N,N-二甲基甲酰胺-三氯甲烷-水体系液液相平衡数据的测定与关联

为获得进一步研究DMF废水萃取回收工艺所需的基础数据,利用液液平衡釜在常压下温度分别为30℃、35℃、40℃时进行N,N二甲基甲酰胺-三氯甲烷-水体系的液液相平衡实验,各物质的平衡组成由气相色谱分析,所得液液相平衡数据用NRTL和UNIQUAC模型进行关联,应用单纯形法求得相应的模型参数。计算值与实验值比较结果表明:NRTL与UNIQUAC模型的计算值与实验数据吻合良好,模型计算的总平均绝对误差分别为0.0032和0.0033,总平均相对误差分别为2.60%和2.97%。

三(2,4-二氯苄基)氯化锡二甲基甲酰胺配位聚合物的合成和结构

在微波甲醇溶剂热中,三(2,4-二氯苄基)氯化锡与二甲基甲酰胺反应,合成三(2,4-二氯苄基)氯化锡二甲基甲酰胺配位物,经红外光谱、核磁共振(1H,13C NMR)和X-射线衍射表征结构。配合物晶体为单斜晶系,空间群P2(1)/c,a=1.453 13(10) nm,b=1.443 84(10) nm,c=1.364 25(9) nm,β=94.525 0(10)°,Z=4,V=2.853 4(3)nm^3,Dc=1.646 mg·m^-3,μ(MoKα)=1.570 mm^-1,F(000)=1 400,S=1.003,Δρmax=4654 e.nm^-3,Δρmin=-980 e.nm^-3,R=0.060 2,wR=0.178 4。在配合物中,锡原子呈五配位畸变三角双锥构型。分子间的弱作用,形成二维超分子配位聚合物结构。以晶体分子结构为模型,进行了分子构象分析,探讨配合物分子构型的稳定性;用Hirshfeld Surface分析方法计算了分子间相互作用的贡献。

氯虫苯甲酰胺的合成及表征

以3-甲基-2-硝基苯甲酸为原料通过RaneyNi加氢还原制得3-甲基-2-氨基苯甲酸,接着与N-氯代丁二酰亚胺(NCS)反应制得3-甲基-2-氨基-5-氯苯甲酸,然后3-甲基-2-氨基-5-氯苯甲酸与氯化亚砜在75～80℃下回流3h后,接着缓慢滴加甲胺水溶液,在室温下搅拌反应12h,得到2-氨基-5-氯-N,3-二甲基甲酰胺。然后再与3-溴-1-(3-氯吡啶-2-吡啶基)-1 H-吡唑-5-甲酸在-5～0℃下滴加甲基磺酰氯反应得到产品氯虫苯甲酰胺,四步总收率37.0%,产品HPLC纯度是96.05%。

Synthesis and characterization of copolyimides from bis(3,4-dicarboxyphenyl)dimethylsilane dianhydride

The silicon-containing poly (amic acid)s were synthesized from bis (3, 4-dicarboxyphenyl) dimethylsilane dianhydride (SIDA), pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (4,4'-ODA) in N, N-dimethylacetamide (DMAc). The poly (amic acid) films were obtained by solution-cast method from DMAc solutions and thermally converted into transparent, flexible and tough polyimide films. The wide-angle X-ray diffraction diagrams revealed that all the polyimides possessed amorphous character, and the regulation of those polyimides were decreased with the increase of the molar ratio of SIDA to PMDA. Differential scanning calorimeter measurements showed that the introduction of SIDA to polyimide backbone would make glass transition temperature shift to lower temperature. Thermogravimetric analyses indicated that the silicon-containing polyimides lowered decomposition temperature as compared with PMDA/4, 4′-ODA polyimides. However, UV-visible transmission and reflection spectra showed that the optical transparency of silicon-containing polyimide thin films was superior to that of PMDA/4, 4'-ODA polyimide thin films.

聚四亚甲基醚二醇羟值含量的测定

介绍使用乙酸酐-N-甲基咪唑-二甲基甲酰胺催化酰化法测定聚四亚甲基醚二醇(PTMEG)的羟值含量,讨论了样品用量、酰化温度、酰化时间和酰化剂含水量及稳定性对测定结果的影响。结果表明:使用乙酸酐-N-甲基咪唑-二甲基甲酰胺催化酰化体系,在50℃下酰化反应时间30 min,测得PTMEG1000和PTMEG2000羟值结果与国标法相接近,且操作简便耗时短,避免使用对人体危害较大的吡啶溶剂,同时酰化剂用量较少,保护了环境。

Simulation of 1,3-Butadiene Production Process by Dimethylfomamide Extractive Distillation

Nowadays, extractive distillation is the main technique to produce 1,3-butadiene. This study simulated the 1,3-butadiene production process with DMF extractive distillation by Aspen Plus. The solvent ratio is the most important parameter to the extractive distillation process. The article has given out the proper solvent ratios, reflux ratios, distillate ratios, and bottom product ratios of the columns. It also discusses the thermal loads of several columns. The results of simulation are consequently compared with the plant data, which shows good accordance with each other.

Solid-Liquid Equilibrium of Terephthalic Acid in Several Solvents

Terephthalic acid(PTA) is practically one of the main materials of polyester. Its corresponding solid-liquid equilibrium data will provide essential support for industry design and further theoretical studies. In this work,solid-liquid equilibriums of terephthalic acid in four solvents, N,N-dimethylformamide, N,N-dimethylacetamide,dimethylsulphoxide and N-methyl-2-ketopyrrolidene, were determined in the temperature range from 293.15 K to 364.6 K by dynamic method. All these data were regressed by λh model, Wilson model and NRTL model, average absolute relative deviations of which are 1.25%, 15.02% and 7.22% respectively. It indicates that λh model is mostsuitable for description of the solid-liquid equilibrium containing PTA.

Measurement and Correlation for Solubility of （S）-（＋）-2,2-Dimethylcyclopropane Carbox Amide in Different Solvents

（S）-（＋）-2,2-dimethylcyclopropane carbox amide is a key intermediate of Cilastatin, an inhibitor of dehydropeptidase-I. Its corresponding solid-liquid equilibrium data will provide essential support for industrial design and further theoretical studies. The solubilities of （S）-（＋）-2,2-dimethylcyclopropane carbox amide in toluene, dichloromethane, trichloromethane, ethyl acetate, ethanol and pure water at different temperature were measured using the synthetic method by a laser monitoring observation technique. The solubility data were correlated with the modified Apelblat equation.The calculated values were good in agreement with the experimental values.

Densities and Viscosities of the Ionic Liquid [C4mim][PF6]＋ N,N-dimethylformamide Binary Mixtures at 293.15 K to 318.15 K

Viscosities and densities for 1-butyl-3-methylimidazolium hexafluorophosphate （[C4mim][PF6]） and N, N-dimethylformamide （DMF） binary mixtures have been measured at the temperature range from 293.15 K to 318.15 K. It is shown that the viscosities and densities decrease monotonously with temperature and the content of DMF. Various correlation methods including Arrhenius-like equation, Sedclon et al.＇s equation, Redlich-Kister equation with four parameters, and other empirical equations were applied to evaluate these experimental data. A model based on an equation of state Ior estimating the viscosity of mixtures containing ionic liquids were proposed by coupling with the excess Gibbs free energy model of viscosity, which can synchronously calculate the viscosity and the molar volume. The results show that the model gives a deviation of 8.29% for the viscosity, and a deviation of 1.05% for the molar volume when only one temperature-independent adjustable parameter is adopted. The correlation accuracy is further improved when two parameters or one temperature-dependent parameter is used.

Kinetics of water–isocyanate reaction in N,N-dimethylformamide

The uncatalyzed reaction of p-tolyl isocyanate(p-TI)with water in N,N-dimethylformamide(DMF)was investigated by high performance liquid chromatography(HPLC).The reactions were carried out at different temperatures from 293 K to 323 K,using various molar ratios of water to p-TI.DMF,as a special amide,was proved to be an efficient catalyst for water–isocyanate reaction.Under the reaction conditions in this study,substituted urea was the only final product observed.An appreciable amount of intermediate p-toluidine was detected.Concentrations of the isocyanate group as well as the amine and urea were determined as a function of time.New kinetic equations were deduced for each of the substance on the basis of a multistep mechanism,instead of a simple second order reaction as usual.Kinetic constants were calculated using the software MATLAB.Furthermore,the effects of temperature and concentrations of reactants on the reaction rate and amine content were discussed.The activation energy of each step was also determined.

SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF IN-COMPLETE CUBANE CLUSTER C(MoCu_3S_3) (O)(μ-dtp)(PPh_3)_3]

A new mixed-metal sulfido incomplete cubane cluster [(MoCuS3) (O) (μ-dtp) (PPh3)3] Cdtp = S2P (OC2H5)2] has been prepared by reaction of (NH4)2MoOS3 with Cu(dtp) (PPh3)2 in dimethylformamide solution. It crystallizes in the triclinic space group P1, a = 13.810(5), b = 19. 753(5), c=11. 719(4) A. α=99. 42(2), β=107. 24(3),γ=88. 05(3)°, V = 3012(2)A3, Dc = l. 51g/cm3and Z = 2. Final R=0. 046, Rw = 0. 056 for 7700 unique intensity data(I≥3σ(I)). The central unit [MoCu3S3]3+ can be described as a distorted incomplete cube with one missing corner. The Mo atom is tetrahedrally coordinated by three μ3-S atoms and one terminal O atom. Two Cu atoms are tetrahedrally coordinated whereas the third Cu atom has a highly distorted trigonal environment. The mean Mo - Cu bond length is 2. 752A. The Cu...Cu distances are in the range of 3. 200(1) -3. 740(1) A which are too long to form bonds.

EPR Study of a New Crystal of the Binuclear Copper(Ⅱ) Cluster Compound- Cu_2(α-C_(10)H_7CH_2CO_2)_4-(DMF)_2 ·(DMF)_2·H_2O

In this paper, single crystal EPR study of a new binuclear copper (Ⅱ) cluster compound-[Cu2(α-C(10) H7CH2CO2)4 (DMF)2]·[DMF]2·H2O](DMF= (CH3)2NCOH) at room temperature is reported. The lines of △Ms=±1 allowing transition and △M=2 forbiding transition are shown in EPR spectra. The experimental data are consistent with the calculated results by the leastsquares fitting prograrn in three principal planes of g and D tensors. The spin Hamiltonian parameters are as follows: gx=2. 1482, gy=2. 0529 ,gz=2. 3905, D= 0. 348 cm￣(-1) and E =0. 01 cm-1. The diagrams of the energy levels have been obtained when the magnetic field is oriented to three principal axes. The polycrystal EPR spectra have been measured at room temperature and 77K, respectively.and the parameters of these spectra are given (g∥= 2. 094, g⊥= 2. 425, D= 0. 37 cm-1,E=0). The parameter of the isotropic magnetic exchange interaction J=-254cm-1 is determined, and that of the anisotropic magnetic exchange J1=-153 cm-1 is calculated. The average magnetic susceptibility of the polycrystal sample χ= 1. 39 ×10-6 (c. g. s) has been measured by Faraday powder method. Thus the average magnetic mornent μ=1. 43 B. M. can be calculated. It is shown that the exchange interactions between the metal ions of the binuclear copper(Ⅱ) cluster compound are confirmed antiferromagnetic In nature.

DFT-Study on Antioxydant of 3-Alkyl-4-P henylacetylam i no-1H-1,2,4-Triazol-5-O nes and Its Derivatives

In this article, we have performed B3LYP/6-31＋G（d） calculations of geometrical and reaction enthalpies of antioxidant mechanisms for ADPHT 1-4 （3-alkyl-4-phenylacetylamino-lH-1,2,4-triazol-5-ones） and its derivatives： HAT （hydrogen atom transfer）, SET-PT （single electron transfer-proton transfer） and SPLET （sequential proton-loss electron transfer） were investigated in gas and solution-phases. Solvent contribution to enthalpies was computed employing integral equation formalism IEF-PCM （integral equation formalism method） method. It turned out that the lowest BDEs （bond dissociation energies） is obtained for C-H bonds due to captodative effect in various media. Results indicate that HAT mechanism represents the most anticipated process in gas-phase from thermodynamic point of view. But, the SPLET represents the thermodynamically preferred reaction pathway in solvents （2-propanol, acetonitrile, DMF （N,N-dimethylformamide） and water）. The authors showed that bond dissociation energies, IP （ionization potential） and PA （proton affinity） are sufficient to evaluate the thermodynamically preferred mechanism.

DFT Investigation of Chelation of Divalent Cations by Some 4-Benzylidenamino-4,5-Dihydro-lH-1,2,4- Triazol-5-One Derivatives

The complexation of BDHTD （4-benzylidenamino-4,5-dihydro-lH-l,2,4-triazol-5-one derivatives） by divalent doubly charged metal ions M2＋ （M = Mg, Ca, Fe and Cu） has been investigated using the density functional method B3LYP. Two distinct coordination modes （k2-O,O and k2-O,N） have been taken into account. Geometry optimizations have been performed in gas-phase and solution-phase： acetonitrile and DMF （N,N-dimethylformamide） with the basis set 6-31G（d,p）. The B3LYP method was also used to calculate the stability and free energies of the 24 complexes of BDHTD with metal ions M2＋ （M = Mg, Ca, Fe and Cu） respectively in gas-phase and solution-phase： acetonitrile and DMF. Results indicate that k2-O,N structures are most stable in gas-phase. The influence of substitution on the stability is sensitive in solution-phase. The interaction energies of complexation process in various media have been calculated at B3LYP/6-31G（d,p） and CCSD（T） level. The MIA （metal ion affinity） of BDHTD with M2＋ （M = Mg, Ca, Fe and Cu） in various media has been explored. The results show that the M1A highly varies with the coordination mode and substitution effect. From the calculated Gibb energies of complexation in various media, it is revealed that the complexation is possible in gas in acetonitrile. The ligand＇s affinity toward individual cation M2＋ （M = Mg, Ca, Fe and Cu） has been analysed. A significant reduce of BDEs observed confirms the decrease of the antioxidant activity by the metal chelation. The charge transfer induced by metal chelation is examined using the NBO analysis.

含锑铁非水相湿法氧化脱硫剂高效吸收H_(2)S的研究

将SbCl_(3)和FeCl_(3)按一定比例引入到N,N-二甲基甲酰胺(DMF)中,构建了一种非水相湿法氧化脱硫体系。对脱硫剂及其产物进行了表征,并通过静态脱硫试验研究了该体系对H 2S的吸收规律。结果表明,该脱硫剂在常温常压下的硫容可达8.91 g/L,添加适量的水及提高一定的温度均有助于提高其脱硫效率。在适量Cu^(2+)存在下,该系统在连续5次脱硫-再生循环后,硫容水平保持在初始硫容的90%以上,再生后的固体产物为高纯硫磺。此外,Sb^(3+)是保证H_(2)S有效吸收的关键组分,适量Cu^(2+)的存在可促进Fe^(2+)向Fe^(3+)转化,以促进体系的氧化再生。

应用遗传算法推算多元溶液热力学数据

应用遗传算法推算溶液热力学数据 ,并对标准遗传算法作了适当的改进 ,得到改进的遗传算法 .举水 +DMF(二甲基甲酰胺 ) ,正丙醇 +DMF ,水 +正丙醇体系推算水 +DMF +正丙醇三元体系为例 ,并与POWELL法比较 .计算结果表明 ,遗传算法比POWELL法不仅在二元参数关联上有更强的能力 。

配合物[Zn(DMF)_2(H_2O)_4]·C_8Cl_4O_4的合成及其结构的研究

采用溶剂挥发扩散法合成了配合物单晶[Zn(DMF)2(H2O)4].C8Cl4O4,其中DMF为N,N′-二甲基甲酰胺。配合物为三斜晶系,P-1空间群,其晶胞参数为a=0.57680(10)nm,b=0.85991(14)nm,c=1.2030(2)nm,α=95.781(3)°,β=102.074(3)°,γ=98.594(2)°,V=0.57154nm3,Z=1,Mr=585.51,Dc=1.701g/cm3,F(000)=298,μ=1.594mm-1,最终偏差因子R1=0.0315,wR2=0.0914,和R1=0.0345,wR2=0.0946,同时采用红外光谱分析、元素分析对其进行表征。

邻硝基苯甲醛的制备与谱学分析

邻硝基苯甲醛是重要的有机中间体,在有机合成和制药方面有着广泛的应用,本文首先合成N,N’-二甲基甲酰胺二甲基缩醛(DMFDMA),采用邻硝基甲苯与DMFDMA经缩合氧化合成邻硝基苯甲醛,并通过1H NMR、13C NMR、FT-IR等谱学手段对产物进行分析,总收率为88.03%、纯度高达99.07% (HPLC)。本合成生产工艺方法经济成本低,收率高,对环境污染小,相较于传统工艺有较为明显的优势。

Studies on Thermodynamic Properties of Some Imidazolinone Derivatives in DMF at 308.15 K

Density,ultrasonic velocity and viscosity of imidazolinone derivatives are studied in dimethyl formamide(DMF) at 308.15 K.From the experimental data,various acoustical parameters,such as specific impedance Z,isentropic compressibilityκs,Rao's molar sound function Rm,van der Waals constant b,relaxation strength r,intermolecular free length Lf,internal pressureπ,solvation number Sn,relative association RA,etc.are evaluated,which helps in understanding the molecular interactions occurring in these solutions.

Study on Drying Process of 3Al_2O_3·2SiO_2 Mullite Gel

Monophasic mullite gel with composition 3Al2O3·2SiO2 was prepared by the sol-gel method using aluminium nitrate nonahydrate, aluminium-tri-isopropoxide, and tetraethylorthosili-cate as reagents. Gels with different drying control chemical additives(DCCAs) and polyvinylpyrrolidone(PVP) as spinning assistant were dried at several temperatures. The influences of temperature, DCCAs and PVP in the drying process were investigated. N,N-dimethylformamide(DMF) was the optimum DCCA at 70℃ in the drying process. PVP decreased the solvent volatilization speed and prevented gel crack to a certain extent. FTIR results revealed that free water, ethanol, and isopropanol were completely removed by the drying procedure.