N-Arylation of azaheterocycles with aryl and heteroaryl halides catalyzed by iminodiacetic acid resin-chelated copper complex

Iminodiacetic acid resin-chelated copper(Ⅱ) complex is effective in cross-coupling reactions between azaheterocycles and aryl or heteroaryl halides,providing N-arylated products in good to excellent yields.The copper catalyst is air stable and can be readily recovered and reused with minimal loss of activity for three runs.

Sorption behavior of iminodiacetic acid resin for indium

In（Ⅲ） was quantitatively adsorbed by iminodiacetic acid resin （IDAAR） in the medium of pH = 4.52. The statically saturated sorption capacity of IDAAR is 235.5 mg·g^-1. 1.0 mol·L^-1 HCl can be used as an eluant. The elution efficiency is 97.9%. The resin can be regenerated and reused without apparent decrease of sorption capacity. The sorption rate constant is k298 = 1.94 × 10-5 s^-1. The apparent sorption activation energy of IDAAR for In（Ⅲ） is 20.1 kJ·mol^-1. The sorption behavior of IDAAR for In（HI） obeys the Freundlich isotherm. The enthalpy change is AH= 17.2 kJ·mol^-1.

Preparation of iminodiacetic acid salts from iminodiacetonitrile with additives assisted in subcritical water

Here, the employment of subcritical water as an environmentally benign media has shown a certain potential for the hydrolysis ofiminodiaeetonitrile （IDAN）. Additives （such as NH3.H2O, （NH4）2CO3, K2CO3） were selected to investigate the reactivity ofiminodiacetonitrile in the solutions of these species in the subcritical region for the possibility of preparing iminodiacetic acid （IDA） salts. A series of reactions were performed in a high temperature and pressure batch reactor with temperature ranging from 200 to 260 ℃, time ranging from 4 to 10 min, pressure ranging from 5 to 25 MPa and varying concentration of additives to consider the influence of these parameters on the yield of IDA salts. Reactivity of IDAN was not illustrated with the conversion but with respect to the yield of resultant IDA salts. The results demonstrate that hydrolysis reactivity of IDAN under the examined conditions has shown a remarkable sensitivity to the pH of the system at initial point of the reaction stage, and temperature effect is also obvious. Based on the results, possible reaction pathway and mechanism were proposed.

Adsorption of Iminodiacetic Acid Resin for Lutetium

The adsorption behavior and mechanism of a novel chelate resin, iminodiacetic acid resin (IDAAR) for Lu(Ⅲ) were investigated. The statically saturated adsorption capacity is 210.8 mg·g^(-1) at 298 K in HAc-NaAc medium. The Lu(Ⅲ) adsorbed on IDAAR can be eluted by 0.5 mol·L^(-1) HCl and the elution percentage reaches 96.5%. The resin can be regenerated and reused without obvious decrease in adsorption capacity. The apparent adsorption rate constant is k_(298)=2.0×10^(-5) s^(-1). The adsorption behavior of IDAAR for Lu(Ⅲ) obeys the Freundlich isotherm. The thermodynamic adsorption parameters, enthalpy change ΔH, free energy change ΔG and entropy change ΔS of IDAAR for Lu(Ⅲ) are 13.1 kJ·mol^(-1), -1.37 kJ·mol^(-1) and 48.4 J·mol^(-1)·K^(-1), respectively. The apparent activation energy is E_a=31.3 kJ·mol^(-1). The molar coordination ratio of the functional group of IDAAR to Lu(Ⅲ) is about 3∶1. The adsorption mechanism of IDAAR for Lu(Ⅲ) was examined by chemical method and IR spectrometry.

Synthesis and Crystal Structure of a Two-dimensional Silver Framework Constructed by H_2idc (H_2idc = Iminodiacetic Acid)

A new compound formulated [Ag2(idc)](NO3)?H2O (H2idc = iminodiacetic acid) was synthesized under mild conditions and characterized by IR spectrum and single-crystal X-ray diffraction. The crystal crystallizes in the monoclinic system, space group of P21/n with a = 5.5029(2), b = 11.1316(5), c = 15.5319 (1) ?, β = 96.038(3)o, V = 946.15(6) ?3, Z = 4, R = 0.0619 and wR = 0.1606. Its structure is a 2D polymer, whose repeat units consist of dinuclear silver cluster coordinated by two bridging iminodiacetic acids. In the complex, the Ag(I) ions adopt three coordinate fashions, and the Ag-Ag metal-metal contacts of 2.8418 ? are observed.

Study on Inspection of Synthetic Reaction for Preparation of N-(phosphonomethyl) iminodiacetic Acid with Iminodiacetic Acid by Precolumn Derivatization-HPLC

The derivatives of the reaction liquid for synthesizing N-（phosphonomethyl） iminodiacetic acid （PMIDA） were synthesized with 9-fluorenyl methyl chlomformate （FMOC-C1） as the derivatization reagent. The separation of the derivatives was performed on a Gemini C18 column at room temperature by isocratic elution. The mobile phase was composed of 60% 0.05 M Nail2 PO4 （pH = 3.5） and 40% CH3 CN at a flow rate of 1 ml/min. The injection volume was 10 td, and the detection wavelength was 265 nm. The linear ranges of the derivatives of iminodiacetonitrile, iminodiacetic acid （IDA） and ammonia were, respectively, 0.02-1.2, 0.02-1.2 and 0.1 -2. 0 mg/ml with correlation coefficients not smaller than 0. 999 8. The detection limits for the derivatives were, respectively, 0. 000 4, 0. 000 4 and 0.003 mg/ml. The average recoveries of 3 derivatives were respectively 99.96%, 99. 86% and 99.89%, respectively, with relative standard deviation values not smaller than 1.6%. The method developed in the present paper could be used for monitoring the reaction system for preparation of PMIDA by IDA.

双甘膦合成草甘膦工艺及优化研究

目的:双甘膦合成草甘膦工艺及优化效果。方法:以双甘膦合成草甘膦为主要研究对象,在对草甘膦的工艺合成原理进行简单介绍之后,着重对双甘膦合成草甘膦工艺的优化进行了研究和分析,将溶剂类型、双氧水氧化温度、双氧水的质量以及硫酸亚铁加入量四项要素作为实验变量,对双甘膦合成草甘膦工艺优化实验进行研究。结果:应用地下水作为溶剂,在67~69℃的温度条件下,双甘膦和双氧水摩尔比为1:1.2,双甘膦和硫酸亚铁摩尔比为100:2.16~2.67,在此配比下作为草甘膦工艺优化的最佳条件。结论:经由本文实验得到的数据,可以证实对双甘膦合成草甘膦工艺进行优化的方法符合工艺生产的要求,也能够体现出良好的经济性,适合在企业生产中推广应用。

亚氨基二乙酸型螯合树脂柱-电感耦合等离子体质谱法测定家禽养殖废水中7种金属元素的残留量

提出了亚氨基二乙酸型螯合树脂柱-电感耦合等离子体质谱法测定家禽养殖废水中铅、锰、钡、镉、铝、铬、钴等7种金属元素残留量的方法。取预处理后的家禽养殖废水样品25 mL,以2.0 mL·min^(−1)流量过活化后的亚氨基二乙酸型螯合树脂柱;用15 mL水清洗,15 mL 5%(体积分数,下同)硝酸溶液洗脱,收集洗脱液,用5%硝酸溶液定容至25 mL;按照电感耦合等离子体质谱仪的工作条件测定得到的待测样品溶液中7种金属元素的含量,内标法定量。结果表明:7种金属元素标准曲线的线性范围均为0.005~8.0μg·L^(−1),检出限(3S/N)为0.006~0.018 ng·L^(−1);加标样品中7种金属元素测定值的相对标准偏差(n=6)为1.7%~3.8%,回收率为82.5%~93.0%。

Investigation on the Use of the Weakly Basic Polyacrylate Anion-Exchanger Amberlite IRA-68 for Sorption and Separation of Iminodiacetate Complexes of Rare Earth Elements

Based on the determined affinity series of rare earth element complexes with IMDA for the anion-exchangers, purification of macroquantities of Nd 3+ from Y 3+, Sm 3+ from Ho 3+, La 3+ from Nd 3+ and La 3+ from Pr 3+ on the weakly basic gel anion-exchanger Amberlite IRA-68 was studied. Using the presented method on 1 L of Amberlite IRA-68 in the acetate form, it is possible to obtain about 240 g Nd 2O 3 purified from Y 2O 3. Great difference in affinity of La 3+ and Nd 3+ as well as Pr 3+ complexes for this anion-exchanger in the acetate form indicates the possibility of applying this process for purification of lanthanum on the increased scale. On 1 L of Amberilte IRA-68 in the acetate form it is possible to obtain about 1125 g La 2O 3 purified from Nd 2O 3. On the basis of these results it can be assumed that unique properties of polyacrylate anion-exchangers enable their application for separation of rare earth elements.

Synthesis of an Indium-iminodiacetate Two-dimensional Layer Network with Rhombus Grids

The title compound, [InCl（C4H5NO4）]n, has been synthesized via the hydrothermal method and characterized by IR, elemental analysis, UV-Vis-Nir spectra and single-crystal X-ray diffraction analysis. Single-crystal X-ray analyses show that it is a carboxylate-bridged two-dimensional layer network indium（III） polymer, catena-poly[[chloroindium（III）]-μ-（iminodiacetate к4N,O,O＇：O＇＇：O＇＇＇]. The crystal is of orthorhombic system, space group Pnma with a = 13.5970（13）, b = 8.7671（10）, c = 6.0427（5）, C4H5ClInNO4, Mr = 281.36, V = 720.33（12）3, Z = 4, Dc = 2.594 g/cm3, F（000） = 536, μ = 3.613 mm-1, R = 0.0245 and wR = 0.0570. The In（III） ion exhibits an approximately octahedral InClNO4 coordination environment, with the two O donor atoms of iminodiacetate and two O atoms belonging to the carboxylate group of two adjacent iminodiacetates occupying the basal positions, and the chlorine ion and one nitrogen atom of iminodiacetate in the apical sites. Carboxylate groups are mutually cis oriented, and each syn-anti carboxylate group bridges two indium（III） ions via two different basal positions, resulting in the formation of a 2-D network with rhombus （4, 4） grids. Each rhombus grid unit is formed from four indium atoms and four iminodiacetate units with the diagonal lengths of 8.767（1） and 6.043（1）.

Synthesis of Bifunctional Poly(Vinyl Phosphonic Acid-<i>co</i>-glycidyl Metacrylate-<i>co</i>-divinyl Benzene) Cation-Exchange Resin and Its Indium Adsorption

Poly(vinyl phosphonic acid-co-glycidyl methacrylate-co-divinyl benzene) (PVGD) and PVGD containing an iminodi-acetic acid group (IPVGD), which has indium ion selectivity, were synthesized by suspension polymerization, and their indium adsorption properties were investigated. The synthesized PVGD and IPVGD resins were characterized using Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and mercury porosimetry. The cation-exchange capacity, the water uptake and the indium adsorption properties were investigated. The cation-exchange capacities of PVGD and IPVGD were 1.2 - 4.5 meq/g and 2.5 - 6.4 meq/g, respectively. The water uptakes were decreased with increasing contents of divinyl benzene (DVB). The water uptake values were 25% - 40% and 20% - 35%, respectively. The optimum adsorption of indium from a pure indium solution and an artificial indium tin oxide (ITO) solution by the PVGD and IPVGD ion-exchange resins were 2.3 and 3.5 meq/g, respectively. The indium adsorption capacities of IPVGD were higher than those of PVGD. The indium ion adsorption selectivity in the artificial ITO solution by PVGD and IPVGD was excellent, and other ions were adsorbed only slightly.

Determination of iminodiacetic acid in the glyphosate by ion chromatography

In this paper,a simple method based on ion chromatography（IC） with conductivity detection was developed for the determination of iminodiacetic acid（IDA） in the herbicide of glyphosate.Under optimized chromatographic conditions,good linear relationship,sensitivity and reproducibility were obtained.The detection limit（LOD） for IDA obtained by injecting 25 μL of sample was 31.8 μg/L（S/N = 3）.Relative standard deviation（RSD） of repeated analysis for the peak areas was less than 1.53%（n = 6）.A spiking study was performed with satisfactory recoveries between 92.8%and 103.6%.It was confirmed that this method could be applied in glyphosate products.

螯合树脂-恒温振荡法提取水中六种重金属的方法研究

采用D402亚胺基二乙酸型螯合树脂为载体,通过恒温振荡法提取水中镉、钴、铜、铅、锌、镍金属离子,实现水中多种重金属离子的快速分离。研究了树脂用量、振荡时间、振荡温度等条件对螯合树脂提取水中多种重金属离子的影响。结果表明,树脂用量3 g,振荡时间40 min,振荡温度55℃可以有效提取水中多种金属离子,该方法的回收率为91.0%~99.5%,精密度为0.4%~3.5%。研究证实了该方法对多种金属离子有很好的提取效果,同时该方法成本低,操作简单,绿色环保,适用于水环境监测实验中六种金属离子的快速准确测定。

Study on the Complexation of Molybdenum（Ⅵ） with Iminodiacetic Acid and Ethylenediamine-N,N′-diacetic Acid by Specific Ion Interaction and Debye-Hückel Theories

Complexation of two ligands, iminodiacetic acid and ethylenediamine-N,N′-diacetic acid, with molybdenum（Ⅵ） was studied in aqueous solutions. Molybdenum（Ⅵ） forms a mononuclear complex with the aforementioned ligands of the type MoO3L^2-. All measurements have been carried out at 25 ℃ and different ionic strengths ranging from 0.1 to 1.0 mol·L^-1 of NaClO4, with the pH justified to 6.0. Equilibrium concentration products and stoichiometry of the complexes have been determined from a combination of potentiometric and UV spectroscopic measurements. Comparison of the ionic strength effect on these complex formation reactions has been made using a Debye-Hückel type equation and Bronsted-Guggenheim-Scatchard specific ion interaction theory （SIT）. Debye-Hückel theory predicted the first order effects on simple electrolyte solutions. Interactions between the reacting species and the ionic medium were taken into account in the SIT model. All of the calculations have been done by the computer program Excel 2000.

亚氨基二乙酸的合成研究

在非晶态合金催化剂下由二乙醇胺和氢氧化钠一步合成亚氨基二乙酸钠 ,采用双极性膜电渗析和反渗透技术取代现行工艺中亚氨基二乙酸钠转化成亚氨基二乙酸的酸化过程。亚氨基二乙酸总收率≥ 95 % ,纯度≥ 99% ,该技术路线成熟可靠 ,指标优良 ,有利于促进我国草甘膦除草剂的开发生产。

非晶态合金催化剂用于二乙醇胺脱氢氧化制备亚氨基二乙酸的研究

用自制的非晶态合金催化剂一步催化脱氢氧化二乙醇胺合成亚氨基二乙酸 ,考察了催化剂与二乙醇胺的质量比、反应温度、时间、压力和pH值对亚氨基二乙酸转化率的影响 ,并与其它RaneyCu类催化剂进行了对比。结果表明 ,使用CSGZ - 0 4非晶态合金催化剂进行二乙醇胺脱氢氧化 ,当反应温度为 16 0～ 180℃、压力为 12～ 18MPa、pH值为 12 6 8、催化剂与二乙醇胺质量比为 16 5∶10 0、反应时间为 2 5～ 3h时 ,亚氨基二乙酸的收率≥ 98% ,CSGZ - 0 4催化剂重复使用2 4次时 ,亚氨基二乙酸的收率≥ 95 %

非晶态合金催化剂用于二乙醇胺氧化合成亚氨基二乙酸

采用自制的非晶态合金催化剂进行二乙醇胺氧化合成了亚氨基二乙酸 ,探讨了催化剂用量、反应温度、反应时间、氢氧化钠用量、反应压力等因素对氧化反应的影响 ,确定了最佳工艺条件 。

亚氨基二乙酸的生产与应用

亚氨基二乙酸是一种用途广泛的重要精细化工中间体。综述了目前亚氨基二乙酸的几种合成方法,比较几种合成方法的优缺点。亚氨基二乙酸目前主要作为合成农药草甘膦的中间体使用,同时在电镀行业、染料、水处理、电子等众多领域也得到不同的应用。目前国内亚氨基二乙酸的生产能力远不能满足需求,因此具有很大的发展潜力。

草甘膦中间体亚氨基二乙酸合成新工艺

研究了一种新的草甘膦中间体亚氨基二乙酸合成工艺。5℃时加入氨水、羟基乙腈及阻聚剂进行氨解反应生成中间体亚氨基二乙腈,在102℃,碱水解该化合物,生成相应的亚氨基二乙酸钠盐。用酸将溶液酸化至亚氨基二乙酸的等电点,亚氨基二乙酸晶体析出,脱色重结晶,抽滤、干燥得产品亚氨基二乙酸。亚氨基二乙酸的收率85%,含量达99.3%。

亚氨基二乙酸树脂吸附钇(Ⅲ)的研究(英文)

The adsorption behavior and mechanism of a novel chelate resin, iminodiacetic acid resin (IDAAR) for Y? were investigated. The statically saturated adsorption capacity is 102mg· g- 1 resin at 298K in HAc NaAc medium at pH 5.7. Y? adsorbed on IDAAR can be reductively eluted by 1.0～ 4.0mol· L- 1 HCl used as eluant and the elution percentages are almost as high as 100% . The resin can be regenerated and reused without apparent decrease in adsorption capacity. The apparent adsorption rate constant is k298=3.36× 10- 5s- 1. The adsorption behavior of IDAAR for Y? conforms to Freundlich′ s model reasonably. The thermodynamic adsorption parameter, enthalpy change Δ H of IDAAR for Y? is 18.6kJ· mol- 1. The complex molar ratio of the functional group of IDAAR to Y? is about 3∶ 1. The adsorption mechanism of IDAAR for Y? was examined by using chemical method and IR spectrometry.