分等级β-Ni(OH)2花状微球的制备及其电化学性能研究
闫慧君*1，李莹莹1，姜艳丽1，张晶1，王丽燕1，白建伟2，王君2
(1. 哈尔滨学院 理学院，黑龙江 哈尔滨 150086；
2. 哈尔滨工程大学 材料科学与化学工程学院 超轻材料与表面技术教育部重点实验室，黑龙江 哈尔滨 150001)
摘要：以L-精氨酸(L-arginine)为结构导向剂，利用水热法合成由纳米片组装成的分等级β-Ni(OH)2花状微球。采用XRD、SEM、TEM及N2吸附脱附对样品的微观结构、表面特性及比表面积进行了表征，深入分析其合成机理，并通过循环伏安、充放电、交流阻抗等测试考察了该电极材料的电化学性能。结果表明，分等级β-Ni(OH)2花状微球具有优异的电化学电容特性，在电流密度为5 mA/cm2时，β-Ni(OH)2的比电容值高达1048.5 F/g，500圈充放电循环后，其比电容仅衰减了9.2%，可见所制得样品是一种理想的超级电容器电极材料。
关键词：分等级；β-Ni(OH)2花状微球；L-精氨酸；超级电容器；电化学性能
中图分类号：O611.64 文献标识码：A 文章编号：0258-3283（2017）
Preparation and Electrochemical Properties of Hierarchical β-Ni(OH)2 Flower-like Microspheres YAN Hui-jun*1，LI Ying-ying1, JIANG Yan-li1, ZHANG Jing1, WANG Li-yan1, BAI Jian-wei2, WANG Jun2 (1. Department of Chemistry, School of Science, Harbin University, Haerbin 150086, China；2. Key Laboratory of Superlight Material and Surface Technology, Ministry of Education, College of MaterialsScience and Chemical Engineering, Harbin Engineering University, Haerbin 150001, China)
Abstract: Hierarchical β-Ni(OH)2 flower-like microspheres with partial open gaps have successfully been prepared via a facile hydrothermal process with the assistance of L-arginine. The microstructure, surface properties, and specific surface area of the as-prepared products have been characterized by means of XRD, SEM, TEM, and N2 adsorption/desorption, respectively. The synthesis mechanism was also analyzed deeply. The electrochemical properties of the as-obtained products were investigated by cyclic voltammograms, galvanostatic charge/discharge curves, and electrochemical impedance spectroscopy. Results show that a maximum specific capacitance of 1048.5 F/g at the current density of 5 mA/cm2 is obtained and the capacitance loss is only approximately 9.2% after 500 cycling tests. Therefore, the as-obtained product was a perfect electrode material of supercapacitor.
Key words: hierarchical; β-Ni(OH)2 flower-like microspheres; L-arginine；supercapacitor; electrochemical performance
基于Dawson型H6P2Mo18O62杂化材料[Ni(2,2′-bipy)3]3(P2Mo18O62)的制备及其吸附性能研究
陈秀云，杨水金，吕宝兰*
(湖北师范大学 化学化工学院 稀有金属化学湖北省协同创新中心，湖北 黄石 435002)
摘要：以H6P2Mo18O62、[Ni(2,2’-bipy)3]Cl2∙5.5H2O为原料，通过化学共沉淀法制备[Ni(2,2’-bipy)3]3(P2Mo18O62)复合材料，采用FTIR、SEM、TG、BET等手段进行表征，并研究其对亚甲基蓝(MB)溶液的吸附性能。探讨了pH、初始浓度、温度等条件对MB溶液吸附效果的影响。结果表明，将H6P2Mo18O62与[Ni(2,2´-bipy)3]Cl2∙5.5H2O进行复合形成复合物[Ni(2,2´-bipy)3]3(P2Mo18O62)后，可有效地克服其水溶性，大大地提高了其液相吸附能力，且温度对其吸附性能影响不大。从实验结果可知，其分别符合Langmuir等温吸附模型和拟二级动力学。热力学参数∆G0 <0，∆H0 <0和∆S0 <0，表明该吸附剂对亚甲基蓝的吸附是自发的且放热，其对其他阳离子染料罗丹明B也有较好的吸附效果。
关键词：[Ni(2,2´-bipy)3]3(P2Mo18O62)；杂多酸；吸附；染料
中图分类号：TQ426.91 文献标识码：A 文章编号：0258-3283（2017）
Synthesis and Adsorption Performance of Hybrid Materials [Ni(2,2´-bipy)3]3(P2Mo18O62) Based on Dawson-type H6P2Mo18O62 CHEN Xiu-yun, YANG Shui-jin, LV Bao-lan* (College of Chemistry and Chemical Engineering, Hubei Collaborative Innovation Center for Rare Metal Chemistry, Hubei Normal University, Huangshi 435002, China)
Abstract：A novel adsorbent [Ni(2,2´-bipy)3]3(P2Mo18O62) was synthesized via chemical coprecipitation method with H6P2Mo18O62 and [Ni(2,2´-bipy)3]Cl2∙5.5H2O as materials. The adsorption ability by removing MB in aqueous solutions was investigated. The influences of the experimental conditions including pH, initial concentration and temperature was explored. The water-soluble of [Ni(2,2´-bipy)3]Cl2∙5.5H2O could be effectively overcame by the compound [Ni(2,2´-bipy)3]3(P2Mo18O62) formed via H6P2Mo18O62 and [Ni(2,2´-bipy)3]Cl2∙5.5H2O. The adsorption capacity in liquid could be greatly increased, on the other hand, a little effect of temperature on the adsorption properties. The Langmuir isotherm model and pseudo-second-order kinetic model was fitted the adsorption process. Thermodynamic parameters’ ∆G0 <0, ∆H0 <0 and ∆S0 <0, illustrated that the MB adsorption onto [Ni(2,2´-bipy)3]3(P2Mo18O62) was spontaneous and exothermic. Besides, the adsorbent [Ni(2,2´-bipy)3]3(P2Mo18O62) towards other cationic dyes such as Rhodamine B also showed good adsorption properties.
Key words：[Ni(2,2´-bipy)3]3(P2Mo18O62); heteropoly acid; adsorption; dye
噻唑并[3, 2-b][1, 2, 4]三唑酮衍生物的合成及抗癌活性研究
李敏，田玉顺*
(延边大学 药学院 药物化学教研部，吉林 延吉 133002)
摘要：以3, 4, 5-三甲氧基苯甲酸为原料，经过Claisen缩合等一系列反应设计合成一系列新的噻唑并[3, 2-b][1, 2, 4]三唑-6-酮稠杂环衍生物并测定其体外抗肿瘤活性。目标化合物经1H-NMR、13C-NMR和高分辨质谱等表征后，在HeLa、HCT116、BEL-7402及L-02细胞中用MTT法测定其抑制细胞增殖的程度，并初步判断化合物的体外抗癌活性。结果表明，与临床常用药顺铂相比，多数化合物具有抑制肿瘤细胞增殖活性。其中，5-(4-苄氧基苯亚甲基)-2-(3,4,5-三甲氧基苯基)噻唑并[3,2-b][1,2,4]三唑-6(5H)-酮、5-(4-乙酰氧基苯亚甲基)-2-(3,4,5-三甲氧基苯基)噻唑并[3,2-b][1,2,4]三唑-6(5H)-酮、5-(α-呋喃亚甲基)-2-(3,4,5-三甲氧基苯基)噻唑并[3,2-b][1,2,4]三唑-6(5H)-酮和5-(α-噻吩亚甲基)-2-(3,4,5-三甲氧基苯基)噻唑并[3,2-b][1,2,4]三唑-6(5H)-酮对HCT116等3种癌细胞的抑制率高于正常细胞L-02，且对癌细胞有选择性抑制作用，而对正常细胞无毒性，具有良好的后续研究价值。5-(4-氟苯亚甲基)-2-(3,4,5-三羟苯基)噻唑并[3,2-b][1,2,4]三唑-6(5H)-酮对BEL-7402等细胞的抑制率有大幅度提高，但对L-02正常细胞的毒性更大。
关键词：噻唑并[3, 2-b][1, 2, 4]三唑酮；抗肿瘤活性；Claisen缩合；MTT法；选择性抑制活性
中图法分类号：R914.5 文献标识码：A 文章编号：0258-3283（2017）
Synthesis and Preliminary Antitumor Activity Evaluation of Thiazolo[3,2-b] [1,2,4]triazol-6(5H)-one Derivatives LI Min, TIAN Yu-shun* (Medicinal Chemistry, College of Pharmacy, Yanbian University, Yanji 133002, China)
Abstract: Using 3,4,5-trimethoxybenzoic acid as a starting material to synthesized a series of novel derivatives of thiazolo[3,2-b][1,2,4]triazol-6-one by a series of reaction, such as Claisen condensation, and detected the anti-tumor activities in vitro. The structures were characterized by 1H-NMR, 13C-NMR, high resolution mass spectrometry and so on, and the growth inhibitory activities in vitro were evaluated by MTT assay against HeLa, HCT116, BEL-7402 and L-02. The results showed that compared with the common positive anticancer drug cisplatin, the most of the synthesized compounds were expressed inhibitory activities against the four cells lines. Among them, compound 5-((4-benzyloxy)benzylidene)-2-(3,4,5-trimethoxyphenyl)thiazolo[3,2-b] [1,2,4]triazol-6(5H)-one, 4-((6-oxo-2-(3,4,5-trimethoxyphenyl) thiazolo[3,2-b][1,2,4]triazol-5(6H)-ylidene) methyl)phenyl acetate 5-(furan-2-ylmethylene)-2-(3,4,5-trimethoxyphenyl)thiazolo[3,2-b][1,2,4]triazol-6 (5H)-one and 5-(thiophen-2-ylmethylene)-2-(3,4,5-trimethoxyphenyl)thiazolo[3,2-b][1,2,4]triazol-6(5H)-one showed excellent anti-tumor activities in vitro against the three cancer cell lines such as HCT116 cells with low toxicity to L-02 normal cells, have good subsequent research values in the future. The anti-proliferation activities of 5-(4-fluorobenzylidene)-2-(3,4,5-trihydroxyphenyl)thiazolo[3,2-b][1,2,4]triazol-6(5H)-one were increased greatly against several cell lines, such as BEL-7402 cell, but more toxic to L-02 normal cells.
Key word: Thiazolo[3,2-b][1,2,4]triazolone; Anti-tumor activity; Claisen condensation; MTT assay; Selective inhibitory effect
5, 15-二苯基-10, 20-二(4-N-咪唑基)苯基卟啉的合成与表征
李维维1，徐维霞*1，李小博1，刘焕婷1，孟凡洋1，李珺2
（1. 咸阳师范学院 化学与化工学院，陕西 咸阳 712000；
2. 西北大学 化学与材料科学学院 合成与天然功能分子教育部重点实验室，陕西 西安 710069）
摘要：采用丙酸法合成了新的5, 15-二苯基-10, 20-二(4-N-咪唑基)苯基卟啉(H2Pp)分子，并对该化合物进行了EA、FT-IR、1HNMR、MS、UV-Vis等表征，确定了所合成卟啉的分子结构。探讨了反应中催化剂的用量、反应温度、反应物比例及反应时间对目标产物产率的影响。结果表明，合成目标化合物的适宜反应时间为1 h，反应温度为140 ℃，在该条件下目标产物的产率可高达36.6%。在400 nm的光激发下，于666 nm处出现最强发射峰，可用作潜在的光学材料。
关键词：5, 15-二苯基-10, 20-二(4-N-咪唑基)苯基卟啉；合成；表征
中图分类号：O641.4 文献标识码：A 文章编号：0258-3283（2017）
Synthesis and Characterization of 5, 15-Di(pheny)-10, 20-di-[(4-N-imidazolyl)phenyl] Porphyrin LI Wei-wei1, XU Wei-xia*1, LI Xiao-bo1, LIU Huan-ting1, MENG Fan-yang1, LI Jun2 (1. College of Chemistry and Chemical Engineering, Xianyang Normal University, Xianyang 712000, China; 2. Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Material Science, Northwest University, Xi′an 710069, China)
Abstract: The novel porphyrin 5, 15-di(pheny)-10, 20-di-[(4-N-imidazolyl) phenyl]porphyrin (H2Pp) was synthesized by the Alder method and confirmed by elemental analyses, FI-IR, 1HNMR, MS and UV-Vis, etc. The effects of the dosage of catalyst, the appropriate ratio of reactants, reaction temperature and time on the yield of target compound were investigated. The results show that the yield of the target compound reaches 36.6% when the suitable reaction time is 1 h and the temperature is 140 ℃. It shows intense fluorescence emission with maximum at 666 nm upon 400 nm excitation at room temperature, indicating that it may be candidate for luminescent material.
Key words: 5, 15-di(pheny)-10, 20-di-[(4-N-imidazolyl) phenyl] porphyrin; synthesis; characterization
新型聚合油溶性稠油降粘剂的合成及性能研究
陈宁宁1，宋立新2，郑云重1，吴超钧1，张明1，何娟*1，游利琴1，张红霞1，
展海军1，谷克仁1
(1. 河南工业大学 化学化工学院，河南 郑州 450001；
2. 河南水利与环境职业学院 环境工程系，河南 郑州 450001)
摘要：研究了自制丙烯酸十八酯、苯乙烯、马来酸酐和丙烯酰胺4种单体分别以物质的量比10︰3︰2︰0.8和6︰1︰2︰0进行四元无规共聚反应，得到两种新型的油溶性的共聚降粘剂。对溶剂用量、反应温度等影响条件进行了优化，探究了降粘剂的加量和温度等因素对降粘效果的影响。结果表明，四元共聚物的降粘效果优于三元聚合物。50 ℃时，降粘剂的加入量占稠油量的10%时，三元和四元共聚物对稠油的降粘率分别达到79.4%和87.6%。
关键词：油溶性；降粘剂；三元共聚物；四元共聚物
中图分类号： TE345 文献标识码：A 文章编号：0258-3283（2017）
Synthetic and Properties Research of a Novel Viscosity Reducing of Oil-soluble Polymers CHEN Ning-ning1, SONG Li-xin2, ZHENG Yun-zhong1, WU Chao-jun1, ZHANG Ming1, HE Juan*1, YOU Li-qin1，ZHANG Hong-xia1，ZHAN Hai-jun1，GU Ke-ren1 (1.School of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou 450001, China; 2. Department of Environmental Engineering，Henan Vocational College of Water Conservancy and Environment, Zhengzhou 450001, China)
Abstract:The novel oil-soluble copolymerization viscosity depressants were synthesized by octadecyl acrylate, styrene, maleic anhydride (MA) and acryl amide with the molar ratio of 10 : 3 : 2 : 0.8 and 6 : 1 : 2 : 0. The dosage of solvent and synthesis temperature affecting the rate of viscosity were optimized. The effects of copolymerization viscosity reducers dosage and temperature were investigated. The results indicated that the effect of viscosity reducing of quaternary copolymer was better than that of the ternary polymer. At 50 ℃ and viscosity agent dosage of 10 wt%, the rate of viscosity reduction of ternary and quaternary copolymers were 79.4% and 87.6%, respectively.
Key word: oil-soluble; viscosity reducer; ternary copolymer; quaternary copolymer
膨化糯米淀粉的制备及性能表征
翟广玉*1, 2，张会丽1，张景亮1，王世广1，刘婕1，张晶晶1，刘金海1
（1. 郑州工业应用技术学院 药学院，河南 郑州 451100；
2. 郑州大学 护理学院，河南 郑州 450052）
摘要：把糯米淀粉放入膨化机内加热加压，可得膨化糯米淀粉，观察其在水中溶解性能及粘接强度大小。膨化糊化比加热糊化和加碱糊化更容易操作，糊化程度容易控制，糊化的更彻底。从TG和DTG可知，膨化糯米淀粉的热稳定性更大；糯米淀粉经过膨化，淀粉颗粒崩解，亲水性羟基裸露在外面的更多，水溶性明显增大，显示在IR光谱图上羟基吸收峰明显变宽变大；从SEM图可看出，膨化糯米淀粉的颗粒表面粗糙，更易与水亲和。结果表明，膨化糯米淀粉易溶于水、粘接强度大，在粘接剂行业、医药领域有广泛的应用。
关键词：膨化；糯米淀粉；粘合剂
中图分类号：TB484；TQ430.1 文献标识码：A 文章编号：0258-3283（2017）
Preparation and Characterization of Puffing Glutinous Rice Starch ZHAI Guang-yu*1,2, ZHANG Hui-li1, ZHANG Jing-liang1, WANG Shi-guang1, LIU Jie1, ZHANG Jing-jing1, LIU Jin-hai1（1. Department of Pharmacy , Zhengzhou university of industrial technology, Zhengzhou 451100; 2. School of Nursing, Zhengzhou University, Zhengzhou 450052，China）
Abstract: To puff glutinous rice starch, observation of dissolved in the water performance, the size of the bonding strength. Put the glutinous rice starch extrusion machine, heating pressure can get puffed glutinous rice starch. Puffing pasting operation more easily than heat gelatinization and pasting the alkaline, gelatinization degree easy to control, pasting more thoroughly. Can know from TG and DTG, thermal stability of puffed glutinous rice starch is greater. Glutinous rice starch after puffing, starch granule disintegration, hydrophilic hydroxyl bare outside more, water-soluble increases obviously, hydroxyl absorption peaks in IR spectra obviously wider bigger. Based on SEM, puffed glutinous rice starch granule surface rough, more easily and water affinity. Puffed rice starch soluble in water, adhesive strength, have wide application in the adhesive industry, medicine field.
Key words: expanding; glutinous rice starch; adhesive
环肽纳米管的合成及应用研究进展
王毅一，马迎慧，范晓龙，陈敏东*
（南京信息工程大学 环境科学与工程学院 江苏省大气环境与装备技术协同创新中心
江苏省大气环境监测与污染控制重点实验室 江苏省环境净化材料工程技术研究中心，江苏 南京 210044）
摘要：环肽纳米管作为一种新兴纳米材料，在生物学、材料学、医学等诸多领域有潜在应用，引起广泛关注。从跨膜离子通道法、模板法、侧链修饰法3个方面综述了合成环肽纳米管的方法，系统的介绍了环肽在跨膜离子通道、药物的传递以及电子器件、催化材料等方面的应用，并对环肽纳米管发展前景进行了展望。
关键词：环肽纳米管；跨膜离子通道；模板法
中图分类号：O629.72 文献标识码：A 文章编号：0258-3283（2017）
Progress in Synthesis and Applications of Cyclic Peptide Nanotubes WANGYi-Yi, MA Ying-Hui, FAN Xiao-long, CHEN Min-Dong*(Jiangsu Engineering Technology Center for Environmental Purification Materials Research，Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, Innovation Center of Atmospheric Environment and Equipment Technology, School of Environmental Science and Engineering, Nanjing University of Information Science and Technology，Nanjing 210044, China)
Abstract: Cyclic peptides nanotubes (PNTS), a newly-developing of nanomaterial, have many potential applications in widely fields such as biology, materials and medical science etc. And it has already drawn a lot of attention. This article is reviewed through three aspects including the transmembrane ion channel, template and side chain modification method. In this work, the application of PNTS in transmembrane ion channels, drug delivery, electronic devices and catalytic material was reported. Meanwhile, the future development of cyclic peptide will be prospected as well.
Key words: cyclic peptide nanotubes; transmembrane ion channel; template
有机小分子催化不对称构建氧化吲哚C(3)位螺环化合物的
研究进展
龙先文，黄伟杰，朱文润，庄冲，蒋才武，林宁*
(广西中医药大学 药学院 广西壮瑶药工程技术研究中心，广西 南宁 530001)
摘要：螺环氧化吲哚结构是很多药理活性分子的核心骨架，其结构复杂且在合成过程中立体选择性难以控制，因此含有该骨架的化合物是药物和有机化学家关注的热点。按吲哚C(3)位上构建的三元螺环、四元螺环、五元螺环和六元螺环进行分类介绍近5年来有机小分子不对称催化构建螺环氧化吲哚化合物的研究进展，以期为该类化合物的合成提供有价值参考。
关键词：螺环氧化吲哚；研究进展；不对称催化
中图分类号：O621.3 文献标识码：A 文章编号：0258-3283（2017）
Progress for Organocatalytic Construction of Chiral Spirooxindoles Based on C(3) Indole LONG Xian-wen, HUANG Wei-jie, ZHU Wen-run, ZHUANG Chong, JIANG Cai-wu, LIN Ning*( Guangxi Zhuangyao Medicine Center of Engineering and Technology, School of Pharmacy, Guangxi University of Chinese Medicine, Nanning 530001, China)
Abstract：The spirooxindole skeletons have captured tremendous attention among synthetic and medicinal chemists, due to the prevalence pharmacological activities, complex structures and stereoselectivity. This work reviews the progress of the organocatalytic construction of chiral spirooxindoles in recent five years, primarily classified according to the three-membered spiro ring, four-membered spiro ring, five-membered spiro ring and six-membered spiro ring compounds fused at the C(3)-position of oxindole core, which provide valuable information for the synthesis of these compounds.
Key words：spirooxindoles; research progress; asymmetric catalysis
电子级N-甲基吡咯烷酮制备及检测研究进展
付浩，徐德锋*
（常州大学制药与生命科学学院，江苏 常州 213164）
摘要：超高纯N-甲基吡咯烷酮（NMP）是电子行业中的常用溶剂，N-甲基吡咯烷酮产品质量直接影响高端电子产品的生产与产品的质量。大规模生产电子级N-甲基吡咯烷酮技术主要被美国、德国、日本等发达国家垄断，目前我国电子企业使用的电子级N-甲基吡咯烷酮主要依靠进口。为提高我国高端电子产品的质量和市场竞争力，开发超高纯N-甲基吡咯烷酮（NMP）十分必要。本文通过文献资料整理，对电子级N-甲基吡咯烷酮的制备及检测技术进展进行总结，积极探索规模化生产电子级N-甲基吡咯烷酮及相应检测技术的方案。
关键词：N-甲基吡咯烷酮；合成；纯化；分析方法
中图分类号：TQ251.3 文献标识码：A 文章编号：0258-3283(2017)
Progress in Preparation and Testing of Electronic-grade N-methylpyrrolidone FU Hao，XU De-feng* (School of Pharmaceutical Engineering & Life Science, Chang zhou University, Chang zhou 213164，China)
Abstract: Ultra-pure N-methyl pyrrolidone(NMP) is a common solvent, widely used in the electronics industry. The quality of NMP directly affects the production of high-end electronic products and the quality of the product. Currently, the preparation technology of large-scale ultra-high purity electronic grade NMP reagent is mainly monopolized by the United States, Germany, Japan and other developed countries, while domestic electronics manufacturers gain NMP mainly via imports. In order to improve the competitiveness of the domestic electronics industry development, it is a serious problem to explore efficient, convenient and suitable for mass production of electronic grade NMP preparation method. This work summarized the advances in preparation and testing technology for electronic grade N-methylpyrrolidone based on literature data, and actively explored program-scale production of electronic grade N- methylpyrrolidone and the corresponding detection technology.
Key words: N-methylpyrrolidone; synthesis; purification; analysis
ICP-MS测量含纳米银生物组织样品中银含量的不确定度评定
郭玉婷，李瑞如，纪英露，谢黎明，吴晓春，葛广路*
(中国科学院 纳米标准与检测重点实验室 国家纳米科学中心，北京 100190)
摘要：利用微波消解-电感耦合等离子体质谱法对含纳米银生物组织样品中银含量进行了测试，对测量结果的不确定度进行了评定。根据实验方法，对主要来源不确定度分量进行了分析和计算，进而计算了样品中银含量的扩展不确定度。计算结果表明，重复性测量实验和银校准曲线的拟合对含纳米银生物组织样品中银含量的测量结果不确定度影响较大。结合计算结果，讨论了测量方法中需要推广及改进的方面，为相关研究的实验室质量控制和不确定度评定提供参考。
关键词：电感耦合等离子体质谱；纳米银；生物组织；不确定度
中图分类号：0657.63 文献标识码：A 文章编号：005648（2017）
Evaluation of Measurement Uncertainty of Silver Content in Biological Tissue Samples Containing Silver Nanomaterials by ICP-MS GUO Yu-ting, LI Rui-ru, JI Ying-lu, XIE Li-ming, WU Xiao-chun ,GE Guang-lu* (Key Laboratory of Standardization and Measurement for Nanotechnology, National Center for Nanoscience and Technology, Chinese Academy of Sciences, Beijing 100190, China)
Abstract：The silver content in biological tissue samples containing silver nanoparticles was measured using ICP-MS with microwave digestion. The uncertainty of measurement results was evaluated. Based on the experimental methods, the components of uncertainty from major sources, and the expanded uncertainty were analyzed and calculated. The results show that the repeatability of measurement and the fitting of the calibration curve have significant influence. The factors that need to be improved was discussed, and the reference for the quality control and uncertainty assessment was provided.
Key words：ICP-MS; silver nanomaterials; biological tissue; uncertainty
9类生态纺织品中24种禁用偶氮染料残留的测定
高杰1, 张勋*2, 杨璐2, 李荣荣2, 李爱军2，赵春美1, 熊龙3, 仲文严3, 李丹4, 刘先德5,
付瑶2,邢燕燕2
(1.长春理工大学 化学与环境工程学院，吉林 长春 130022；2.吉林出入境检验检疫局，吉林 长春 130062;3.江苏豪森药业集团有限公司，江苏 连云港 222047; 4.吉林省安信食品技术服务有限责任公司，吉林 长春 130000; 5.敦化市市场和质量监督管理局，吉林 敦化 133700)
摘要：建立了气相色谱-串联质谱法快速测定全棉织物、聚酯织物、羊毛织物、腈纶织物、合成革织物、棉和氨纶复合织物、羊毛和腈纶复合织物、棉和聚酯复合织物、羊毛和聚酯复合织物9类生态纺织品织物中24种禁用偶氮染料的检测方法。不同种类的纺织品根据成分的不同进行了不同的前处理过程，然后用甲醇进行定容。考察了不同样品基质对回收率的影响，方法的定量限为0.05 ～ 0.20 mg/kg，不同基质不同浓度的加标回收率在29.4% ～ 102.8%之间（添加水平为0.20、0.40、1.0 mg/kg，n = 6），相对标准偏差＜6.8%，该方法的检出限小于我国和欧盟检测标准中对24种禁用偶氮染料的限量要求。
关键词：禁用偶氮染料；生态纺织品；气相色谱-串联质谱法
中图分类号：O765.63 文献标识码：A 文章编号：0258-3283（2017）
Determination of 24 Banned Azo Colourants in 9 Textiles GAO Jie1, ZHANG Xun*2, YANG Lu2, LI Rong-rong2, LI Ai-jun2, ZHAO Chun-mei1, XIONG Long3, ZHONG Wen-yan3, LI Dan4, LIU Xian-de5, FU Yao2,XING Yan-yan2（Changchun University of Science and Technology,School of Chemistry and Environmental Engineering, Changchun 130022,China; 2. Jilin Entry-exit Inspection and Quarantine Bureau, Changchun 130062,China；3.Jiangsu Hanson Pharma, Lianyungang 222047,China; 4. The Essence of Jilin Province Food Technology Service company, Changchun 130000,China;5. Dunhua Market and the Administration of Quality Supervision ,Dunhua 133700,China)
Abstract：A rapid determination method was developed for 24 banned azo colourants in cotton fabric, polyester fabric,wool fabric,acrylic fabric,synthetic leather fabric,compound fabric of cotton and spandex,compound fabric of wool and acrylic,compound fabric of cotton and polyester and compound fabric of wool and polyester by gas chromatography-mass spectrometry. The different pretreatment process were used depend on difference of textures of cotton fabric . Finally samples was diluted with methanol. The influence of different sample matrix on recovery was investigated. The limits of detection of method were 0.05 ～ 0.20 mg/kg for different compounds, the recoveries of different matrixes and concentrations ranged from 29.4% ～ 102.8% at the spiked levels of 0.20,0.40 and 1.0 mg/kg. The relative standard deviations were less than 6.8%.The detection limit of above methods was less than the limited requirements of testing standards of China and European Union.
Key words：banned azo colourants; textiles; gas chromatography-mass spectrometry
紫外分光光度法测定小儿清热宁颗粒中黄芩苷的含量
郧海丽，周冉，雷霓，申晓雷
（石家庄学院 化工学院，河北 石家庄 050035）
摘要：建立了一种用紫外分光光度法测定小儿清热宁颗粒中黄芩苷含量的方法。以90%乙醇溶液为空白溶剂，采用紫外分光光度法在276 nm下测定小儿清热宁颗粒中黄芩苷的含量。黄芩苷乙醇溶液在3.04 ～ 9.12 mg/L浓度范围内与吸光度呈良好的线性关系，相关系数为0.9998，平均回收率为99.9%，相对标准偏差为0.70%（n = 9）。该方法简便快捷，数据准确可靠。
关键词：紫外分光光度法；小儿清热宁颗粒；黄芩苷
中图分类号：O657 文献标识码：A 文章编号：0258-3283（2017）
Determination of Baicalin in Xiaoer Qingrening Granula by UV-Spectrophotometry YUN Hai-li*，ZHOU Ran，LEI Ni，SHEN Xiao-lei (Department of Chemical Engineering，Shijiazhuang University，Shijiazhuang 050035, China)
Abstract: The method of determination of baicalin in xiaoerqingreninggranula by UV-spectrophotometry was established. The content of baicalin was determined by UV-spectrophotometry at 276 nm with the blank was 90% ethanol solution. The content of the baicalinethanol solution showed a better linear relationship with the absorbance in the range of 3.04 ～ 9.12 mg/L, correlation was 0.9998. The average recovery was 99.9%, RSD was 0.70%(n = 9). The method was easy-to-handle with good accuracy and reproducibility.
Key words: UV-Spectrophotometry；xiaoer qingrening granula；baicalin
量子点荧光猝灭法测定太湖河蚌中微囊藻毒素-RR
孟元华*，朱鹏飞，龚燕，凌霞
(江苏省无锡市疾病预防控制中心，江苏 无锡 214023)
摘要：建立了一种量子点(QDs)荧光猝灭法测定河蚌中微囊藻毒素-RR(MC-RR)的方法。将QDs与MC-RR单克隆抗体共价结合，形成QDs-MC-RR单克隆抗体生物共轭体。加入MC-RR，该生物共轭体发生荧光猝灭现象。在pH 7.17、反应温度为37 ℃、QDs浓度为2.0 mg/mL条件下，生物共轭体荧光猝灭程度和MC-RR浓度呈较好的线性关系。结果显示，该方法的检出限可达4.5 × 10-10 mol/L，相对标准偏差为8.9%，加标回收率为76.4% ~ 87.3%。该方法操作简便、快速，可用于河蚌中微囊藻毒素-RR的检测。
关键词：量子点；荧光；河蚌；微囊藻毒素-RR
中图分类号：O657.6 文献标识码：A 文章编号：0258-3283（2017）
Determination of Microcystin-RR in River Clam of TaihuLake Based on Fluorescence Quenching of Quantum Dots MENG Yuan-hua*, ZHU Peng-fei, GONG Yan, LING Xia (Wuxi Center for Disease Control and Prevention, Wuxi 214023, China)
Abstract: To establish a method for the determination of microcystin-RR (MC-RR)in river clam by quantum dots (QDs) fluorescence quenching. Monoclonal anti-MC-RR antibody was conjugated to the modified QDs to form the bioconjugates. The fluorescence intensity of the bioconjugates between QDs and monoclonal anti-MC-RR antibody was quenched in the presence of MC-RR. Under temperature of 37 ℃, to an aqueous QDs solution (pH 7.17) with the concentration of 2.0 mg/mL, a linear relationship between the fluorescence quenching percentage of the bioconjugates and the concentration of MC-RR was observed. The detection limit of method was 4.5×10-10 mol/L with relative standard deviation of 8.9%.The average recoveries were 76.4% to 87.3%. The method is fast, simple and it could be used for the determination of microcystin-RR in river clam.
Key words：quantum dots; fluorescence; river clam; microcystin-RR
固绿分光光度法测定土壤中的痕量四溴双酚A
雷禄a，凌绍明*b，刘惠斌b
（百色学院 a. 预科教育学院；b. 化学与环境工程学院，广西 百色 533000）
摘要：四溴双酚A对Fenton反应产生的羟基自由基氧化固绿反应具有抑制作用，建立分光光度法测定土壤中痕量四溴双酚A分析方法。探讨了硫酸用量、硫酸亚铁用量、固绿FCF用量、H2O2用量、温度以及时间等因素对体系的影响。结果表明，该方法操作简单、便于快速分析。在最佳实验条件下，方法的线性范围为2.67×10-6 ～ 3.33×10-5 g/L，相关系数R为0.9992，检出限为1.6×10-7 g/L。方法应用于土壤中痕量四溴双酚A的测定时，测定结果的相对标准偏差为2.9% ～ 4.1 %，回收率为90.8% ～ 109.4 %。
关键词：Fenton反应；分光光度法；四溴双酚A
中图分类号：O656.31；O656.33 文献标识码：A 文章编号：0258-3283（2017）
Determination of Trace Tetrabromobisphenol A in Soil by Fast Green Spectrophotometry LEI Lua, LING Shao-ming*b, LIU Hui-binb (a. Pre-undergraduate Education School; b.college of Chemistry and environment engineering, Baise University, Baise 533000, China)
Abstract: Tetrabromobisphenol A can inhibit oxidative reaction of hydroxyl radical produced by Fenton reaction on discoloring fast green FCF. Based on the reaction with inhibition principle, a new spectrophotometric method for the determination of trace Tetrabromobisphenol A in soil was established. The effects of some factors such as dosage of sulfate acid, dosage of ferrous sulfate, dosage of fast green FCF, dosage of H2O2, temperature and time, on the system were investigated. The results indicated that the method has the advantages of simple operation and quick analysis. Under the optimum conditions, the linear range of tetrabromobisphenol A was from 2.67×10-6 ～ 3.33×10-5 g/L with the linearity relation coefficient R was 0.9992，and the detection of limit is 1.6×10-7 g/L. For the determination of trace level of tetrabromobisphenol A in soil, the relative standard deviation of the determination was from 2.9% ～ 4.1% and the recovery rate was from 90.8% ～ 109.4%.
Keywords: Fenton reaction; spectropotometry; tetrabromobispherol A
超声波法降解氯氰菊酯的工艺条件优化
宋小利*，高立国
(榆林学院 化学与化工学院，陕西 榆林 719000)
摘要：为了研究降解氯氰菊酯有机氯农药的最佳工艺条件，用超声波并通过响应曲面法(RSM)来优化最佳工艺条件。用气相色谱及气质-联用色谱仪对氯氰菊酯进行了定性及定量检测，实验结果表明氰菊酯的超声波降解最优工艺条件为：超声波处理时间为28.64 min，超声波处理温度为26.85 ℃，超声波功率为223.65 W，在此条件下的降解率为44.9%。
关键词：氯氰菊酯；响应曲面法；超声波法
中图分类号：O641 文献标识码：A 文章编号：0258-3283（2017）
Optimization of Degradation of Cypermethrin by Ultrasonic Wave SONG Xiao-li*, GAO Li-guo (School of Chemistry and Chemical Engineering, Yulin University ,Yulin 719000, China)
Abstract: In order to elucidate the best conditions of the degradation of cypermethrin, in this work, cypermethrinwas degraded by ultrasonic wave and using response surface methodology (RSM) to investigate the conditions of degradation technology. The Qualitative and quantitative detection of cypermethrin were investigated by chromatograph and gas chromatography-mass spectrometer. The results showed that ultrasonic treatment time is 28.64 min, ultrasonic treatment temperature is 26.85 ℃, ultrasonic power is 26.85 ℃. In conditions of the optimal degradation, the degradation rate of cypermethrin is 44.9%.
Key words: cypermethrin; response surface method; ultrasonic method
甜菊醇和异甜菊醇与DNA作用方式的研究
李建*1，隋晓辰2，王小侠2，张珏1
(1. 江苏省原子医学研究所 卫生部核医学重点实验室 江苏省分子核医学重点实验室，江苏 无锡 214063；
2. 江南大学 化学与材料工程学院 食品科学与技术国家重点实验室，江苏 无锡 214122)
摘要：甜菊醇是新型甜味剂甜菊糖在人体内的代谢产物，在酸性环境中可重排成异甜菊醇，它们都是重要的药物合成中间体。研究甜菊醇和异甜菊醇和DNA的作用方式有助于理解它们的药理或细胞毒性。以小牛胸腺DNA（CT-DNA）为模板，通过考察甜菊醇和异甜菊醇对CT-DNA熔点和粘度的影响，以及甜菊醇和异甜菊醇与CT-DNA体系紫外吸收的变迁，初步推断甜菊醇和异甜菊醇都是以沟槽方式与CT-DNA结合；异甜菊醇与CT-DNA的作用比甜菊醇与CT-DNA作用强。
关键词：甜菊醇；异甜菊醇；DNA；沟槽方式
中图分类号：O641.3 文献标识码：A 文章编号：0258-3283（2017）
Binding Modes of Steviol and Isosteviol with DNA LI Jian*1, SUI Xiao-chen2, WANG Xiao-xia2, ZHANG Jue1 (1. Key Laboratory of Nuclear Medicine, Ministry of Health, Jiangsu Key Laboratory of Molecular Nuclear Medicine, Jiangsu Institute of Nuclear Medicine, Wuxi 214063, China；2. State Key Laboratory of Food Science and Technology, School of College of Chemical & Material Engineering, Jiangnan University, Wuxi 214122, China)
Abstract: This work reported the interaction between steviol or isosteviol and CT-DNA by observing the changes on UV, viscosity and melting point of the CT-DNA before and after the interaction. Based on the results, it could be inferred that the binding of steviol and isosteviol with CT-DNA is a groove binding, and the interaction between isosteviol and CT-DNA is stronger than that of steviol and CT-DNA.
Key words: steviol; isosteviol; DNA; groove binding
2-(2-吡啶)-5, 6, 7, 8-四氢吡啶并[4, 3-d]嘧啶及其衍生物的合成
罗维*1a，徐运启2，苑丽红1b，李保庆1b
（1. 广东环境保护工程职业学院 a. 实训中心；b. 环境监测系，广东 佛山 528216；
2. 南方医科大学 南方医院，广东 广州 510515)
摘要：以N-叔丁氧羰基-4-哌啶酮为原料，设计合成了一种新型的2-(2-吡啶)-5, 6, 7, 8-四氢吡啶并[4, 3-d]嘧啶及其3种衍生物。通过1HNMR、LC-MS和HPLC确证了3种衍生物的结构。实验证明，所合成的3种衍生物能够高效抑制白血病K562细胞系的增殖，并能够有效抑制卵巢癌HO-8910细胞的增殖。
关键词：2-(2-吡啶)-5, 6, 7, 8-四氢吡啶并[4, 3-d]嘧啶；衍生物；合成；抗癌
中图分类号：O626.2 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of 2-(pyridin-2-yl)-5,6,7,8-tetrahydropyrido[4,3-d]pyrimidine and Derivatives LUO Wei*1a, XU Yun-qi2, YUAN Li-hong1b, LI Bao-qing1b (1. a. Practice Centre; b. Department of Environment Monitoring, Guangdong Polytechnic of Environmental Protection Engineering, Foshan 528216, China; 2. Nanfang Hospital, Southern Medical University, Guangzhou 510515, China)
Abstract: Based on tert-butyl 4-oxopiperidine-1-carboxylate, a new type of 2-(pyridin-2-yl)-5,6,7,8- tetrahydropyrido[4,3-d]pyrimidine and three derivatives were synthesized. The structures were confirmed by 1HNMR，LC-MS and HPLC. The results showed that the three derivatives can effectively inhibit the proliferation of K562 cell line, and can inhibit the proliferation of ovarian cancer HO-8910 cells.
Key words: 2-(pyridin-2-yl)-5,6,7,8-tetrahydropyrido[4,3-d]pyrimidine; derivatives; synthesize; anticancer
碘代咔唑类DNMT抑制剂中间体的合成
潘琪，王凯，莫灿，周文，刘博*
(广州中医药大学 第二临床医学院，广东 广州 510006)
摘要：以咔唑和碘为原料，经碘化、N-烷基化、开环得到目标化合物1,3-双（3,6-二碘-9-H-咔唑-9-基）-2-丙醇，总收率36.5%。产物的结构经1HNMR、13CNMR和MS表征。对基于I2/DMSO体系的关键碘化反应进行了机理阐释和条件优化，确定了最优反应条件为n（咔唑） ：n（I2）= 2 : 3，110 ℃下反应4 h，平均产率为85.2%。
关键词：DNMT抑制剂；1,3-双（3,6-二碘-9-H-咔唑-9-基）-2-丙醇；3,6-二碘咔唑；碘代；合成
中图分类号: TQ251.3 文献标识码:A 文章编号: 0258-3283（2017）
Synthesis of DNMT inhibitor intermediate with iodine substituted carbazole PAN Qi*, WANG Kai, MO Can, ZHOU Wen, LIU Bo* (The Second Clinical Medical College, Guangzhou University of Chinese Medicine, Guangzhou 510006, China)
Abstract:1,3-bis(3,6-diiodo-9H-carbazol-9-yl)propan-2-ol was synthesized from carbazole and iodine by iodination, N- alkylation and ring-opening. The total yield is 36.5%. The target compounds were confirmed with 1HNMR, 13CNMR, and MS. The mechanism of the key iodination based on the I2/DMSO system was explained and the condition of iodination was optimized. In the presence of n (carbazole) : n (I2) = 2 : 3 as starting materials, DMSO as solvent, 4 h under 110 ℃, the average yield of the iodination was up to 85.2%．
Key words: DMNT inhibitor ; 1,3-bis(3,6-diiodo-9H-carbazol-9-yl)propan-2-ol; 3,6-diiodocarbazole; iodination; synthesis
超声辐射下双吲哚甲烷衍生物的合成
尹晓刚，吴小云，王野，陈治明，陈卓*
（贵州师范大学 化学与材料科学学院 贵州省功能材料化学重点实验室，贵州 贵阳 550001）
摘要：以吲哚、醛为原料，蒙脱土固载路易斯酸为催化剂，超声条件下合成双吲哚甲烷类衍生物。得到最优合成条件为：吲哚与醛的物质的量比为n（吲哚）∶n（醛）= 2.0∶1.1，蒙脱土负载氯化铜为催化剂，二氯甲烷作溶剂，反应温度为50 ℃，超声时间为15 min。产率最高达99.3%，催化剂循环3次产率仍可达81.3%。产物通过核磁、红外、熔点进行表征。
关键词：蒙脱土负载；超声；双吲哚甲烷
中图分类号：O626.13 文献标识码：A 文章编号：0258-3283（2017）
Preparation of Bis(indolyl) alkanes Derivatives under Ultrasonic Conditions YIN Xiao-gang, WU Xiao-yun, WANG Ye, CHEN Zhi-ming, CHEN Zhuo* (School of Chemistry and Materials Science，Guizhou province Chemical Key Laboratory of Functional Materials，Guizhou Normal University, Guiyang 550001，China)
Abstract: A series of bis ( indolyl) alkanes derivatives were synthesized via the reaction between indole and aromatic aldehydes catalyzed by Lewis acid loaded montmorillonite under ultrasonic condition. The optimal synthesis conditions: montmorillonite supported copper chloride as catalyst, molar ratio of indole and aldehyde is 2.0∶1.1, CH2Cl2 as a solvent, ultrasonic time is 15 min and the reaction temperature is 50 ℃. The yields can reach up to 99.3% under optimal conditions and 81.3% after catalyst recycled three times. The products were confirmed by 1HNMR, IR and MP.
Key words: loaded montmorillonite; ultrasonic assisted; bis( indolyl) alkanes
乙酰阿魏酸薄荷醇酯的合成与表征
张海龙1，鲍远志2，翁士兵2，柴多里*1
(1.合肥工业大学 化学与化工学院，安徽 合肥 230009；
2. 六安市捷通达化工有限责任公司，安徽 六安 237158)
摘要：以香兰素和乙酸酐为原料，无水乙酸钠为催化剂，采用Perkin反应合成乙酰阿魏酸，再与氯化亚砜反应合成乙酰阿魏酰氯后，以三聚磷酸钠为缚酸剂与薄荷醇反应合成标题化合物，产率78.5％。采用FT-IR、1HNMR、13CNMR、元素分析、MS对目标化合物进行了表征并确认了产物的结构。
关键词：香兰素；薄荷醇；三聚磷酸钠；乙酰阿魏酸薄荷醇酯
中图分类号：TQ245.2 文献标识码：A 文章编号：0258-3283(2017)
Synthesis and Characterization of Menthol Ester Acetylferulate ZHANG Hai-long1, BAO Yuan-zhi2, WENG Shi-bing2, CHAI Duo-li*1 (1. Schoolof Chemistry and Chemical Engineering, Hefei University of Technology, Hefei 230009, China ; 2. Lu’anJietongda Chemical Co. , Ltd. ,Lu’an 237158,China)
Abstract：Acetylferulic acid was prepared from vanillin, acetic anhydride and sodium acetate by Perkin reaction, then acetylferulic acid was reacted with thionyl chloride, and obtained acetylferuloyl chloride. Lastly menthol ester acetylferulate was synthesized from acetylferuloyl chloride, menthol and sodium tripolyphosphate. The yield of the compound was 78.5%. The product was characterized by FT-IR,1HNMR,13CNMR, elementar, MS.
Key words：vanillin；menthol；sodium tripolyphosphate；menthol esteracetylferulate
4, 5, 6, 7-四氢吡唑并[1, 5-a]哌嗪-3-甲酸乙酯
陈寿林，滕大为*
（青岛科技大学 化工学院，山东 青岛 266042）
摘 要：以4-氯-3-氧代丁酸乙酯为原料，经与叔丁醇钾醚化、DMF-DMA缩合、水合肼环合、脱叔丁基、羟基氧化、还原氨化、分子内环合以及氢化脱苄等反应合成了4,5,6,7-四氢吡唑并[1,5-a]哌嗪-3-甲酸乙酯。并对其中关键步骤羟基氧化反应和分子内环化反应的工艺条件进行了优化，获得了较优的工艺条件：在羟基氧化反应中以二氧化锰为氧化剂，氯仿为溶剂；在分子内环化反应中选择以甲基磺酰氧基(OMs)为离去基团。目标产品的总收率为39.5%。目标化合物结构经1HNMR、13CNMR、MS和元素分析进行了确定。
关键词：4,5,6,7-四氢吡唑并[1,5-a]哌嗪；4-氯-3-氧代丁酸乙酯；环合反应
中图分类号：O626.1 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of 4, 5, 6, 7-Tetrahydro-pyrazolo[1, 5-a] piperazine-3-carboxylic Acid Ethyl Ester CHEN Shou-lin, TENG Da-wei* (College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China)
Abstract: 4,5,6,7-Tetrahydro-pyrazolo[1,5-a]pyrazine-3-carboxylic acid ethyl ester was synthesized from 4-chloro-3-oxo-butyric acid ethyl ester by the reactions of etherification with KOtBu, condensation with DMF-DMA, cyclization with N2H4·H2O, removal of t-butyl group, oxidation of hydroxyl group, reductive amination with N-benzyl ethanolamine, intramolecular cyclization and hydrogenation debenzylation. The optimum conditions of oxidation of hydroxyl group and intramolecular cyclization were obtained. For oxidation of hydroxyl group: MnO2 as oxidizing agent, chloroform as solvent. For intramolecular cyclization: Methylsulfonyloxy group(OMs) as leaving group. The overall yield is 39.5%. The aimed compound was confirmed by 1HNMR,13CNMR, MS and elemental analysis.
Key words: 4,5,6,7-tetrahydropyrazolo[1,5-a]piperazine; 4-Chloro-3-oxo-butyric acid ethyl ester; cyclization
2, 2-二氟-1, 3-苯二氧戊环-4-甲醛的合成
付青存*，李戎，甘争艳，
（新疆轻工职业技术学院 化工技术分院，新疆 乌鲁木齐 830021）
摘要：标题化合物是合成杀菌剂咯菌腈的重要原料，考察了以邻香兰醛为原料制备2, 3-二羟基苯甲醛，然后与二氟二氯甲烷反应直接合成得到目标中间体的方法。通过优化反应条件，得到最佳反应条件为0.5 mol/L双氧水、3.5 mol/L氢氧化钠，反应温度60 ℃、水解得2, 3-二羟基苯甲醛。再以DMSO为反应溶剂，3.0 mol/L二氟二氯甲烷在80 ℃下通过环合反应得到标题化合物，总收率75%，纯度97%。
关键词：2,2-二氟-1,3-苯二氧戊环-4-甲醛；二氟二氯甲烷；咯菌腈
中图分类号：TQ42 文献标识码：A 文章编号：0258-3283（2017）
Synthesis Process of 2,2-difluorobenzo[1,3]dioxole-4-carbaldehyde Fu QingCun*, Li Rong, Gan Zhengyan (Chemical Technology Branch ，Xinjiang Vocational College of Light Industry，Urumqi 830021, China)
Abstract: 2,2-Difluorobenzo[1,3]dioxole-4-carbaldehyde was an important intermediate to synthesize fludioxonil. Taking 2-hydroxy-3-methoxybenzaldehyde as the starting materials. The key intermediate 2,3-dihydroxybenzaldehyde was obtained via hydrolysis reaction. And the target compound 2,2-difluorobenzo[1,3]dioxole-4-carbaldehyde was obtained via the cyclization reaction with dichlorodifluoromethane. The optimal reaction conditions were 0.5 mol/L H2O2, 3.5mol/L NaOH, setting 60 oC as the hydrolysis temperature, and using 3.0 mol/L dichlorodifluoromethane via cyclization reaction under the temperature of 80 oC. The total yield of the product was 75%, and the purity was 97%.
Key words: 2,2-difluorobenzo[1,3]dioxole-4-carbaldehyde; dichlorodifluoromethane; fludioxonil
杀菌剂氟环唑的合成新方法
邱勇波*，张晓蕾
（内蒙古化工职业学院 化学工程系 ，内蒙古 呼和浩特 010070）
摘要：氟环唑作为重要的一类三唑类杀菌剂，市场应用前景广阔。考察了以邻氯苄氯与α-氯代-4-氟-苯乙酮为原料，经格氏反应得到格氏产物，进一步与1, 2, 4-三氮唑反应得到重要中间体接三唑化合物。同时以此为原料，通过溴素与双氧水溴化，以及在碱性条件下分子内的环合反应得到目标化合物氟环唑。通过反应条件优化，实验确定的最佳反应条件为四氢呋喃为格氏反应溶剂，1,2,4-三氮唑用量为0.9 mol，接三唑反应温度为75 ℃，溴化反应温度为60℃，环氧反应的缚酸剂为1.5 mol氢氧化钠。产品总收率58%，含量96%。
关键词：氟环唑；格氏反应；溴化反应
中图分类号：TQ 文献标识码：A 文章编号：0258-3283(2017)
A new method of synthesis of epoxiconazole QIU Yong-bo*，ZHANG Xiao-lei ( Department of Chemical Engineering , Inner Mongolia Vocational College of Chemical Engineering, Hohhot 010070, China)
Abstract: Epoxiconazol is an important triazole with a good inpetus and vast potential development. Taking 2-chloro benzyl chloride and 2-Chloro-4'-fluoroacetophenone as the starting material, the Grignard product was obtained. The key intermediate triazole derivative was synthesized via reacting with 1,2,4-triazole. Under the brimination reaction of Br2/H2O2 and intermolecular cyclization reaction, the aimed product epoxiconazol was formed. With the optimal reaction conditions, the triazole derivative was synthesized under 75 ℃ with THF as the Grignard reaction solvent and 0.9 mol 1,2,4-triazole. The product was obtained viathe brimination reaction under 60 ℃ and taking 1.5 mol NaOH as the base. The total yield of epoxiconazol reached 58%. The purity of the product was 96%.
Key words: epoxiconazol; grignard reaction; brimination reaction
