高纯磷酸盐的应用、生产工艺及分析方法研究进展
顾小焱1, 凌芳*1, 刘清龙1, 刘征宙2, 洪亚云2, 赵红莉2
（1.国药集团化学试剂有限公司，上海 200002; 2.华东理工大学 化学与分子工程学院，上海 200237）
摘要：近年来，随着对食品级、医药级、电子级和半导体级等高纯磷酸盐的需求日益增加，发展并进一步完善高纯磷酸盐的生产工艺、提高磷酸盐产品纯度、建立产品技术指标及分析检测方法对日益发展的高纯磷酸盐产业具有重要意义。综述了高纯磷酸盐的应用领域、主要生产工艺和纯化方法，以及国内外高纯磷酸盐技术指标比对及分析检测方法，主要以磷酸二氢钾（KH2PO4）为例进行说明。
关键词：高纯磷酸盐；应用；生产工艺；分析方法
中图分类号：P578.92 文献标识码：A 文章编号：0258-3283（2017）
Research Progress in Application, Production Technology and Analytical Methods of High Purity Phosphate GU xiao-yan1, LING Fang*1 , LIU Qing-long1 , LIU Zheng-zhou1 , HONG Ya-yun2, ZHAO Hong-li2 (1.Sinopharm Chemical Reagent Co., Ltd, Shanghai 200002, China;2.School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China), Huaxue Shiji, 2017, 39(10)
Abstract: In recent years, because of the increased demand for high purity phosphate, such as food grade, electronic grade, metal-oxide-semiconductor grade (MOS reagents), it is significant to develop and improve the production technology and to establish the technical indicators and analytical methods of phosphate. In this paper, the application, main production and purification technology of high purity phosphate were firstly reviewed. And then, we compared and commented the technical indicators and analytical methods of phosphate at home and abroad. In most of cases, potassium dihydrogen phosphate (KH2PO4) was used as an example to illustrate.
Key words: high purity phosphate; application; production technology; analytical methods
锂离子吸附球形树脂的合成及其性能研究
蔡静，梁渠*，赵晓乐，庞莎莎，刘凯
（成都理工大学 材料与化学化工学院，四川 成都 610059）
摘要：为实现高镁锂比盐湖卤水的锂镁分离，合成了一种新的锂离子吸附球形树脂。该树脂采用对锂离子有特定螯合作用的二苯并-14-冠-4为功能单元，并与有机磷酸酯形成对锂离子的协同萃取体系，以聚氨酯为树脂骨架，通过悬浮聚合得到锂离子吸附球形树脂。悬浮聚合以二甲基硅油为分散介质、以粒度为300 ~ 400目的碳酸钙为稳定剂、n(羟甲基化产物)︰n(有机磷酯)︰n(甲苯二异氰酸酯) = 1︰1︰28，以聚醚多元醇为交联剂、锂溶液为模板致孔剂，反应温度为80 ℃，时间为10 h，搅拌速度为280 r/min，得到粒度范围为55.36 ~ 76.33 μm的球形树脂。热分析表明，树脂是均质的，具有较高的热稳定性。树脂经索氏抽提8 h的溶损率为1.5%，说明其水中使用是稳定的。在pH 7、恒温振荡温度为25 ℃、振荡时间为4 h时，得到树脂对锂的最大吸附容量为0.6099 mmol/g，其对锂镁选择性系数为β = 39；5次再生实验，其树脂饱和吸附容量下降仅为1.8%，表明树脂可多次使用。
关键词：悬浮聚合；冠醚；锂离子球型吸附树脂；锂镁分离
中图分类号：O622.3 文献标识码：A 文章编号：0258-3283（2017）
Synthesis and Properties of Lithium Ion AbsorptionSpherical Resin CAI Jing，LIANG Qu，ZHAO Xiao-le，PANG Sha-sha，LIU Kai（Department of Chemistry, College of Material and Chemical Engineering, Cheng Du University of Technology, Cheng du 610059, China）, Huaxue Shiji, 2017, 39(10)
Abstract：In this work, a new kind of lithium ion adsorption spherical resin was synthesized. It was used to extract lithium ion from salt lake brine with high magnesia/lithium ratio. By using dibenzo-14-crown-4(DB14C4) as functional group for chelating lithium ion，the synergistic extraction system being formed with organic phosphorus together, adsorption resin was synthesized by means of suspension polymerization, using polyurethane as basic skeleton of the resin, and methyl silicone oil as dispersing medium, calcium carbonate(particle size is 300~400 mesh) as stabilizer, molar ratio of suspension polymerization of hydroxymethylation products, organophosphorus ester, toluene diisocyanate 1︰1︰28, polyether glycol as crosslinking agent, lithium solution as template pyrogenic agent, reaction temperature being 80 ℃, reaction time being 10 h, stirring speed 280 r/min, the particle size range 55.36 ～ 76.33 μm of lithium ion adsorption spherical resin was obtained. Thermal analysis showed that the resin was homogeneous and had high thermal stability. Soluble loss rate was only 1.5%. And it is stable using in water. The maximum adsorption capacity of the resin is 0.6099mmol/g.The optimal condition is pH = 7, constant temperature T = 25 ℃, shock time t = 4 h. The lithium magnesium selective coefficient of resin is β= 39. The regeneration of the resin for saturated adsorption capacity decline was only 1.8%, which shows the resin could be used repeatedly.
Key words：suspension polymerization; crown ether; lithium ion adsorption spherical resin; separation of lithium and magnesium
N-双嘧啶取代芳胺的合成及其抗氧化损伤研究
杨飞a，陈俊a，李琪琪a，李佳鹏b，廖兴华b，叶龙*a
（武汉科技大学 a. 化学与化工学院，b. 生物医学研究院，湖北 武汉 430081）
摘要：报道了一种N-双嘧啶取代芳胺衍生物2-(3-氯苯基)-N-(2-(3-氯苯基)-6-甲基嘧啶-4-基)-N-(2-甲氧苯基)-6-甲基嘧啶-4-胺的合成、表征及其抗氧化生物活性，该N-双嘧啶取代芳胺衍生物是以3-氯苄腈为原料经4步反应合成而得到，其结构通过1HNMR、13CNMR、HR-MS进行了表征和确认。化合物的抗氧化作用与细胞毒作用分别通过是否进行双氧水处理的SH-SY5Y细胞与CCK-8试剂盒进行检测，通过荧光探针DCFH-DA标记检测细胞内ROS含量。结果表明，该化合物具有抗双氧水氧化损伤的可能，能够显著提高细胞存活率且没有明显的细胞毒性。
关键词：N-双嘧啶取代芳胺衍生物；双氧水；抗氧化活性；SH-SY5Y细胞
中图分类号：R914.5 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of Bipyrimidine-substituted Aryl Amine Derivatives and Anti-oxidative Damage Assay YANG Feia, CHEN Juna, LI Qi-qia, LI Jia-pengb, LIAO Xing-huab, YE Long*a ( a.School of chemistry and chemical engineering, b. Institute of biology and medicine, Wuhan University of Science and Technology, Wuhan 430081, China), Huaxue Shiji, 2017, 39(10)
Abstract: This work describes the synthesis, characterization of a bipyrimidine-substituted aryl amine derivative 2-(3-chlorophenyl)-N-(2-(3-chlorophenyl)-6-methylpyrimidin-4-yl)-N-(2-methoxyphenyl)-6-methylpyrimidin-4- amine and its anti-oxidative activity. The bipyrimidine-substituted aryl amine derivative is synthesized via four
steps reactions starting from 3-chlorobenzonitrile. The structure of the compound was confirmed with 1HNMR,
13CNMR and HR-MS. The anti-oxidative effect and cytotoxicity of the compound are tested with CCK-8 assay kit and SH-SY5Y cells treated with or without hydrogen peroxide. The intracellular accumulation of ROS assay was done with fluorescent probe DCFH-DA. The results suggest that this bipyrimidine-substituted aryl amine derivative is able to protect cells from oxidative stress-induced death and significantly increase the cell viability without evident toxicity.
Key words: bipyrimidine-substituted aryl amine derivatives; hydrogen peroxide; anti-oxidative activity; SH-SY5Y cells
H6P2Mo9W9O62/Zn(BDC)(Bipy)0.5复合材料催化合成3,4-二氢嘧啶-2(H)酮衍生物
向诗银，杨水金*
（湖北师范大学 化学化工学院，湖北 黄石 435002）
摘要：采用水热法分别合成杂多酸H6P2Mo9W9O62及有机金属骨架Zn(BDC)(Bipy)0.5，使用浸渍法合成H6P2Mo9W9O62/Zn(BDC)(Bipy)0.5复合材料，用该复合材料催化醛、乙酰乙酸乙酯和尿素通过Biginelli反应，乙醇作溶剂，合成6种3,4-二氢嘧啶-2(H)酮衍生物。通过IR、1HNMR、13CNMR确定其结构，通过m. p.确定其纯度。实验结果表明：n (醛)︰n (乙酰乙酸乙酯)︰n (尿素) = 1︰1.4︰1.5，2.0 wt% H6P2Mo9W9O62/Zn(BDC)(Bipy)0.5，反应温度为105 ℃，反应时间为 60 min，产物收率为40.1% ～ 91.5%。
关键词：H6P2Mo9W9O62/Zn(BDC)(Bipy)0.5；Biginelli反应；3,4-二氢嘧啶-2(H)酮衍生物
中图分类号：TQ460 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of 3,4-Dihydropyrimidine-2(1H)-one Derivatives with H6P2Mo9W9O62/Zn(BDC)(Bipy)0.5 as Catalyst XIANG Shi-yin, YANG Shui-jin*(College of Chemistry and Chemical Engineering, Hubei Normal University, Huangshi 435002, China), Huaxue Shiji, 2017, 39(10)
Abstract: Six kinds of 3,4 -dihydropyrimidine-2 (1H)-one derivative were prepared via Biginelli-typecondensation with ethyl acetoacetate, aromatic aldehyde and urea as starting materials, anhydrous ethanol as solvent andH6P2Mo9W9O62/Zn(BDC)(Bipy)0.5 as catalyst.H6P2Mo9W9O62and Zn(BDC)(Bipy)0.5was prepared by hydrothermal method, The catalyst was prepared by loading of heteropoly acid on metal organic skeleton by impregnation method．Structures were confirmed by IR,1H NMR,13C NMRand melting point determination. The results showed that under the conditions of fixed aromatic aldehyde feed of 0. 04 mol, n( aromatic aldehyde) ∶n( ethyl acetoacetate) ∶n( urea) = 1∶1.4∶1.5, the dosage of catalyst at 2. 0% of total mass of the starting materials, reactiontemperature at 105℃ and reaction time of 60 min. The yield of the target products achieves 40.1% ～ 91.5%.
Key words: H6P2Mo9W9O62/Zn(BDC)(Bipy)0.5；Biginelli reaction；3, 4-dihydropyrimidine -2(1H)-onederivative
基于Mn掺杂ZnS室温磷光量子点检测盐酸洛美沙星方法的研究
牛娟，张直峰，闫桂琴*
（山西师范大学 生命科学学院，山西 临汾 041000）
摘要：利用水相合成法制备了三巯基丙酸包裹的Mn掺杂ZnS量子点(MPA-Mn/ZnS QDs)，基于该量子点的室温磷光性质，构建了一种定量检测盐酸洛美沙星（LFLX）的新方法。在最优实验条件下（pH 7.4，反应时间10 min），LFLX浓度在0.002 ～ 1.4 μg/mL范围内与MPA-Mn/ZnS QDs的磷光猝灭强度呈良好的线性关系(r ＝ 0.993)，方法检出限为0.7 × 10-3 μg/mL。该方法相对无共存物质的干扰，并适用于LFLX眼药水及人体尿样中LFLX的快速检测。
关键词：Mn掺杂ZnS量子点；室温磷光；盐酸洛美沙星；检测
中图分类号：O657.3 文献标识码：A 文章编号：0258-3283（2017）
Detection MethodofLomefloxacin Hydrochloride Based on Room Temperature Phosphorescence of Quantum Dots NIU Juan, ZHANG Zhi-feng, YAN Gui-qin*( College of Life Science, Shanxi Normal University, Linfen 041000, China), Huaxue Shiji, 2017, 39(10)
Abstract：The 3-mercaptopropionate acid (MPA)-capped Mn-doped ZnS quantum dots(Mn/ZnS QDs) were prepared using water phase synthesis. Based on the room temperature phosphorescence(RTP) properties of QDs, a new method for detecting lomefloxacin hydrochloride(LFLX)was established. Under the optimal conditions (pH 7.4, reaction time: 10 min), the phosphorescence quenching strength ratio of MPA-Mn/ZnS QDs had a good linear relationship (r＝0.993) with concentration of LFLX in the range of 0.002 to 1.4 μg/mL. The detection limit for LFLX was 0.7×10-3 μg/mL.The proposed method was relatively free of interference from coexisting substances, and this method could be applied in the rapid detection of LFLXeye drops andurine samples.
Key words: MPA-capped Mn-doped ZnS quantum dots (MPA-Mn/ZnS QDs); room temperature phosphorescence (RTP); lomefloxacin hydrochloride(LFLX); detection
两个苯并咪唑羧酸稀土配合物的合成、晶体结构及荧光性质
张倩*，陈垒，叶英杰，吴家进
（河南工程学院 材料与化学工程学院，河南 郑州 450007）
摘要: 合成了1, 3-二羧甲基苯并咪唑有机配体，并与氯化铕、氯化钐反应得到了两个新的稀土配合物，通过元素分析、X-射线单晶衍射及X-射线粉末衍射对其进行表征。晶体结构表明，两个配合物均为两个金属中心被4个配体桥联形成Ln2O8型双核次级结构基元，这些次级基元通过(κ1-κ1-μ2)-(κ1)-μ3配位模式与配体形成(4, 4)拓扑的二维网络结构。同时测定了这两个配合物的热稳定性及Eu配合物的荧光性质。
关键词：稀土配合物；苯并咪唑羧酸；二维网络结构；荧光性质
中图分类号：O614. 7 文献标识码：A 文章编号：0258-3283（2017）
Synthesis, Crystal Structure and Luminescent Property of TwoRare Earth ComplexesConstructed from Benzimidazolyl-carboxylic Acid ZHANG Qian*, CHEN Lei, YE Ying-jie, WU Jia-jin (School of Materials and Chemical Engineering, Henan Universty of Engineering, Zhengzhou 450007, China), Huaxue Shiji, 2017, 39(10)
Abstract：A organic ligand 1, 3-bis(carboxymethyl) benzimidazolium was synthesized, and two new rare earth complexes were obtained by the ligand reacting with EuCl3 and SmCl3 under the solution condition. The complex structure was confirmed by elemental analysis, X-ray crystal diffraction and X-ray powder diffraction. The results indicated that two metal center were bridged by four bidentate ligands to generate binuclear secondary building block of Ln2O8, which are furthermore linked to each other resulting in the formation of 2D (4,4) network structure. In addition, the thermos ability of the two complexes and luminescent property of the Eu3+complex were investigated.
Key words: rare earth complex; benzimidazolyl carboxylic acid; 2D network structure; luminescent property
噻吩并嘧啶酮类PDE7抑制剂的特征结构及作用机制研究
高庆平*1，吴倩2，孟丹丹2，李燕3，杨凌4
(1.潍坊职业学院 化学工程学院，山东 潍坊 262737；2. 潍坊学院 化学化工与环境工程学院，山东 潍坊 261061；3. 大连理工大学 化工与环境生命学部，辽宁 大连 116024；
4. 中国科学院大连化学物理研究所 药物资源开发研究组，辽宁 大连 116023)
摘要：基于定量构效关系和分子对接研究理论，以34个噻吩并嘧啶酮类磷酸二酯酶7(PDE7)抑制剂为研究对象，采用比较分子相似性指数法(CoMSIA)和GOLD分子对接法研究其特征结构信息以及与靶标的作用机制。结果表明，所建CoMSIA模型的预测能力较强(Q2= 0.53，Rncv2 = 0.96，Rpre2 = 0.89)，结合分子对接结果还发现，抑制剂与PDE7间的作用力以氢键作用力和π-π堆积作用为主；大体积的亲水性氢键供体R1取代基、亲水性R2取代基有利于化合物活性的增强，且哌啶环上益于结合氢键的受体基团。所得模型和信息为后续新型PDE7抑制剂的设计开发提供理论指导。
关键词：噻吩并嘧啶酮类PDE7抑制剂；比较分子相似性指数法；分子对接；作用机制
中图分类号：Q67 文献标识码：A 文章编号：0258-3283（2017）
Structural Features and Interaction Mechanismof Thienopyrimidinonesas PDE7Inhibitors GAO Qing-ping*1,WU Qian2, MENG Dan-dan2, LIYan3,YANG Ling4(1. School of Chemical Engineering, Weifang Vocational College, Weifang 262737, China; 2. Department of Chemical and Environmental Engineering, Weifang University, Weifang 261061, China; 3. Department of Materials Science and Chemical Engineering, Dalian University of Technology, Dalian 116024, China; 4. Lab of Pharmaceutical Resource Discovery, Dalian Institute of Chemical Physics, Graduate School of the Chinese Academy of Sciences, Dalian 116023, China）, Huaxue Shiji, 2017, 39(10)
Abstract: Based on quantitative structure-activity relationship and molecular docking theory, the structural features and interaction mechanism of 34 thienopyrimidinone derivatives as phosphodiesterase 7 (PDE7) inhibitors were investigated by comparative molecular similarity indices analysis (CoMSIA)and GOLD molecular docking methods. The CoMSIA model shows a strong predictability (Q2=0.53，Rncv2=0.96，Rpre2=0.89). Meanwhile, from the CoMSIA contour maps and docking results, it can be concluded that H-bond and π-π stacking interactions are crucial in determining the binding affinity to PDE7. And R1 groups should select the bulk, hydrophilic and H-bond donor ones. R2 partis the steric sensitive region, introduction of the hydrophilic groups into this region are the excellent options. Furthermore, the substituents acting as H-bond acceptor at piperidine ring are conducive to the activity increase. This model and the derived information may help to provide better understanding of the structure features of PDE7 inhibitors and binding mode between the acceptor and ligands, facilitating corresponding novel inhibitors design.
Key words: thienopyrimidinones PDE7 inhibitors; CoMSIA; molecular docking; interaction mechanism
PEG4000/(NH4)2SO4双水相
制备超顺磁性Fe3O4纳米粒子及性能表征
于文国*1，杜会茹1，黄文杰1 ，王麟1，张天纬2
（1. 河北化工医药职业技术学院 制药工程系，河北 石家庄 050018；
2. 北京诺禾致源生物科技有限公司，北京 100080）
摘要：以PEG4000和(NH4)2SO4为双水相体系、二异丙胺为沉淀剂，对共沉淀法进行改进，合成了四氧化三铁（Fe3O4）纳米粒子。采用XRD、TEM、VSM、FT-IR等对Fe3O4进行性能表征，证明合成的Fe3O4粒子为具有反尖晶石结构、稳定性和分散性良好、尺寸均一、粒径大小为11 nm左右的球形纳米粒子，具备优异的超顺磁性和高磁化强度等特性。并对反应温度及铁离子浓度比、PEG4000/(NH4)2SO4的质量浓度对双水相体系的形成进行条件探索，确定出了最优工艺方案为n(Fe2+) : n(Fe3+) = 2 : 3、1.0 g FeCl2·4H2O、1.2 g FeCl3、10 mL二异丙胺，PEG4000/(NH4)2SO4双水相体系中PEG4000的质量浓度为18%、(NH4)2SO4的质量浓度为25%，反应温度为60 ℃，反应时间为1 h。
关键词：Fe3O4；纳米粒子；双水相体系；合成
中图分类号：R318.08 文献标识码：A 文章编号：0258-3283（2017）
Preparation and Analysis of Super-paramagnetic Fe3O4 Nanoparticles by EG4000/(NH4)2SO4 Aqueous Two-phase System YU Wen-guo*1, DU Hui-ru1, HUANG Wen-jie1, WANG Lin1, ZHANG Tian-wei2（1. Department of Pharmaceutical Engineering, Hebei Chemical and Pharmaceutical College, Shijiazhuang 050018, China; 2. Novogene Bio Technology Co., Ltd., Beijing 100080, China）, Huaxue Shiji, 2017, 39(9)
Abstract: Fe3O4 of super-magnetic nanoparticles were obtained by PEG/(NH4)2SO4 aqueous two-phase system under the diisopropylamine as precipitating agent. The nanoparticles of Fe3O4 were characterized systematically by means of XRD, FT-IR, VSM and TEM. The conditions for the preparation of Fe3O4 magnetic nanoparticles were optimized, with the molar ratio of Fe2+ (1.0 g)and Fe3+(1.2 g)of 2 : 3, under the diisopropylamine as precipitating agent, reaction temperature at 60 ℃, by PEG/(NH4)2SO4 aqueous two-phase system. The results revealed that the magnetic nanoparticles were spheroid shaped, and dispersed with narrow size, and the average diameter of 11 nm, and had excellent superparamagnetism and high saturated magnetization.
Key words：Fe3O4；magnetic nanoparticles；aqueous two-phase system; synthesis
联烯类化合物[3+2]环加成反应的研究进展
周睿，李兴，常宏宏，高文超，魏文珑*
(太原理工大学 化学化工学院，山西 太原 030024)
摘要：联烯是具有丙二烯结构单元的一类不饱和化合物，由于其特殊结构，使其具有多种反应活性，可与许多含不饱和键的化合物发生环加成反应来制备许多环状化合物。综述了近几年来联烯类化合物与含各种不饱和键化合物[3+2]环加成反应的研究进展，并对其发展方向进行了展望。
关键词：联烯；环加成；不饱和键
中图分类号：O626.1；O624.12 文献标识码：A 文章编号：0258-3283（2017）
Progress in the [3+2] Cycloaddition Reactions of Allenes ZHOU Rui, LI Xing, CHANG Hong-hong, GAO Wen-chao, WEI Wen-long* (College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China), Huaxue Shiji, 2017, 39(9)
Abstract：Allenes, an unsaturated compounds with structural unit of propadiene, exhibit various reactivity due to the special structure. Therefor, can react with various unsaturated compounds to give kinds of cyclic compounds. The recent progress in the [3+2] cycloaddition reactions of allenes compounds with various compounds is reviewed. Moreover, the prospects of future development are also discussed.
Key words：allenes; cycloaddition; unsaturated bond
分子印迹流动注射化学发光测定胞嘧啶核苷
向辉1，谭利1，袁丝兰1，张罗一览1，郑红*1, 2, 3
（1. 重庆师范大学 化学学院，重庆 401331；2. 中国科学院青海盐湖研究所，青海 西宁 810008；3. 青海师范大学 化学系，青海 西宁 810008）
摘要：以胞嘧啶核苷为目标分子，合成对其有专一性识别的分子印迹聚合物(MIP)。在酸性条件下，利用HCl-KMnO4-HCHO发光体系，结合流动注射化学发光（FI-CL）分析方法，创建对胞嘧啶核苷测定有特异性识别的MIP-FI-CL分析方法，其线性范围为8×10-5 ～ 1×10-3 mol/L，检出限是4×10-5 mol/L。利用此方法测定复杂样品中胞嘧啶核苷的含量，结果令人满意。
关键词：胞嘧啶核苷；分子印迹；流动注射；化学发光
中图分类号： 文献标识码：A 文章编号：0258-3283（2017）
Determination of Cytidine by Molecular Imprinting-flow Injection Chemiluminescence Method XIANG Hui1, TAN Li1, YUAN Si-lan1, ZHANG-LUO Yi-lan1, ZHENG Hong*1, 2, 3(1. Department of Chemistry, Chongqing Normal University, Chongqing 401331, China;2. Qinghai Institute of Salt Lakes, Chinese of Academy of Sciences, Xining 810008, China; 3. Department of Chemistry, Qinghai Normal University, Xining 810008, China), Huaxue Shiji, 2017, 39(10)
Abstract: A molecularly imprinted polymer was prepared by molecular imprinting technique using cytidine as the template molecule. This polymer was used for the identification of cytidine molecule. Under acid condition, a MIP-FI-CL method for the determination of cytidine was established by using cytidine-imprinted polymers as recognition material and potassium permanganate and formaldehyde as detection system. The linear range was8×10-5_ 1×10-3 mol/L and the detection limit was 4×10-5 mol/L. The method was applied to the determination of cytidine in medicine with satisfactory results.
Key words: cytidine; molecularimprinting; chemiluminescence; flow injection
电还原邻硝基苯酚合成邻氨基苯酚的高效液相色谱分析法
栗彧君，郭磊，殷跃，李彦威*
（太原理工大学 化学化工学院，山西 太原 030024）
摘要：建立了一种反相高效液相色谱法同时测定邻硝基苯酚和邻氨基苯酚的新方法。采用Shim-pack VP-ODS（250 mm×4.6 mm，4.6 m）色谱柱，选用纯甲醇为流动相，以285 nm为检测波长，流速为0.8 mL/min，柱温为35 ℃，以外标法进行定量分析。实验结果表明，邻硝基苯酚和邻氨基苯酚的质量浓度在1.0 ~ 40.0 g/mL范围内呈良好的线性关系，其相关系数分别为r = 0.9995(n = 9)和r = 0.9998(n = 9)，测定其在10.0、20.0和30.0 g/mL这3个不同浓度下的方法精密度，其相对标准偏差分别≤1.28%和≤1.04%。将本方法应用于以邻硝基苯酚为原料电解合成邻氨基苯酚反应液的分析，其加标回收率分别在93.0% ~ 106.0%和90.0% ~ 107.0%之间，相对标准偏差分别≤3.75%和≤1.44%。实验结果表明，该方法可用于邻硝基苯酚和邻氨基苯酚两种组分的同时测定。
关键词：高效液相色谱法；邻硝基苯酚；邻氨基苯酚
中图分类号：O657.7 文献标识码：A 文章编号：0258-3283（2017）
High Performance Liquid Chromatography for the Synthesis of o-Aminophenol by Electroreductiono-Nitrophenol LI Yu-jun，GUO Lei，YIN Yue，LI Yan-wei*（College of Chemistry and Chemical Engineering，Taiyuan University of Technology，Taiyuan 030024，China）, Huaxue Shiji, 2017, 39(10)
Abstract: A new method for the simultaneous determination of o-nitrophenol and o-aminophenol by reversed - phase high performance liquid chromatography was developed. HPLC was carried out on a VP-ODS Shim-pack column (250 mm × 4.6 mm, 4.6 m), using pure methanol as mobile phase and the detection was performed by UV detector at 285nm, of which flow rate was 0.8 mL/min and the column temperature was 35 ℃ through the external standard method. The results showed that the o-nitrophenol and o-aminophenol concentration ranged from 1.0 g/mL to 40.0 g/mL can obtained a good linear relationship, the correlation coefficient were 0.9995 (n = 9) and 0.9998 (n = 9)respectively. Determination of the 10.0 g/mL, 20.0 g/mL, 30.0 g/mL three different concentration sample solutions of precision, the relative standard deviations were not more than 1.28% and 1.04%, respectively. It has been used to determine the product in the process of electrolytic synthesis of o-aminophenol with o-nitrophenol as raw material, the recoveries were between 93% ～ 106% and 90% ～ 107%, the relative standard deviations were not more than 3.75% and 1.44%. The results show that the method can be used not for simultaneous determination of o-nitrophenol.
Key words: high performance liquid chromatography; o-nitrophenol; o-aminophenol
卡尔费休库仑法测定熔结环氧粉末水分含量
韩冰*，李爱贵，那骥宇，娄亮杰，孔宪刚
（中国石油集团工程技术研究院，天津 塘沽 300451）
摘要：通过对卡式炉温度、终点判定模式、滴定反应时间的实验分析研究，建立了卡尔费休库仑法测定熔结环氧粉末中水分含量的优化实验方法。实验条件为卡式炉温度100 ℃，延迟时间终止模式，滴定时间18 min。该方法适用于水分含量＜0.70%的熔结环氧粉末的水分测定，精密度实验相对标准偏差为1.14%，回收率范围为93.6% ～ 99.4%。
关键词：水分含量；熔结环氧粉末；卡尔费休库仑法；卡式炉
中图分类号：O657.12 文献标识码：A 文章编号：0258-3283（2017）
Determination of Moisture Content in Fusion Bonded Epoxy Powder by Karl Fischer Coulometry Method HAN Bing*, LI Ai-gui, NA Ji-yu, LOU Liang-jie, KONG Xian-gang (CNPC Research Institute of Engineering Technology, Tanggu 300451, China), Huaxue Shiji, 2017, 39(10),
Abstract：The measure method of the moisture content in fusion bonded epoxy powder by Karl Fischer coulometry was established based on the tube oven drying temperature, the model of titration end judgment and titration reaction time. The experimental conditions were as follows: Drying temperature is 100 ℃, delay time end judgment, setting titration time is 18 mins. The method is suitable for the fusion bonded epoxy powder with moisture content less than 0.70%. The RSD of precision tests was 1.14%. The recovery rate was 93.6% ～ 99.4%.
Key words：moisture content; fusion bonded epoxy powder; Karl Fischer coulometry; tube oven
气相色谱/串联三重四级杆质谱法测定辛辣食品中25种有机磷农药残留
高尧华1，滕爽2，周婷婷*3，宋卫得1，刘冰1
(1. 日照出入境检验检疫局，山东 日照 276826；2. 南京农业大学 农业部肉及肉制品质量监督检验测试中心（南京），江苏 南京 210095；3. 山东大学 化学与化工学院，山东 济南 250100）
摘要：采用气相色谱/串联三重四级杆质谱法（GC/MS/MS）建立了分析葱、蒜、洋葱及其制品中25种有机磷的分析方法。葱、蒜、洋葱及其制品经提取、净化处理后，采用气相色谱/串联三重四级杆质谱法检测，25种有机磷农药在线性范围内均呈现良好的线性关系，线性系数＞0.99。该方法的检出限（LOD）为0.001 ～ 0.005 mg/kg。三水平六平行的实验结果表明，该类化合物的回收率为63% ～ 115%，相对偏差（RSD）为0.67% ～ 13.7%。方法重现性好、精密度高、操作简单，适用于葱、蒜、洋葱及其制品中多种有机磷的检测。
关键词：25种有机磷化合物；气相色谱/串联三重四级杆质谱法；特征离子
中图分类号：O657.63 文献标识码：A 文章编号：0258-3283(2017)
Determination of 25 Organophosphorus Pesticides in Spicy Food by Gas Chromatography /Triple Quadrupole Mass Spectrometry GAO Yao-hua1, TENG Shuang2, ZHOU Ting-ting*3, SONG Wei-de1, LIU Bing1(1. Rizhao Entry-Exit Inspection and Quarantine Bureau, Rizhao 276826, China; 2. , Nanjing Agricultural University, Nanjing 210095, China; 3. School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China), Huaxue Shiji, 2017, 39(9)
Abstract: A method was developed for the determination of 25 organophosphorus pesticides in scallions, garlic, onion and its products by gas chromatography/triple quadrupole mass spectrometry(GC/MS/MS). The scallions, garlic, onion and its products were extracted and purified, and then tested by gas chromatography/triple quadrupole mass spectrometry (GC/MS/MS), the calibration curves of 25 organophosphorus pesticides with good linearity (coefficients of determination, R2>0.99).The limit of detection (LOD) of 0.001 ~ 0.005 mg/kg, and the recoveries of 25 organophosphorus compounds at the three spiked levels of six parallel were in the range of 63% ～ 115%, with relative standard deviations (RSDs) were between 0.67% ～ 13.7%. The method with good reproducibility, high precision, simple operation. Therefore, it is suitable for analysis of organophosphorus pesticides in scallions, garlic, onions, and its products.
Key words: 25 organophosphorus pesticides; gas chromatography/triple quadrupole mass spectrometry; characteristic ions
钆配合物的合成及光电性能的研究
胡超1，吴喆*2，向莉丽1，施念1，何桂美1，王娟1
（1. 湖北大学 化学化工学院，湖北 武汉 430062；2. 湖北科技学院 基础医学院，湖北 咸宁 437100）
摘要：以磷钼酸和烟酸为配体，采用水热合成法合成了一种新颖的含稀土钆的配合物，并对该配合物进行了元素分析、红外、紫外、荧光、电化学、热重等一系列表征。结果表明该配合物在218 nm和261 nm处有两个很强的紫外吸收峰；在323 nm的光激发下，配合物在377 nm处有一个强的荧光发射峰；在－0.6 ～ 0.6 V（以饱和甘汞电极为参比电极）的电势范围内，配合物出现了两对氧化还原峰，电化学性能良好。且该配合物具有较好的热稳定性。
关键词：钆；磷钼酸；合成；光电性能
Synthesis, Luminescence and Electrochemical Properties ofGadolinium Complex HU Chao1, WU Zhe*2, XIANG Li-Li1, SHI Nian1, HE Gui-Mei1, WANG Juan1(1. School of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062, China; 2. School of Basic Medicine, Hubei University of Science and Technology, Xianning 437100, China), Huaxue Shiji, 2017, 39(10)
Abstract: A novel rare earth gadolinium complex was synthesized with phosphomolybdic acid and nicotinic acid as ligands by hydrothermal method and characterized by a series of methods, such as elemental analysis, IR, UV, fluorescence, electrochemical analysis and thermal gravimetric analysis. The complex had two very strong UV absorption peaks at 218 nm and 261 nm and the complex had a strong emission peak at 377 nm under the excitation of 323 nm light. The complex had two pairs of redox peaks in the potential range of -0.6～0.6 V(a saturated calomel electrode was regarded as a reference electrode) which showed its good electrochemical activity. The thermal stability was good.
Key words: gadolinium; phosphomolybdic acid; synthesis; luminescence and electrochemical property
3-溴-5氯水杨醛缩间苯二胺的热氧降解过程及动力学研究
蒲小华*，金哲珺雨，焦飞
（宝鸡文理学院 化学化工学院，陕西 宝鸡 721013）
摘要：以3-溴-5-氯水杨醛和间苯二胺为原料，通过缩合反应生成一种新的席夫碱BCMP，用紫外-可见光谱、红外光谱、核磁共振等对化合物的结构进行表征。同时采用TG/DTG联用技术，分别测定了BCMP在5、10、15、20 K/min不同升温速率下的热氧降解曲线。通过单扫描速率法和多重扫描速率法相结合的方法，确定其最可几的机理函数，计算反应的活化能。
关键词：席夫碱；3-溴-5-氯水杨醛缩间苯二胺；热氧降解过程；动力学研究
中图分类号： O643.1 文献标识码：A 文章编号：0258-3283(2017)
Thermal Oxidation Degradation Process and Kinetics of 3 - Bromo - 5 - chlorosalicylaldehyde - m- phenylenediamine PU Xiao-hua*, JINZHE Jun-yu, JIAO Fei (1.College of Chemistry and Chemical Engineering , Baoji University of Arts and Sciences, Baoji 721013, China), Huaxue Shiji, 2017, 39(10)
Abstract：A new Schiff base of 3-bromo-5-chlorosalicylaldehyde-m-phenylenediamine was obtained by the condensation reaction of 3-bromo5-chlorosalicylaldehyde and m-phenylenediamine (abbreviated as BCMP ) and confirmed by UV-Vis, IR and NMR. TG and DTG were used to elucidate the thermal oxidation degradation process and kinetics of BCMP in air at various heating rates of 5, 10, 15, 20 K/min.The activation energy and pre-exponential factor were calculated by the single scanning method and multiple scanning method.
Key words：Schiff base；3-bromo-5-chlorosalicylaldehyde-m-phenylenediamine；thermal oxidation degradation process；kinetics studies
手掌面不锈钢客体遗留印迹的显现研究
王丽婷
（宁夏大学 ，宁夏 银川 750021）
摘要：考察了手掌面不锈钢客体遗留印迹的直接显现和转移后再显现的方法体系。以Lab色彩模式为评价指标，研究了红菲罗啉、邻菲罗啉、TPTZ、苯基-2-吡啶基酮肟和PDT 这5种试剂对手掌面不锈钢遗留印迹的显现效果。结果发现，对于手握不锈钢客体5 min以上的手掌印迹，使用5种试剂配方（其中任意一种）直接显色时，均可达到中等以上的分辨率。转移显现时，让手掌面按压在喷洒过30 g/L抗坏血酸的客体上1 min，再在客体上喷洒适量1g/L 的5种显色剂（其中任意一种），等待3 min后拍照固定，此法快速、灵敏、可靠，可将手掌上的不锈钢遗留印迹转移后成功显出。
关键词：法庭科学；不锈钢；显现
中图分类号：D918 文献标识码：A 文章编号：0258-3283（2017）
Detection and Determination of Imprint Left by Stainless Steel on Hands WANG Li-ting（ , Ningxia University, Yin chuan 750021, China）, Huaxue Shiji, 2017, 39(10)
Abstract: Based on the comparison with iron traces on hands，the methods of detection and transferring for hand imprint left by stainless steel were investigated. The Lab color mode was applied to evaluate the color reaction results of five reagent including 4:7-diphenyl-1:10-phenanthroline, 1:10-phenanthroline, 2,4,6-3-(2-pyridyl)-l,3,5-triazine, phenyl-2-pyridyl ketoxime and PDT. The results showed that for hand imprint contacting with stainless steel more than 5 minutes, the five reagents could be used to detect the hand imprint, the resolution can be achieved “strong” or “medium” level. Besides, spraying one of the five reagents (1 g/L) on the transferring objects on which pressing the hands for 1 min and had been sprayed reducing agent(30 g/L), then taking a photo after 3 mins, using this method, hand imprint contacting with stainless steel more than 5 minutes can be transferred and detected. This method was rapid, sensitive and reliable, which can be used to detect the suspects.
Key words: forensic science; stainless steel; detection
固相一步合成碳负载磁性吸附材料及其在染料废水中的应用
胡鹏，牛静*，王娇娇，薛首峰
(黄淮学院 化学与制药工程学院，河南 驻马店 463000)
摘要：以农业生物质甘蔗渣为碳源、氯化钴和氯化镍为前驱体，通过固相一步热还原法制备了Co-Ni/C磁性吸附材料，并将之用于对亚甲基蓝的吸附和磁性分离。利用生物质碳和磁性纳米粒子的协同作用，室温条件下在6 h内该磁性吸附剂对染料的吸附率达99%。这种廉价、高效的吸附剂有望实现大规模制备，并在将来的水污染处理领域中发挥重要的作用。
关键词：生物质；磁性材料；亚甲基蓝
中图分类号：O621. 25 文献标识码：A 文章编号：0258-3283（2017）
One Step Solid-phase Synthesis of Magnetic Adsorbent Supported by Carbon Materials and Application in Dye Wastewater HU Peng, NIU Jing*, WANG Jiao-jiao, XUE Shou-feng (College of Chemistry and Pharmaceutical Engineering, Huanghuai University, Zhumadian 463000, China), Huaxue Shiji, 2017, 39(9)
Abstract：In this work, a Co-Ni/C magnetic absorbent was synthesized by facile thermal reduction using bagasse, cobalt chloride and nickel chloride as precursors. The adsorption and magnetic separation efficiency were investigated using methylene blue for the model molecules. Taking advantage of the synergy of biomass carbon and magnetic nanoparticles, 99% of the dye molecules was removed within six hours under room temperature. This kind of inexpensive and efficient adsorbent is expected to achieve large-scale preparation and play an important role in the field of water pollution treatment in the future.
Key words：biomass; magnetic material; methylene blue
升华提纯法制备三氯叔丁醇高纯试剂的研究
李清洁1，费荣杰1，丁春玉1，王志刚1，成义祥*2
（1. 南京化学试剂股份有限公司, 江苏 南京 210047；2. 南京大学 化学化工学院, 江苏 南京 210023）
摘要:采用升华提纯法制备半水合三氯叔丁醇高纯试剂，探索了升华温度和升华时间对升华工艺的影响。利用气相色谱仪(GC)和电感耦合等离子体质谱(ICP-MS)测试升华前后半水合三氯叔丁醇的纯度和金属离子含量的变化。参照美国西格玛试剂指标对样品进行检测分析，结果表明：半水合三氯叔丁醇在100 ℃下升华14 h收率达98.2%，不出现分解，所得试剂纯度高达99.96%，并具有较低的金属离子含量。
关键词: 升华提纯；半水合三氯叔丁醇；高纯试剂；升华温度
中图分类号：O642.5 文献标识码：A 文章编号：0258-3283（2017）
Preparation of High Purity Reagents of Chlorobutanol by Sublimation Purification Method
LI Qing-jie1, FEI Rong-jie1, DING Chun-yu1, WANG Zhi-gang1, CHENG Yi-xiang*2(1.Nanjing Chemical Reagent Co., Ltd., Nanjing 210047, China; 2. College of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China), Huaxue Shiji, 2017, 39(10)
Abstract: The preparation of high purity reagent of hemihydrate chlorobutanol was investigated by changing sublimation temperature and sublimation time. The purity of hemihydrate chlorobutanol and the change of metal ions content were measured by gas chromatography (GC) and inductively coupled plasma mass spectrometry (ICP-MS) before and after sublimation, respectively. The purity of the obtained hemihydrate chlorobutanol can reach as high as 99.96% and the yield is 98.2% with lower metal ions content at 100℃ for 14 h sublimation time.
Key words: sublimation purification; hemihydrate chlorobutanol; high purity reagent; sublimation temperature
三草酸合铁(Ⅲ)酸钾合成工艺的优化
马少妹，袁爱群*，白丽娟，韦冬萍，黄增尉，周泽广，尹显洪，钟莲云
(广西民族大学 化学化工学院 广西林产化学与工程重点实验室，广西 南宁 530006)
摘要：以硫酸亚铁铵、草酸为主要原料，双氧水为氧化剂合成制备三草酸合铁(Ⅲ)酸钾。采用响应面法优化三草酸合铁(Ⅲ)酸钾的制备工艺，用XRD、FT-IR、SEM对产物进行表征。结果表明，制备的产物化学式为K[Fe(C2O4)3]·3H2O，形貌为微米块状颗粒。优化工艺条件为：草酸亚铁制备中草酸用量为28.00 mL、反应时间为18.00 min；氧化配位反应中草酸钾、H2O2用量分别为6.00、17.00 mL，时间为18.00 min，清除H2O2时间为5.00 min；酸溶配中草酸用量为11.00 mL，产品均为翠绿色晶体，产率可达90.80%。在该条件下重复实验，产率分别为89.89%、90.57%。
关键词：硫酸亚铁铵；三草酸合铁(Ⅲ)酸钾；响应面法优化
中图分类号：O611.4 文献标识码：A 文章编号：0258-3283（2017）
Improvement for the Preparation Teachnolgy of Potassium Trioxalatoferrate MA Shao-mei, YUAN Ai-qun*, BAI Li-juan, WEI Dong-ping, HUANG Zeng-wei, ZHOU Ze-guang, YIN Xian-hong, ZHONG Lian-yun(Guangxi Key Laboratory of Chemistry and Engineering of Forest Products，School of Chemistry and Chemical Engineering，Guangxi University for Nationalities，Nanning 530006, China）, Huaxue Shiji, 2017, 39(9)
Abstract: Potassium trioxalato ferrate was synthesized by using ammonium ferrous sulfate and oxalic acid as materials, and hydrogen peroxide as the oxidant. The experimental conditions has been optimized by response surface method. The obtained product were confirmed by XRD, SEM, IR and chemical analysis. The results showed that the structure product is K[Fe(C2O4)3]·3H2O and a micron particle with morphology bulk shape. The improved conditions are oxalic acid dosage is 28.00 mL, the reaction time of 18.00 min during the preparation of ferrous oxalate. Potassium oxalate, H2O2 dosage are 6.00 mL respectively, time is 18.00 min, removal of H2O2 time is 5.00 min during the oxidation of coordination reaction. Oxalic acid dosage is 11.00 mL in acid soluble ligand process. The product are green crystals, the yield can reach 90.80%. The yield still reach 89.89% and 90.57% under the repeated experiment of improved condition.
Key words: ammonium ferrous sulfate; potassium trioxalatoferrate(III); response surface method
一种酚羟基苄基保护基的脱除方法
杨礼寿1, 2，李齐激2，杨娟2，杨小生* 1, 2
（1. 贵州大学 药学院，贵州 贵阳 550025；
2. 贵州省中国科学院天然产物化学重点实验室，贵州 贵阳 550014）
摘要：提出了一种脱除酚类化合物羟基苄基保护基的方法。采用多聚磷酸（PPA）-浓盐酸-乙醇体系脱除苄基保护基，通过单因素实验考察PPA的物质的量、浓盐酸与PPA体积比、反应时间以及反应温度对产率的影响。结果表明，PPA的物质的量为0.2 mmol、V（浓盐酸）︰V（PPA）= 100︰1、反应时间为3 h、反应温度为85 ℃为最佳反应条件。采用优化条件得到9个脱苄基化合物，产率为70.4% ~ 92.7%，其中2'-苄氧基取代查尔酮脱掉苄基的同时环合得到二氢黄酮。所得产物结构经MS、1HNMR及13CNMR进行确证。
关键词：多聚磷酸；浓盐酸；脱苄基；二氢黄酮；合成
中图分类号：O621. 3 文献标识码：A 文章编号：0258-3283（2017）
Removal of Benzyl Protective Groups of Phenolic Hydroxyl Groups YANG Li-shou1,2, LI Qi-ji2, YANG Juan2, YANG Xiao-sheng* 1,2(1.College of Pharmacy, Guizhou University, Guiyang 550025, China; 2.The Key Laboratory of Chemistry for Natural Products of Guizhou Province and Chinese Academy of Sciences, Guiyang 550014, China), Huaxue Shiji, 2017, 39(10)
Abstract：A method for removal of benzyl-type protective groups of phenolichydroxyl groups in phenolic compounds was reported. Removing benzyl-type protective groups was carried out with polyphosphoric acid(PPA)-concentrated hydrochloric acid-ethanol system. Effects of PPA equivalent, volume ratio of concentrated hydrochloric acid to PPA, reaction time and reaction temperature on the yield were investigated via single factor tests. Results indicated that PPA equivalent, volume ratio, suitable reaction time and reaction temperature was 0.2 mmol, 100︰1, 3 h and 85 ℃ respectively. 9 products were prepared at the optimum conditions in good yields of 70.4% ～ 92.7%. Specifically, corresponding flavanones were formed in the deprotection procedure of benzyl group of 2'-benzyloxy substituted chalconesusing this reaction system. Structures of all compounds were confirmed by MS,1HNMR and 13CNMR.
Key words：polyphosphoric acid; concentrated hydrochloric acid; debenzylation; synthesis of flavanonols
吉法酯有关物质的合成研究
李永，范钰新，陈文章，朱高峰，王建塔，汤磊*
（贵州医科大学 药学院，贵州 贵阳 550004）
摘要：为了控制治疗胃溃疡药物吉法酯产品的质量，现根据吉法酯的结构及合成工艺，制备了可能存在的 3 个有关物质，分别为3, 7, 11-三甲基-1, 3, 6, 10-十二碳-四烯、(4E, 8E)-法呢基乙酸橙花醇酯和(4Z, 8E)-法呢基乙酸橙花醇酯，并经MS、1HNMR和13CNMR确证其结构，以作为吉法酯质量研究的参照物。
关键词：吉法酯；有关物质；合成
中图分类号：R914.5 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of Related Substances for Gefarnate LI Yong, FAN Yu-xin, CHEN Wen-zhang, ZHU Gao-feng, WANG Jian-ta, TANG Lei* (College of Pharmacy, Guizhou Medical University, Guiyang 550004, China), Huaxue Shiji, 2017, 39(10)
Abstract: Based on the structure of gefarnate and its synthetic process, three related substances: (3E, 6E)-3, 7, 11-Trimethyl-1,3,6,10-dodecatetraene, (4E, 8E)-farnesyl neryl acetate and (4Z, 8E)-farnesyl neryl acetate were synthesizedand confirmed by MS, 1HNMR and 13CNMR. These substances were taken as the references for the quality control of gefarnate.
Key words: gefarnate; related substance; synthesis
槲皮素苯甲酸酯的合成与表征
刘秋伟1，李金玉2，陈佳敏1，翟广玉*1
（1. 郑州工业应用技术学院 药学院，河南 新郑 451100；2. 河南大学 药学院，河南 开封 475004）
摘要：以槲皮素为原料、浓硫酸作催化剂，85 ℃与苯甲酰氯反应，TLC板监测反应完毕，过滤、氯仿/甲醇重结晶合成槲皮素苯甲酸酯。UV表征显示，槲皮素的两个特征吸收峰均发生蓝移，这是形成新化合物共轭体系引起的。IR中ν-OH峰明显减弱，说明槲皮素的5个羟基中有的羟基发生了反应；νc=o位于1745.32 cm-1，酯羰基峰明显增强；νc-o位于1295.66 cm-1，峰变宽增强。1HNMR中3-OH、3′-OH、4′-OH上面的氢消失，说明与苯甲酰氯发生了酯化反应；同时，在δ 7.6 ～ 8.8处有苯甲酰基的多重峰。MS中m/z 615.2为槲皮素三苯甲酸酯的分子离子峰。因此，槲皮素与苯甲酰氯反应可以得到槲皮素三苯甲酸酯。
关键词：槲皮素；苯甲酰氯；槲皮素酯；合成；表征
中图分类号：TQ28 文献标识码：A 文章编号：0258-3283（2017）
Synthesis and Characterization of Quercetin Benzoate LIU Qiu-wei1, LI Jin-yu2, CHEN Jia-min1, ZHAI Guang-yu*1(1. Department of Pharmacy, Zhengzhou University of Industrial Technology, Zhengzhou 451100,China; 2. College of Pharmacy, Henan University, Kaifeng 364500, China), Huaxue Shiji, 2017, 39(9)
Abstract: Quercetin as raw material, sulfuric acid as a catalyst, 85 ℃ reacted with benzoyl chloride, TLC plate monitor completion of the reaction, filtration, chloroform/methanol recrystallization to synthesize quercetin benzoate. UV absorption of quercetin shows two characteristic peaks are blue shift, which is the formation of new compounds conjugated system caused by the change. IRν-OH peak in significantly reduced, indicating that quercetin five hydroxy some of the hydroxyl groups reaction, νc = o located 1745.32 cm-1, significantly enhanced peak of the ester carbonyl group, νc-o located 1295.66 cm-1, widened enhanced. 1HNMR of 3-OH, 3'-OH, 4'-OH the above hydrogen disappeared, indicating esterification with benzoyl chloride occurred at the same time, the department has benzoyl 7.6 ～ 8.8 multiplet. MS 615.2 in molecular ion peak of quercetin three benzoate. Quercetin can be reacted with benzoyl chloride to obtain quercetin tribenzoate.
Key words: quercetin; benzoyl chloride; quercetin ester; synthesis; characterization
多苯基氨基吡唑啉酮衍生物的合成
马学林，段丽萍*
(包头师范学院 化学学院 材料化学与物理重点实验室，内蒙古 包头 014030)
摘要：常温条件下，乙醇作溶剂，以1-苯基-3-甲基-5-吡唑啉酮、芳香醛和芳香胺为原料，在Zn-Tb-MCM-41催化下，通过三组分“一锅法”合成8种新型多苯环氨基吡唑啉酮衍生物，产率为79% ～ 89%。产物通过IR、1HNMR和元素分析确定。该方法具有操作简单、条件温和、产率高、选择性高等特点。
关键词：吡唑啉酮衍生物；三组分；一锅法
中图分类号：O643.37 文献标识码：Ａ 文章编号：0258-3283(2017)
Synthesis of Multi Phenyl Amino Derivativeswith Pyrazolone MA Xue-lin, DUAN Li-ping*(Key Laboratory of Materials and Physical Chemistry, College of Chemistry, Baotou Normal College, Baotou 014030, China), Huaxue Shiji, 2017, 39(10)
Abstract: In the presence of catalysts of Zn-Tb-MCM-41, 1-phenyl-3-methyl pyrazole-5 can react directly with aromatic aldehydes and aromatic amines by three component ‘one pot’ in ethanol at 25 ℃ to afford the novel multi phenyl amino derivatives of pyrazolone with the yield of 79% ～ 89%.The products are confirmed by IR, 1HNMR and elemental analysis. This process has advantages of simple, mild conditions, high yield and high selectivity.
Key words: pyrazolone derivatives; three component; one pot
硝酸依柏康唑的合成新方法
程炜*，汤俊梅，顾准
（苏州健雄职业技术学院 生物与化学工程系，江苏 太仓 215411）
摘要：硝酸依柏康唑是一种外用广谱抗真菌感染药物，以邻苯二甲酸酐和3, 5-二氯苯乙酸为原料，首先经缩合、催化加氢、环合3步反应制备得到关键中间体2, 4-二氯-10, 11-二氢-5H-二苯并[a, d]环庚烯-5-酮，然后经还原、氯化、N-烃基化、成盐等4步反应制备得到硝酸依柏康唑。该合成方法缩短了硝酸依柏康唑的合成路线，提高了总收率，不产生有机磷废弃物，更适于工业化生产。
关键词：硝酸依柏康唑；抗真菌感染；合成方法
中图分类号：R914.5 文献标识码：A 文章编号：0258-3283（2017）
Novel Synthesis of Eberconazole Nitrate CHENG Wei*, TANG Jun-mei, GU Zhun (Department of Biological and Chemical Engineering, Suzhou Chien-Shiung Institute of Technology, Taicang 215411, China), Huaxue Shiji, 2017, 39(10)
Abstract: Eberconazolenitrate is an external used broad-spectrum antifungal drug. In this work, the key intermediate 2,4-dichloro-10,11-dihydro-5H-dibenzo[a, d] cyclohepten-5-one was synthesized by condensation, catalytic hydrogenation, cyclization from phthalic anhydride and 3,5-dichlorophenylacetate. Then, the eberconazole nitrate was synthesized by the key intermediate via reduction, chlorination, N-alkylation and salification. The method is suitable for large-scale production due to shorter synthetic route, improved yield and no organic phosphorus waste.
Key words:eberconazole nitrate; antifungal infection; synthetic method
绿色氧化溴代新进展
郭建国*1,2，顾金凤1,2，凌芳1,2，陈浩云1，郑琦1,2
（1. 上海化学试剂工程技术研究中心，上海 200002；2. 国药集团化学试剂有限公司，上海 200002）
摘要：综述了近年来国内外在绿色氧化溴代方面的研发进展，尤其是国药集团化学试剂有限公司以溴离子为溴源，在绿色氧化溴代方面的进展，包括不同底物的溴代、不同氧化剂和溴离子作为溴源的组合，并对这些技术的产业化进行了展望。
关键词：绿色氧化溴代；溴原子利用率；4-溴邻苯二甲酸；2-溴-4-叔丁基苯酚；4-溴甲苯；N-溴代丁二酰亚胺（NBS）；氯化溴
中图分类号： O643 文献标识码：A 文章编号： 0258-3283(2017)
Progress on Green Oxidative Bromination GUO Jian-guo*1,2，GU Jin-feng1, 2，LING Fang1,2，CHEN Hao-yun2, ZHENG Qi1, 2（1. Shanghai Engineering Technology Reaserch Center of Chemical Reagent, Shanghai 200002,China; 2. Sinopharm Chemical Reagent Co., Ltd, Shanghai 200002, China）, Huaxue Shiji, 2017, 39(10)
Abstract: The progress on green oxidative bromination recent years has been summarized. Including Br-1and sodium hypochlorite( or sodium chlorite) as bromine source reacting with different reagents: benzoic acid, toluene, phenol etc. The development trends in the industrial future are proposed.
Key words: green oxidative bromination; bromine atom utilization; 4-bromo phthalic acid; 2-bromo-4-t-butylphenol; 4-bromotoluene; NBS; bromine chloride
