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