetic acid dimethylamine salt （[NH2（CH3）2][C24H31O3]） was synthesized and structurally determined. It is of monoclinic system, space group P21/c with a = 14.731（2）, b = 10.1185（10）, c = 17.065（2） A^°, β = 98.293（10）° ,Z = 4, V = 2517.0（6）A^°^3, Dc = 1.091 g/cm^3, F（000） = 904 and Mr= 413.58. The dihedral angle defined by two benzene rings is 98.23°.

Synthesis, Structure and Quantum Mechanical Calculations of Methyl 2-(5-((Quinolin-8-yloxy)-methyl)-1,3,4-oxadiazol-2-ylthio)-acetate

The title compound was synthesized by the base catalyzed reaction of 5-（（quinolin- 8-yloxy）methyl）-1,3,4-oxadiazole-2（3H）-thione with methyl chloroacetate. The structure was supported by the spectroscopic data and unambiguously confirmed by single-crystal X-ray diffraction studies. It crystallizes from a methanol solution in the triclinic space group Pi with unit cell dimensions a = 7.4509（9）, b = 10.2389（12）, c = 12.2299（15）A, a = 74.771（2）, β = 77.956（2）, 7 = 69.263（2）°, V = 834.98（17） A3 and Z = 2. In order to gain some valuable insights into the molecular structure, the quantum mechanical calculations were performed using both HF and time-dependent density functional theory at the B3LYP/6-31G（d,p） level. The molecular geometry from X-ray determination of the title compound in the ground state has been compared using the Hartree-Fock （HF） and density functional theory （DFT） with the 6-31G（d） basis set. The calculated results show that the DFT and HF can well reproduce the structure of the title compound. The energetic behavior of the title compound was examined using the B3LYP method with the 6-31G（d） basis set. The harmonic vibrational frequencies calculated have been compared with the experimental FTIR and FT-Raman spectra. The restricted Hartree-Fock and density functional theory-based nuclear magnetic resonance （NMR） calculation procedure was also performed, and it was used for assigning the 13C and 1H NMR chemical shifts of the title compound. Moreover, molecular electrostatic potential and thermodynamic parameters of the title compound were investigated by theoretical calculations.

Synthesis,Characterization,X-ray Crystal Structure and Safener Activity of Chiral 2-(3-Methyl-2,3-dihydrobenzo[b][1,4]oxazin-4-yl)-2-oxoethyl Acetate

The new title compound, chiral 2-（3-methyl-2,3-dihydrobenzo[b][1,4]oxazin-4-yl）- 2-oxoethyl acetate, has been synthesized via reduction, cyclization and acylation reaction. The structure of the product has been confirmed by IR, 1H NMR, 13C NMR, LC-MS （ESI） and single-crystal X-ray diffraction. （R）-2-（3-methyl-2,3-dihydrobenzo[b][1,4]oxazin-4-yl）-2-oxoethyl acetate crystallizes in monoclinic, space group P21/c with a = 11.867（2）, b = 8.4087（2）, c = 14.325（6） A^°, β = 117.59（2）°, Z = 4, V = 1266.9（6） A^°3, Dc = 1.307 g/cm^3, F（000） = 528, μ（MoKα） = 0.097 mm-1, R = 0.0453 and wR = 0.1237; （S）-2-（3-methyl-2,3-dihydrobenzo[b][1,4]oxazin-4-yl）-2-oxoethyl acetate belongs to the triclinic system, space group P with a = 8.2647（17）, b = 8.7034（17）, c = 9.5479（19） A^°, α = 105.33（3）, β = 100.95（3）, γ = 105.14（3）°, Z = 2, V = 614.1（2） A^°3, Dc = 1.348 g/cm^3, F（000） = 264, μ（MoKα） = 0.10 mm-1, R = 0.0613 and wR = 0.1037. Both of the molecules prefer to form crystal packing through C–H…O hydrogen bonds.

Study on Performance and Emission Characteristics of a Compression Ignition Engine Fueled with Diesel-2 Ethoxy Ethyl Acetate Blends

Diesel engines are the major contributors of various types of air polluting gases like carbon monoxide, oxides of nitrogen, smoke, etc. Improvement of fuel properties is essential for suppression of Diesel pollutant emissions along with the optimization of design factors and after treatment equipment. Studies conducted in the past have shown that a significant reduction were obtained in the emissions using oxygenates. This paper investigates the performance and emission characteristics of a direct injection Diesel engine fueled with 2 Ethoxy Ethyl Acetate (EEA) blends. Different fuel blends which contain 5%, 10% and 15% of EEA were prepared and the effect of these blends on performance and emissions were studied on a single cylinder direct injection Diesel engine. The blends were tested under different load conditions and the result showed that EEA blended fuels improves the performance of the engine and reduce the emission level significantly.

Rendering of Cellulose Acetate Fabrics Self-Cleaning through Treatment with TiO₂Nano Particles

Finishing using TiO2-nanosol treatment of cellulose acetate (CA) fabrics before and after the latter were pretreated with H2O2was undertaken with a view to impart unique properties to CA fabrics, notably, self-cleaning. Finishing was performed as per the pad-dry-cure method. The finishing treatment involved dispersing the nano-sized TiO2particles in a mixture of water and ethylene glycol (1:1) and application of the dispersions to CA fabrics was made under a variety of conditions. Self cleaning ability of the fabrics is favored by 1) increasing the concentration of TiO2-nanosol to certain limit;2) prolongation of curing time up to 15 second;3) raising the microwave power from 80% to 100% but with the certainty that power of 90% is the most proper. Besides, exposure time-to UV radiation-up to 90 minutes is essential to have remarkable self cleaning properties while keeping other technical properties, namely, strength, roughness and wettability practically unaltered. Incorporation of binder in the finishing pad-bath helps stabilizing the deposition of TiO2 with excellent self-cleaning. Pretreatment of CA fabrics with H2O2 is a pre requisite to guarantee excellent self-cleaning ability. Thermofixation and microwave fixation produces fabrics with very comparable technical properties.

Ni/ZrO_(2)-SO_(4)^(2-)催化剂的制备及其催化甲烷与CO_(2)制乙酸性能

以Zr(NO_(3))4·5H_(2)O和Ni(NO_(3))2·6H_(2)O为原料、(NH4)2CO_(3)为沉淀剂,采用溶胶凝胶-硫酸酸化两步法制备了Ni/ZrO_(2)-SO_(4)^(2-)催化剂,采用XRD,FTIR,SEM,N_(2)吸附-脱附,H_(2)-TPR,NH3-TPD等方法对Ni/ZrO_(2)-SO_(4)^(2-)催化剂进行表征,考察了Ni的引入方式对催化剂的结构和性能的影响。实验结果表明,与共沉淀方式引入Ni制备的Ni/ZrO_(2)-SO_(4)^(2-)催化剂相比,采用溶胶凝胶方式引入Ni制备的催化剂的四方相ZrO_(2)占比更高,表面酸量更多,且具有良好的热稳定性和较强的L酸性;采用溶胶凝胶方式引入Ni制备的Ni/ZrO_(2)-SO_(4)^(2-)催化剂的乙酸生成量明显优于共沉淀方式引入Ni制备的Ni/ZrO_(2)-SO_(4)^(2-)催化剂。四方相ZrO_(2)、酸性位点和过渡金属Ni之间的协同作用促进了甲烷与CO_(2)直接反应合成乙酸。

PEI功能化乙酸锌辅助机械化学法合成的ZIF-8吸附CO_(2)性能研究

为开发高效且适合大规模生产的CO_(2)吸附剂,采用乙酸锌为辅助研磨物,ZnO为金属前驱体,利用机械化学法高效合成高比表面积的ZIF-8材料,考察了机械化学法的合成条件及优势,采用湿浸渍法将聚乙烯亚胺(PEI)负载到ZIF-8材料中,通过X射线衍射(XRD)、扫描电镜(SEM)、红外光谱(FT-IR)和N2吸附-脱附等进行表征,评价其CO_(2)吸附性能。结果表明:机械化学法可在短时间内高效合成ZIF-8材料,其收率高达80.7%。机械化学法显著减少了有机溶剂和有机配体的用量,所合成的ZIF-8具有更小的粒径。PEI的加入显著提高了ZIF-8的CO_(2)吸附性能,其中PEI负载量为60%(质量分数)的吸附剂在50℃的吸附量最高,达到90.21 mg/g,较ZIF-8提高约14倍。此外,该复合材料还表现出良好的稳定性和再生性,在CO_(2)吸附领域具有广阔的应用前景。

Synthesis,Crystal Structure and Antitumor Activity of a Novel Zn(Ⅱ)Complex with 2-(Nicotinoyloxy)acetic Acid Ligand

A novel Zn（Ⅱ） complex, [ZnL2（H2O）4]·H2O（1, HL = 2-（nicotinoyloxy）acetic acid）, was synthesized using Zn（OAc）2·2H2O and 2-（nicotinoyloxy）acetic acid as raw materials. Its structure has been elucidated by elemental analysis, IR and single-crystal X-ray diffraction. The structural analysis revealed that complex 1 crystallizes in triclinic, space group P1 and the Zn（Ⅱ） atom is six-coordinated with two N atoms from two different 2-（nicotinoyloxy）acetate anion ligands and four O atoms from coordinated water molecules. Complex 1 forms a 3D network structure by O–H···O hydrogen bonds. The antitumor activities of 2-（nicotinoyloxy）acetic acid ligand and its Zn（Ⅱ） complex were evaluated against human lung adenocarcinoma A549 cells, human hepatoma SMMC-7721 cells and human colon carcinoma Wi Dr cells.

Synthesis and Structural Determination of (2R,4S,SS)-(+)-Threo-5-(2,2-dichloroacetamido)-4-(4-nitrophenyl)-2-aryl-1,3-dioxanes

(2R,4S,SS)-(+)-threo-5-(2,2-dicloroacetamido)-4-(4-nitrophenyl-2aryl-l,3dioxanes, were synthesized with high diastereoselectivity and good yields. The structuresofacetals were determined and the configurations were confirmed by 2D-NMR (NOESY).

镧改性Cu/SiO_(2)催化剂的乙酸甲酯高效加氢催化性能研究

采用蒸氨法制备了镧(La)改性的负载型铜硅(Cu/SiO_(2))催化剂,并对其乙酸甲酯(MeOAc)气相加氢制乙醇(EtOH)的催化性能进行了研究。采用N2吸附-脱附(N2adsorption-desorption)、X射线粉末衍射(XRD)、电感耦合等离子体发射光谱(ICP-OES)、氢气程序升温还原(H2-TPR)、傅里叶红外光谱(FT-IR)、高分辨透射电镜(HRTEM)、光电子能谱(XPS)和原子发射光谱仪(AES)等手段对催化剂进行了的表征,发现La物种的加入产生了较多的层状硅酸铜,增强了Cu和La物种之间的相互作用。La物种的加入在结构方面提高了催化剂的比表面积,降低了铜物种的粒径,提高了铜物种的分散度;在电子还原调控方面提高了Cu+的含量,增强了催化剂吸附酰基和甲氧基的能力。与未改性的Cu/SiO_(2)催化剂相比,镧改性后Cu/SiO_(2)催化剂的乙酸甲酯加氢性能得到大幅提升;其中La掺杂量0.5%的Cu/SiO_(2)催化剂表现出最佳的催化性能,乙酸甲酯转化率达98.5%,乙醇的总收率为97.0%。

Synthesis of Acetic Acid on Pd-H_4SiW_(12)O_(40)-Based Catalysts by Direct Oxidation of Ethylene

Synthesis of acetic acid by direct oxidation of ethylene on Pd-H4SiW12O40-based catalysts was studied in a fixed-bed integral reactor and a pulse differential reactor. From the performance of the catalysts with different compositions and configurations, it is proposed that acetic acid is predominantly produced via an intermediate of acetaldehyde. This can be easily confirmed by comparing the product distributions in the integral and the differential reactors. The active sites for acetic acid formation are considered to exist mainly at the boundaries between the H4SiW12O40 and the Pd particles. The Pd-based catalysts reduced by H2/N2 have higher activities than those reduced by hydrazine, as explained by the degree of Pd dispersion obtained from the characteristics of hydrogen chemical adsorption. It was found that the Pd-Se-SiW12/SiO2 catalyst with selenium tetrachloride as a precursor was more active than that with potassium selenite, and that the acetic acid yield can be greatly increased by adding a suitable amount of dichloroethane (C2H4C12/C2H4 mole ratio=0.03) to the reactants.

Synthesis,Structure,and Surface Photo-electric Properties of a New Zn(Ⅱ)Coordination Complex Constructed from 2-(1H-benzotriazol-1-yl)acetic Acid and 1,10-Phenanthroline Ligands

A new binuclear Zn^Ⅱ coordination complex,Zn2（bta）（phen）2（Cl）3（1,Hbta = 2-（1Hbenzotriazol-1-yl）acetic acid and phen = 1,10-phenanthroline）,has been synthesized and characterized by single-crystal X-ray diffraction,IR spectroscopy,elemental,and photoluminescent analysis.Complex 1 crystallizes in triclinic system,space group P1 with a = 9.3040（19）,b = 10.694（2）,c =16.841（3） A°,α = 101.18（3）,β = 105.77（3）,γ = 91.72（3）°,V= 1575.8（5） A°3,C（32）H（22）Zn2Cl3N7O2,Mr =773.66,Dc = 1.631 g/cm^3,Z = 2,F（000） = 780,μ = 1.820 mm^-1,the final R = 0.1238 and wR =0.1131.X-ray diffraction analyses indicate that 1 displays two crystallographic independent Zn^Ⅱmetal centers with a distorted tetragonal pyramidal（ZnN4O） and a tetrahedral（ZnNCl3） geometries,respectively.The phen serves as a common N,N＇-bidentate ligand,and the bta^- as a unique N,O-bridged ligand in 1.In the crystal,1 forms a stable 3D supramolecular architecture by trifurcated hydrogen bonding C-H…C1 interactions and C-H…π,π…π stacking.1 showed photo-electric conversion properties.

醋酸纤维素水性高分子/SiO_(2)纳米复合皮革涂饰剂的制备

以A50为亲水剂,通过转换反应位点和反应官能团,调节分子链软硬段比例,引入纳米SiO_(2)提升乳液涂膜综合性能,制备WSCDA/SiO_(2)纳米复合乳液。结果表明,亲水剂A50用量为10.8%(质量分数),复合乳液及涂膜性能最优。最优条件下合成的复合乳液的平均粒径为109.5nm,粒径分布均匀,涂膜表面致密光滑,柔韧性、附着力、耐水性、耐黄变性、机械性能和热稳定性良好。WSCDA/SiO_(2)纳米复合乳液成膜时,在涂膜表面形成许多小“乳突”,产生荷叶效应,提高涂膜耐水、耐介质及耐黄变等性能。

Synthesis of Vanillin 1, 2-Propylene Glycol Acetal Catalyzed by H3PMo6W6O40·nH2O

Vanillin 1, 2-propylene glycol acetal was synthesized from vanillin and 1, 2-propylene glycol using H3PMo6W6O40·nH2O as catalyst, The factors influencing the synthesis were discussed and the better reaction conditions were found as follows： The amount of vanillin was 3.8 g, the molar ratio of vanillin was 1, 2-propylene glycol 1.0 to 2.4, the amount of catalyst was 1.6% in proportion to the total reacting materials, the volume ofcyclohexane as the water-carrying agent 4 mL, the refluxing time was 2 h at 88-96℃ and thus the product yield reached over 87%. The results show that the catalyst＇s activity is high and the reaction time is short.

Syntheses, Characterization and Antitumour Activities of Rare Earth Metal Complexes with 2-(((4,6-dimethyl)-2-Pyrimidinyl)thio)-Acetic Acid

Eight rare earth metal （ Ⅲ ） complexes with 2- （ （（4,6-dimethyl）-2-pyrimidinyl） thio）-acetic acid, LnL3· n H2O [HL = 2-（（（4,6-dimethyl）-2-pyrimidinyl）thio）-acetic acid; Ln = La, Ce, Pr, Nd, Sm Eu, Gd, Tb; n = 4 or 5], were prepared and characterized by elemental analysis, complexometric titration, thermal analysis, conductivity, IR and ^1H- NMR. The results reveal that carboxyl group of the hgand coordinates with rare earth ions in bidentate mode after deprotonated. The water molecules exist as crystal water in the complexes. The anti-tumour activities of HL and some complexes were tested by both the MTT and SRB methods. The results show that the suppression ratios of some complexes against the tested tumour cells （HL-60 human leukemia cell lines, BGC-823 human gastric carcinoma cell lines, hela human cervix adenocarcinoma cell lines and Bel-7402 human hepatic carcinoma cell lines） are superior to HL.