卡宾与醚C—H键插入反应的理论研究(Ⅲ)CX_2(X=H,F,Cl)与甲乙醚C—H键插入反应

用量子化学从头计算方法在 MP2 / 6-31 G( d)水平上研究了 CX2 ( X=H,F,Cl)与甲乙醚的 C— H键插入反应 .在甲乙醚的 3个不同的 C— H键 (即甲基中α -C— H键 ,乙基中α-C— H键和β-C— H键 )上 ,反应势垒分别为 1 2 3.8,32 .5,1 57.3k J/ mol( X=Cl)和 2 54.3,1 30 .0 ,30 4 .2 k J/ mol( X=F) .亚甲基与毗邻氧原子的各 C— H键插入反应没有势垒 ,与乙基中 β-C— H键插入势垒仅 3.4 k J/ mol.甲乙醚中乙基 α-C上的C— H键最有利于 CX2 的插入 ,甲基上的 C— H键次之 ,乙基 β-C上的又次之 .

二乙二醇甲乙醚的合成及其合成条件优化

以二乙二醇单乙醚(DEGME)和氯甲烷为基本原料,氢氧化钠为催化剂、苯为带水剂,通过Williamson反应合成了二乙二醇甲乙醇(DEGMEE);用正效实验法对DEGMEE的合成条件进行了优化,气相色谱法分析了产品中DEGMEE的含量、FT IR和1H NMR法表征了产物结构。实验结果表明适宜的反应条件为:反应温度为60.0°C、醚化时间为4.0 h、n(CHCl)/n(DEGME)=1.15、n(NaOH)∶(DEGME)=1.30;在此条件下二乙二醇甲乙醚的收率可达93%以上。

二乙二醇甲乙醚的合成及应用

本文介绍了二乙二醇甲乙醚的基本合成方法并比较了不同制备方法的各自特点,提出了以二乙二醇单乙醚和卤甲烷为基本原料,借助于带水剂的作用合成二乙二醇甲乙醚的新方法;与其它方法相比这一方法将有更大的发展优势。同时通过对二乙二醇甲乙醚在不同行业中应用情况的介绍和分析,指出二乙二醇甲乙醚将具有良好的市场发展前景。

顶空气相色谱测定季铵盐中甲乙醚的含量

建立了用顶空进样-气相色谱法测定季铵盐中甲乙醚的定量分析方法。甲乙醚的检出限3.0g/L,线性范围20g/L～480g/L,相关系数0.9992,相对标准偏差3.1%。甲乙醚的加标回收率97.6%～99.4%。该方法操作简单,适合产品质量控制及相关质监部门快速测定其含量。目前对甲乙醚的测定国内属空白。

全氟聚醚润滑油添加剂抗氧抗腐蚀机理研究及分子设计──Ⅱ.N-取代聚全氟甲乙醚苯酰胺的合成和测试

依据前期研究全氟聚醚润滑油抗氧抗腐添加剂的结构特征，选择并合成了３个Ｎ－取代聚全氟甲乙醚苯酰胺抗氧抗腐添加剂．经光谱分析发现，合成的３个产物中苯环的紫外特征吸收峰分别在２４０．７，２１５．４和 ２３０．１ｎｍ附近；Ｃ＝Ｏ的红外特征吸收峰分别在１７１３．９，１７１２．２和１７１０．８ ｃｍ－１附近．测试合成的３个添加剂抗氧抗腐性能发现：加入合成的添加剂后，能将氟醚润滑油失重较空白样分别减少１／７，１／９，１／２５倍，可将Ａｌ２Ｏ３催化下的热分解温度提高１９～２２℃．理论和实验研究表明：含氮杂原子的聚全氟甲乙醚苯酰胺化合物，既能接受ＲｆＯ的电子，生成稳定的加合物，阻止ＲｆＯ反应；又能给出电子与金属发生化学吸附，形成保护膜，具有较好的抗氧抗腐蚀性能；在这类化合物的Ｎ原子上引入供电子基团或苯基，可增加添加剂的抗氧抗腐蚀性能．研究结果可为设计新的抗氧抗腐添加剂提供有用的信息．

甲醛的特殊性

甲醛是一种重要的有机物,不少相关习题涉及到甲醛在组成、结构和性质上的特殊性,所以它的特殊性往往成为解题的关键．一．结构的特殊性甲醛分子中的4个原子是共平面的．例1 已知甲醛(HVHO)分子中的4个原子是共平面的．下列分子中所有原子一定不可能同时存在于同一平面上的是( )．

Effect of Calcination Temperature on Catalytic Activity and Textual Property of Cu/HMOR Catalysts in Dimethyl Ether Carbonylation Reaction

The effect of calcination temperature on the catalytic activity for the dimethyl ether （DME） carbonylation into methyl acetate （MA） was investigated over mordenite supported copper （Cu/HMOR） prepared by ion-exchange process. The results showed that the catalytic activity was obviously affected by the calcination temperature. The maximal DME conversion of 97.2% and the MA selectivity of 97.9% were obtained over the Cu/HMOR calcined at 430 ℃ under conditions of 210 ℃, 1.5 MPa, and GSHV of 4883 h^-1. The obtained Cu/HMOR catalysts were characterized by powder X-ray diffraction, N2 absorption, NH3 temperature program desorption, CO temperature program desorption, and Raman techniques. Proper calcination temperature was effective to promote copper ions migration and diffusion, and led the support HMOR to possess more acid activity sites, which exhibited the complete decomposing of copper nitrate, large surface area and optimum micropore structure, more amount of CO adsorption site and proper amount of weak acid centers.

Synthesis of Methyl Acetate by Dimethyl Ether Carbonylation over Cu/HMOR： Effect of Catalyst Preparation Method

Dimethyl ether carbonylation to methyl acetate was comparatively investigated over mor- denite supported copper （Cu/HMOR） catalysts prepared by different methods including evaporation, urea hydrolysis, incipient wetness impregnation and ion-exchange. The results showed that Cu/HMOR prepared via iron-exchange method exhibited the highest catalytic activity due to the synergistic effect of active-site metal and acidic molecular sieve support. Conversion of 95.3% and methyl acetate selectivity of 94.9% were achieved under conditions of 210℃, 1.5 MPa, and GSHV of 4883 h-1. The catalysts were characterized by nitrogen absorption, X-ray diffraction, NH3 temperature program desorption, and CO temperature program desorption techniques. It was found that Cu/HMOR prepared by ion-exchange method possessed high surface area, moderate strong acid centers, and CO adsorption centers, which improved catalytic performance for the reaction of CO insertion to dimethyl ether.

有机化学中的信息给予题与推断题

有机化学中的信息给予题与推断题逢丰海近几年的高考题中屡屡出现信息给予题、推断题。现就这两种题型剖析如下：一、信息给予题信息给予题是一种学以致用的新颖题型，它是由题干──提供信息部分和要解决的若干具体问题部分组成。解答这类题目最关键的就是要仔细审题、抓...

Experimental Study on Dimethyl Ether Combustion Process in Homogeneous Charge Compression Ignition Mode

Experimental study on homogeneous charge compression ignition （HCCI） combustion process was carried out on a single-cylinder direct injection diesel engine fueled with dimethyl ether（DME）. The influence of inert gas CO2 on the ignition and combustion process was investigated. The research results indicate that because of the high cetane number of DME, the stable HCCI operating range is quite narrow while the engine has a high compression ratio. The HCCI operating range can be largely extended when the inert gas is inducted into the charging air. HCCI combustion of DME presents remarkable characteristic of two-stage combustion process. As the concentration of inert gas increases, the ignition timing of the first combustion stage delays, the peak heat release rate decreases, and the combustion duration extends. Inducting inert gas into charging air cannot make the combustion and heat release of DME occur at a perfect crank angle position. Therefore,to obtain HCCI operation for the fuel with high cetane number,other methods such as reducing engine compression ratio should be adopted. Emission results show that under HCCI operation, a nearly zero NOx emission can be obtained with no smoke emissions. But the HC and CO emissions are high, and both rise with the increase of the concentration of inert gases.

Brφsted-acidic ionic liquids as efficient catalysts for the synthesis of polyoxymethylene dialkyl ethers

Acetalation of formaldehyde(HCHO)with dialkyl formal or aliphatic alcohol to prepare polyoxymethylene dialkyl ethers(RO(CH2O)nR,n≥1)catalyzed by Br?nsted‐acidic ionic liquids has been developed.The correlation between the structure and acidity activity of various ionic liquids was studied.Among the ionic liquids investigated,1‐(4‐sulfonic acid)butyl‐3‐methylimidazolium hydrogen sulfate([MIMBs]HSO4)exhibited the best catalytic performance in the reaction of diethoxymethane(DEM1)with trioxane.The influences of ionic liquid loading,molar ratio of DEM1to HCHO,reaction temperature,pressure,time,and reactant source on the catalytic reaction were explored using[MIMBs]HSO4as the catalyst.Under the optimal conditions of n([MIMBs]HSO4):n(DEM1):n(HCHO)=1:80:80,140°C,and4h,the conversion of HCHO and selectivity for DEM2?8were92.6%and95.1%,respectively.The[MIMBs]HSO4catalyst could be easily separated and reused.A feasible mechanism for the catalytic performance of[MIMBs]HSO4was proposed.

Study on Vapor Liquid Equilibrium for C_9 Separation by Azeotropic Distillation

In this work,ethylene glycol monomethylether(EE) was chosen as an entrainer for the azeotropic distillation of 1,3,5-trimethylbenzene+1-methyl-2-ethylbenzene system to investigate the influence of the entrainer on vapor liquid equilibrium(VLE) of this system.Three sets of binary VLE data in the system consisting of EE + 1,3,5-trimethylbenzene +1-methyl-2-ethylbenzene were measured using the Dvorak-Boublik still.The binary parameters of NRTL model were correlated by using the likelihood method.The ternary VLE data of the system were measured as well and were predicted by using the binary parameters of NRTL model.The test results indicated that the binary data passed the thermodynamic consistency tests,and the difference between the predicted values of ternary VLE and the experimental data reached the research standard for VLE data.Addition of EE had a great influence on the relative volatility between 1,3,5-trimethylbenzene and 1-methl-2-ethyl-benzene:when the ratio of solvent was 4,and the relative volatility between 1,3,5-trimethylbenzene and 1-methyl-2-ethylbenzene increased from 1.0125(without solvent addition) to 1.283.

Fuel consumption study on introducing pyrolyzed DME or ethanol into diesel engine

The present work studied fuel consumption through experiments on a diesel engine. In order to obtain lower BSFC （brake specific fuel consumption）, DME （dimethyl ether） is heated and introduced into air intake, together with fueling emulsified fuel to diesel engine. Results show that BSFC can decrease about 10% and diesel fuel consumption alone can decrease 18%. High saving rate of BSFC up to 10% is also acquired using ethanol instead of DME. To achieve high saving rate of BSFC, the heating temperature of about 1000 K is needed for DME operation, while the diesel engine exhaust temperature of about 750 K is suitable for ethanol. Hydrogen produced in DME or ethanol pyrolysis and the combustion characters of emulsified fuel are considered as main reasons for the excellent fuel saving. Besides, the technique adopted in the present work is extremely easy to be utilized, and may be firstly adopted on diesel engines for power plants, trains, and ships etc.

In Vitro Activity of Lawsonia inermis （Henna） on Some Pathogenic Fungi

The present study was conducted to investigate antifungal activity ofLawsonia inermis （Henna plant）. Leaf samples of the plants were collected from Eastern Nile of Khartoum state, Sudan. Ethanol and petroleum ether extracts in various concentrations were obtained by maceration （cold method）. The extracts were bioassay in vitro to know their bioactivity to inhibit the growth of tested fungi. The cup plate agar diffusion method was adopted to assess the antifungal activity of the extracts against tested yeasts while agar incorporated method was used for other molds. Both extracts revealed anti fungal activity against all yeast strains except Pichiafabianii which was found resistant to both ethanol and ether extracts. The results displayed antifungal activity against tested fungi. Minimum mould concentration （MMC） of the extracts was determined. The obtained results revealed antifungal activity of henna leaves extracts which support the traditional use of the Henna in therapy of fungal infections. The possibility of therapeutic use of Sudanese henna as antifungal agents is recommended.

解有机试题的思路和技巧例析

研究解有机试题的思路和技巧,特别是研究巧解妙算,对启迪学生思维、培养学生能力非常重要。现举例说明。 一、巧用平均式量 速推物质组成 例1.某气态烷烃和气态单烯烃的混和气体2.24升,完全燃烧后可产生3.36升CO2气体和4.05克水。另取2.24升（上述气体体积都为标准状况下的体积）原混和气体。

1989年全国中学生化学竞赛试题及参考答案

一、写出制备金属硫化物的几类方法（按:铜、铁……等分别和硫作用均归属金属和硫反应类）。二、写出制备二氧化硫的几类方法（按:铜、锌……等分别和浓硫酸作用归为同一类反应）。三、1.磁性材料Fe2O3可由FeSO4热分解反应制得。写出反应方程式。 2.在醋酸溶液中K4Fe（CN）6和NaNO2反应可得纯NO。写出反应方程式。 3.在酸性溶液中NaNO2和KI反应可得纯NO。写出反应方程式。

Synthesis and Enhanced Photocatalytic Activity of Regularly Shaped Cu2O Nanowire Polyhedra

A series of unique nanowire superstructures, Cu2O nanowire polyhedra, have been synthesized through a cost-effective hydrothermal route. Three types of nanowire polyhedra, namely octahedra, concave octahedra, and hexapods, were formed in high morphological yields （90%） by reducing cupric acetate with o-anisidine or o-phenetidine in the presence of carboxylic acids. The architectures of these Cu2O nanowire polyhedra were examined by electron microscopy, which revealed ordered, highly aligned CU2O nanowires within the polyhedral outlines. The growth of the Cu2O nanowire polyhedra is controlled by the orientation and growth rates of the nanowire branches which are adjusted by addition of carboxylic acids. Compared to the Cu2O samples reported in the recent literature, the Cu2O nanowire octahedra exhibit notably enhanced photocatalytic activities for dye degradation in the presence of H202 under visible light, probably due to the high-density charge carriers photoexcited from the branched nanowires with their special structures. Additionally, the discussion in the recent literature of the photocatalytic activity of Cu2O in the absence of H2O2 for direct photodegradation of dyes seems questionable.

Curing the fundamental issue of impurity phases in two-step solution-processed CsPbBr3 perovskite films

Inorganic lead halide perovskite CsPbBr3 offers attractive photophysical properties and phase stability for high-performance optoelectronic devices.However,CsPbBr3 films produced by the classic solution-based two-step method are always accompanied with impurity phases of CsPb2Br5 and Cs4PbBr6,which represents a major efficiency-limiting factor for future advances of CsPbBr3-based devices.The challenge lies in the complexity of the Cs-Pb-Br phase system,requiring both spatially and temporally precise control of the precursor stoichiometry during solution-phase growth of CsPbBr3 films.By adopting 2-methoxyethanol as the solution conversion medium instead of commonly applied methanol,the reaction between CsBr and PbBr2 can be finely controlled to yield single phase CsPbBr3 films within a few minutes;extending the solution-conversion step to 24 h does not alter the phase purity of resulting CsPbBr3 films.The present work paves the way to regulate the crystal growth behaviors of two-step solution-processed CsPbBr3 films by simple solvent engineering.

Technical assessment of synthetic natural gas (SNG) production from agriculture residuals

This paper presents thermodynamic evaluations of the agriculture residual-to-SNG process by thermochemical conversion, which mainly consists of the interconnected fluidized beds, hot gas cleaning, fluidized bed methanation reactor and Selexol absorption unit. The process was modeled using Aspen Plus soft-ware. The process performances, i.e., CH4 content in SNG~ higher heating value and yield of SNGexergy efficiencies with and without heat recovery, unit power consumption, were evaluated firstly. The results indicate that when the other parameters remain unchanged, the steam-to-biomass ratio at carbon boundary point is the optimal value for the process. Im proving the preheating temperatures of air and gasifying agent is beneficial for the SNG yield and exergy effi ciencies. Due to the effects of COz removal efficiency, there are two optimization objectives for the SNG produc tion process： （I） to maximize CH4 content in SNC or （II） to maximize SNG yield. Further, the comparison among different feedstocks indicates that the decreasing order of SNG yield is： corn stalk 〉 wheat straw 〉 rice straw. The evaluation on the potential of agriculture-based SNG shows that the potential annual production of agriculture re sidual-based SNG could be between 555 108 - 611 108 m3 with utilization of 100% of the available unexplored resources. The agriculture residual-based SNG could play a significant role on solving the big shortfall of China＇s natural gas supply in future.