多基硫脲类Schiff碱的合成及生物活性及离子识别
李庆伟，刘峥*，李海莹，赵永，江道勇
(桂林理工大学 化学与生物工程学院，广西 桂林 541004)
摘要：以异硫氰酸苯酯、氨基硫脲、乙二胺、氨基脲和二乙撑三胺作为原料，合成了异硫氰酸苯酯-氨基甲酰肼(PITCAM)、异硫氰酸苯酯-硫代氨基脲(PITCTSC)，双异硫氰酸苯酯-1, 2-二氨基乙烷(PITCE)和双异硫氰酸苯酯-二乙撑三胺(PITCD)4种多基硫脲类Schiff碱，其结构经1HNMR、IR、ESI-MS和元素分析进行表征。对4种合成的化合物进行抑制大肠杆菌、金黄色葡萄球菌以及欧文氏草生杆菌的生物活性的测定，结果表明4种合成的多基硫脲类Schiff碱化合物均具有一定的生物抑菌活性，其中合成的化合物PITCAM的生物抑菌活性最好；测试其对不同金属离子的荧光响应光谱，实验结果表明PITCAM对Cu2+响应明显。
关键词：硫脲；Schiff碱；合成；抑菌活性；离子识别
中图分类号：X832 文献标识码：A 文章编号：0258-3283（2017）
Synthesis, Biological Activityand Ion identification of Multi-thiourea Schiff Base Derivatives LI Qing-wei, LIU Zheng*, LI Hai-ying, ZHAO Yong, JIANG Dao-yong（Guilin Chemical and Biological Engineering＆the Key Laboratory of organic synthesis of theGuangxiZhuangAutonomousRegion，Guilin University of Technology，Guilin 541004，China）, Huaxue Shiji, 2017, 39(4),
Abstract: Phenylisothiocyanate - semicarbazide (PITCAM), phenylisothiocyanate - thiosemicarbazone (PITCTSC), double phenylisothiocyanate 1, 2-diaminoethane (PITCE) and double phenylisothiocyanate -
diethylenetriamine(PITCD) were synthesized by using phenyl isothiocyanate, thiosemicarbazide, ethylenediamine, semicarbazide and diethylenetriamine as the raw materials. The structures were confirmed by 1HNMR, IR, ESI-MS and elemental analysis. The antimicrobial activities of the Schiff base against S.aureus, E.herbicola and E.coli, were investigated. The results showed that the Schiff base exhibited certain biological activities, and PITCAM was the best one. Based on the fluorescence spectra of Schiff base for different metal ions, PITCAM showed significant response for Cu2 +.
Key words: thiourea; Schiff base; synthesis; antifungal activity; ion identification
PdAg、PdAu合金纳米晶的制备及其催化性能研究
贾晓丹1, 2，谢朝晖2，华达银1，尹宏峰*2
（1. 宁波大学 理学院，浙江 宁波 315211；2. 中国科学院宁波材料技术与工程研究所，浙江 宁波 315201）
摘要：采用硼氢化钠一步还原法，首先得到PdAg和PdAu双金属合金纳米颗粒。利用XRD、TEM以及紫外可见光光谱表征技术对其进行了表征分析。结果表明，PdAg和PdAu两种合金都具有纳米颗粒分散均匀且颗粒尺寸小等优点。随后采用胶体沉积法将两种合金均匀地负载在Al2O3上，成功获得PdAg/Al2O3和PdAu/Al2O3两种金属纳米催化剂。在邻氯硝基苯加氢反应中，与Pd/Al2O3纳米催化剂相比，PdAg/Al2O3催化剂显示出95.5%的选择性，而PdAu/Al2O3催化剂更是显示出高达98.7%的选择性，这可能归因于Pd与Ag或Pd 与Au金属间的协同效应。
关键词：PdAg；PdAu；催化加氢；邻氯硝基苯；选择性
中图分类号：O643.3 文献标识码：A 文章编号：0258-3283（2017）
Preparation and Catalytic Performance of PdAg and PdAu Alloy Nanocrystals JIA Xiao-dan1,2, Xie Zhao-hui2, Hua Da-yin1,Yin Hong-feng*2 (1. Faculty of Science, Ningbo University, Ningbo 315211,China; 2.Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Science, Ningbo 315201,China)，Huaxue Shiji, 2017, 39(4),
Abstract: The PdAu and PdAg bimetallic nanoparticles were synthesized by one-step reduction with sodium borohydrid and characterized by XRD, TEM and UV-visible spectroscopy. The results show that Pd and Ag, or Pd and Au can both form alloy structure, the nanoparticles are monodisperse. PdAg/Al2O3 and PdAu/Al2O3 bimetallic nanocatalysts were successfully prepared by homogeneous loading of bimetallic nanoparticles on Al2O3 by colloid deposition. The catalyst was probe-tested in the selective hydrogenation of o-chloronitrobenzene, compared with the Pd/Al2O3 catalyst, the PdAg/Al2O3 catalyst showed 95.5% selectivity and PdAu/Al2O3 catalysts showed higher selectivity up to 98.7%, which could be attributed to the synergistic effect of Pd and Ag or Pd and Au.
Key words: PdAg; PdAu; catalytic hydrogenation; o-nitrochlorobenzene; selectivity
2-二乙硫基亚甲基-3-羰基（羟基）丁酸乙酯与吲哚衍生物的（脱硫）偶联反应
王金娟，裴学海，黄克俊，王文琛，杨志翔，陈治明*
（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：在回流条件下，二甲亚砜（DMSO）作溶剂，在20 mol%联萘酚酸存在下，2-二乙硫基亚甲基-3-羰基丁酸乙酯与吲哚衍生物能有效地进行脱硫偶联反应，高产率生成b-吲哚基-b-乙硫基不饱和羰基化合物。在相同条件下，2-二乙硫基亚甲基-3-羟基丁酸乙酯与吲哚衍生物能有效地进行偶联反应，高产率生成a-吲哚基二硫缩烯酮。该反应具有催化剂经济易得及其用量少、反应条件温和、环境友好和易操作等优点。
关键词：b-吲哚基-b-乙硫基不饱和羰基化合物；a-吲哚基二硫缩烯酮；联萘酚酸；吲哚衍生物
中图分类号：O626 文献标识码：A 文章编号：0258-3283（2017）
(Desulfurization) Coupling Reaction of Ethyl 2-(bis(ethylthio)me-thylene)-3-(oxo)hydroxybutanoate with Indole Derivatives WANG Jin-juan, PEI Xue-hai, HUANG Ke-jun, WANG Wen-chen, YANG Zhi-xiang, CHEN Zhi-ming* (Key Laboratory of Functional Materials Chemistry of Guizhou Province，School of Chemistry and Materials Science，Guizhou Normal University，Guiyang 550001, China), Huaxue Shiji, 2017, 39(4),
Abstract: The desulfurization coupling reaction of ethyl 2-(bis(ethylthio)methylene)-3-oxobutanoate and indole derivatives was efficiently performed in the presence of 2,2＇-dihydroxy -1,1＇-dinaphthyl-3,3＇-dicarboxylic acid was (20 mol%) at reflux in DMSO, affording b-indolyl-b-ethylsuleenyl unsaturated carbonyl-compounds in excellent yields. The coupling reaction of ethyl 2-(bis(ethylthio)methylene)-3-hydroxybutanoateand indole derivatives was efficiently performed in the same conditions, affording a-indolyl ketene dithioacetals in excellent yields. The procedure has the advantages of lower amount of inexpensive catalyst, mild reaction condition, environmentally benign and simplicity.
Key words: b-indolyl-b-ethylsuleenyl unsaturated carbonyl-compounds;a-indolyl ketene dithioacetals; 2,2＇-dihydroxy-1,1＇- dinaphthyl-3,3＇- dicarboxylic acid; indole derivatives
基于三维框架材料H3PW6Mo6O40/Zn(BDC)(4,4´-Bipy)0.5高效吸附亚甲基蓝
龚文朋，刘炜烽，杨水金*
(湖北师范大学 化学化工学院 污染物分析与资源化技术湖北省重点实验室，湖北 黄石 435002)
摘要: 采用溶剂热法，用H3PW6Mo6O40对金属有机骨架Zn(BDC)(4,4´-Bipy)0.5进行改性，制备出金属有机骨架复合材料H3PW6Mo6O40/Zn(BDC)(4,4´-Bipy)0.5。利用IR、XRD、TG、SEM对其结构进行分析。同时，以亚甲基蓝溶液模拟染料废水进行了吸附实验，考察了初始pH、温度对吸附容量的影响，探究了其吸附等温线和动力学特征。实验结果表明，H3PW6Mo6O40/Zn(BDC)(4, 4´-Bipy)0.5对亚甲基蓝有很好的吸附性能，在20 ℃和pH 2的条件下的吸附量达588.24 mg/g，且该吸附符合Langmuir等温吸附型和拟二级动力学方程，吸附过程是一个自发和放热过程。
关键词：金属有机骨架；H3PW6Mo6O40；吸附；亚甲基蓝
中图分类号：X703.5 文献标识码：A文章编号：0258-3283（2017）
Efficient Adsorption of Methylene Bule by the Composites Based Three-dimensional Framework H3PW6Mo6O40/Zn(BDC)(4,4´-Bipy)0.5 GONG Wen-peng, LIU Wei-feng, YANG Shui-jin* (College of Chemistry and Chemical Engineering, Institute for Advanced Materials, Hubei Key Laboratory of Pollutant Analysis & Reuse Technology , Hubei Normal University, Huangshi 435002, China), Huaxue Shiji, 2017, 39(4),
Abstract：In this work, H3PW6Mo6O40/Zn(BDC)(4,4´-Bipy)0.5 were synthesized by the solvothermal synthesis method, and the metal organic framework Zn(BDC)(4,4´-Bipy)0.5 were modified by H3PW6Mo6O40. The structures of the composite were confirmed by IR, XRD, TG, SEM, Meanwhile, methylene blue dye solution is used to simulate waste water and to explore the influences of the adsorption process containing the initial pH, temperature. Its adsorption isotherm and kinetic model were also explored. The results show that H3PW6Mo6O40/Zn(BDC)(4,4´-Bipy)0.5 has great adsorption capacities for the methylene blue. It’s maximum adsorption capacity value reached 588.24 mg/g at 193K and pH 2. The experiment data could be well described by the Langmuir equations and pseudo-second-order kinetic model. The adsorption process of the composites on methylene blue was spontaneous and exothermic.
Key words：metal organic frameworks; H3PW6Mo6O40; adsorption; methylene blue
川芎嗪-丁苯酞衍生物的设计、合成及抗血小板聚集活性研究
朱桃，李毅，樊玲玲，陈文章，汤磊*
（贵州医科大学 药学院，贵州 贵阳 550004）
摘要：以邻苯二甲酸酐和川芎嗪为原料，经自由基取代、正丁基锂亲核加成、对甲基苯磺酸催化脱水、Pd/C加氢还原、水解、酯化等反应合成了3个川芎嗪与丁苯酞拼合衍生物，其结构经1HNMR、13CNMR和HRMS确证。其中(3, 5, 6-三甲基吡嗪-2-基)甲基-2-戊酰基苯甲酸酯（1）对由腺苷二磷酸(ADP)诱导的血小板聚集活性抑制率IC50为0.26 mmol/L，优于母体化合物川芎嗪和丁苯酞，是具有良好开发前景的候选化合物。
关键词：川芎嗪；丁苯酞；合成；抗血小板聚集活性
中图分类号：R914.5 文献标识码: A 文章编号：0258-3283（2017）
Design, Synthesis and Anti-platelet Aggregation Activity Evaluation of Ligustrazine and 3-n-butylphthalide Derivatives ZHU Tao, LI Yi, FAN Ling-Ling, CHEN Wen-Zhang, TANG Lei*(Guizhou Medical university, Guiyang 550004, China)
Abstract : Using phthalic anhydride and ligustrazine as the ingredients, three conjugated derivatives of ligustrazine and 3-n-butylphthalide were designed and synthesized via free-radical substitution, n-BuLi nucleophilic addition, p-tolunenesulfonic acid dehydration, Pd/C catalysis-hydrogenation, hydrolysis, esterification. and their structures were confirmed by 1H NMR, 13C NMR and HRMS. The inhibitory activity of the target compound (3,5,6-trimethylpyrazin-2-yl)methyl-2-pentanoylbenzoate (1) against adenosine diphosphate(ADP) induced platelet aggregation was 0.26 mmol/L. In comparison with ligustrazine and 3-n-butylphthalide (NBP), the compound 1 possessed better antiplatelet aggregation activity. Therefore, they may be utilized as lead compound for further investigation.
Key words：ligustrazine; 3-n-butylphthalide; synthesis; antiplatelet aggregation activity
一种S-亚硝基二硫醇的合成及特性分析
胡常杰，张汉桥，张梦林，谢卫红，糜志远，苏江涛*
(湖北工业大学 生物与食品工程学院，湖北 武汉 430068)
摘要：设计合成了一种一氧化氮供体化合物S-亚硝基二硫醇，并通过1HNMR、13CNMR和IR对结构进行了表征；同时对其释放一氧化氮（NO）的速度和影响释放速度的因素（铜离子、光和pH）进行了考察；另外，通过高效液相色谱法对分解产物进行鉴别，确定释放一氧化氮（NO）的同时主要形成含分子内环二硫键的分解产物。
关键词：S-亚硝基二硫醇；一氧化氮(NO)；环二硫键
中图分类号：O623 文献标识码：A 文章编号：0258-3283（2017）
Synthesis and Evaluation of a Novel S-nitrosated Dithiols HU Chang-jie, ZHANG Han-qiao, ZHANG Meng-lin, XIE Wei-hong, MI Zhi-yuan, SU Jiang-tao* (Department of Biological and Food Engineering College, Hubei University of Technology, Wuhan 430068, China), Huaxue Shiji, 2017, 39(4),
Abstract：A novel nitric oxide donor compound S-nitrosated dithiols was synthesized and confirmed discriminatively by 1HNMR and 13CNMR and IR. The decomposition kinetics by Cu2+, light and pH value was also investigated. The intramocular cyclic disulfide compound was proved to be the main decomposition product besides nitric oxide (NO).
Key words：S-nitrosated dithiols; nitric oxide (NO); cyclic disulfide
Keggin型磷钨钒杂多酸季铵盐的合成、表征及抑菌效果的研究
白丽明a*，吕振兴b，张伟东b，宋天舒a
（齐齐哈尔大学 a. 化学与化学工程学院，b. 材料科学与工程学院，齐齐哈尔 黑龙江 161006)
摘要：以不同钒原子数取代Keggin型磷钨杂多酸并与十六烷基三甲基溴化铵反应合成了3种杂多酸季铵盐。通过红外光谱（IR）、X-射线衍射（XRD）、紫外（UV）等表征手段确定了杂多酸以及杂多酸季铵盐的结构。结果表明，在红外光谱中，引入钒原子后阴离子负电荷增加，导致相应的特征峰出现红移现象；从X-射线衍射谱图中确定了杂多酸季铵盐的二级结构，最后通过热重分析（TG）得出杂多酸季铵盐所含结晶水的数目。通过杯碟法测试了目标产物对大肠杆菌、金黄色葡萄球菌、枯草芽孢杆菌、蜡样芽孢杆菌的抑菌性能，结果表明杂多酸季铵盐对枯草芽孢杆菌的抑菌能力最好，并且钒原子所占比例越高，抑菌效果越好。
关键词：磷钨钒杂多酸季铵盐；合成；表征；杂多酸活性
中图分类号： 文献标识码：A 文章编号：0258-3283（2017）
Synthesis, Characterization and Antibacterial Activities of Quaternary Ammonium Salts of Tungstovanadophosphoric Heteropolyacid with Keggin Structure BAI Li-minga *, LV Zhen-xingb, ZHANG Wei-dongb, SONG Tian-shua (a. College of Chemistry and Chemical Engineering; b. College of Materials Science and Engineering, Qiqihar University, Qiqihar 161006, China), Huaxue Shiji, 2017, 39(4),
Abstract: Three kinds of quaternary ammonium salts were synthesized with tungstophosphoric acidwith Keggin structurereplaced by the different number of vanadium atoms, andreacted with hexadecyltrimethyl ammonium bromide. The heteropolyacids and the quaternary ammonium salts were characterized by IR,XRD and UV. The results show that red shift of the corresponding characteristic peak,due to the increase of anion negative charge after the introduction of vanadium atoms, is observed in the IR spectrum, the secondary structure of the quaternary ammonium saltsis confirmed based on X-ray diffraction spectra, and the number of crystal water in the quaternary ammonium salts is measured by TG. Antibacterial activities of the target products on E. coli, Staphylococcus aureus, Bacillus subtilis, Bacillus cereus were investigated by Cylinder Plate Method (i.e, Oxford Cup ). Antibacterial activity of the quaternary ammonium saltson Bacillus subtilis is the best, and antibacterialeffect is better when the proportion of vanadium atoms is the higher.
Key words: quaternary ammonium salts of tungstovanadophosphoric heteropoly acid; synthesis; characterization; activities
硝基酚类化合物的样品前处理技术与检测方法研究进展
杨玉明，刘妧晨，许志刚*
（昆明理工大学 理学院，云南 昆明 650500）
摘要：硝基酚类化合物应用广泛，但其在环境残留中引发的安全问题备受关注，因此对环境中的硝基酚类化合物进行分析检测十分重要。系统介绍了近5年来关于硝基酚类化合物的样品前处理方法，包括固相萃取、固相微萃取、超临界流体萃取、超声波辅助提取等，综述了硝基酚类化合物的各种检测方法，包括电化学检测法、色谱检测法和光谱分析法，并对硝基酚类化合物的样品前处理和分析检测进行了总结和展望。
关键词：硝基酚类化合物；样品前处理；检测方法
中图分类号：O652.6；O658.2 文献标识码：A 文章编号：0258-3283（2017）
Progresson Sample Preparation and Detection of Nitrophenols YANG Yu-ming, LIU Yuan-chen, XU Zhi-gang* (Faculty of Science, Kunming University of Science and Technology, Kunming 650500, China), Huaxue Shiji, 2017, 39(4),
Abstract:Nitrophenolic compounds are widely used, but its residues in environment have attracted much attention. It is important to analysize nitrophenols in the environment. In this work, the sample preparation methods of nitrophenols in recent five years were introduced in detail, including solid phase extraction, solid phase microextraction, supercritical fluid extraction and ultrasonic extraction. And the detection methods of nitrophenols were also reviewed, including electrochemical detection, chromatographic detection and spectroscopy detection. Finally, the sample preparation and detection methods for nitrophenols were summarized and prospected.
Key words: nitrophenolic compounds; sample preparation; detection methods
京尼平及其衍生物抗阿尔兹海默病作用的研究进展
王玉骏1, 2，陈默函1，张艳春*1, 2，钟华1，陈姝琴1，夏庆凯1
(1. 安徽中医药大学 药学院，安徽 合肥 230012；
2. 安徽省中医药科学院药物化学研究所，安徽 合肥 230012)
摘要：京尼平(Genipin)是具有环烯醚萜结构的化合物，具有抗血栓、降血糖、抗肿瘤、抗炎和抗老年痴呆等多种药理活性。近年来，人们通过对其结构修饰改造，获得一系列具有抗阿尔兹海默病(AD)活性的京尼平衍生物。对京尼平及其衍生物抗阿尔兹海默病作用的研究进展进行综述，为京尼平的开发利用提供依据。
关键词：京尼平；京尼平苷；衍生物；阿尔兹海默病；研究进展
中图分类号：R914 文献标识码：A 文章编号：0258-3283（2017）
Progress of Genipin and Its Derivativeson Anti-Alzheimer’s Disease WANG Yu-jun1,2, CHEN Mo-han1, ZHANG Yan-chun*1,2, ZHONG Hua1, CHEN Shu-qin1, XIA Qing-kai1 (1. College of Pharmacy, Anhui University of Chinese Medicine, Hefei 230012, China; 2. Department of Medicinal Chemistry, Anhui Academy of Chinese Medicine, Hefei 230012, China), Huaxue Shiji, 2017, 39(4),
Abstract: Genipin is an iridoid compound, and has shown anti-thrombus, antidiabetics, antitumor, anti-dementia, anti-inflammatory and other pharmacological activities. In recent years, people obtain a series of genipin derivatives on anti-Alzheimer’s disease activity by the structure modification. In this work, a review of genipin and its derivatives on anti-Alzheimer’s disease activity has been provided.
Key words:Genipin; Geniposide; derivatives; Alzheimer’s disease; research progress
浅谈药品标准物质/标准样品
朱红激*
（国药集团化学试剂有限公司，上海 200002）
摘要：随着全球化进程的加快，遵守世界公认的一致标准成为产业发展的前提条件。作为已经发展成为全球化典型产业的食品药品、生物制药等产业，遵守世界公认的标准尤为重要，对中国此类产业发展而言更是当务之急。就药品标准物质/标准样品的类型、使用、管理进行分析论述，为标准物质使用者提供参考。
关键词：药品标准物质/标准样品；标准物质应用和管理；定值
A Brief Introduction of Pharmaceutical Reference Materials ZHU Hong-ji* (Sinopharm Chemical Reagent Co., Ltd., Shanghai 200002, China), Huaxue Shiji, 2017, 39(4),
Abstract: With the rapid development of globalization, obeying rules with universally recognized standards has become a prerequisite for the development of industries. For typical global industries such as Food and Drug and Biopharmaceutical, it is especially important for them to obey universally recognized standards. In China, development of industries is also essential. This paper briefly introduces and analyze stypes, application and management of pharmaceutical reference materials and provides references for users of reference materials.
Key words: pharmaceutical reference materials; application and management of reference materials；characterization of reference materials
基于液相色谱-串联质谱法检测多种食品中的16种合成着色剂
张勋1，赵韫慧1，胡婷婷1，高杰*2，李婷婷2，熊龙3，仲文严3，付瑶1，邢燕燕1
(1. 吉林出入境检验检疫局，吉林 长春 130062；2. 长春理工大学 化学与环境工程学院，吉林 长春 130022；3. 江苏豪森药业集团有限公司，江苏 连云港 222047)
摘要：针对多种食品基质(葡萄酒、汽水、黄酒、植物蛋白饮料、乳饮料、花生酱、芝麻酱和糕点)建立了同时测定赤藓红、亮蓝、诱惑红、日落黄、靛蓝、柠檬黄、苏丹红Ⅰ、苏丹红Ⅱ、苏丹红Ⅲ、苏丹红Ⅳ、酸性红1、酸性红4、酸性红8、酸性红14、酸性红88和酸性红97这16种合成着色剂的高效液相色谱-质谱联用分析方法。根据样品种类和所含成分的差别，建立了不同的样品预处理方法，并且通过对提取溶剂的讨论，采用了混合溶剂V（甲醇）︰V（乙腈）= 2︰3作为提取试剂，比单一溶剂的提取效率更高。萃取液经Kromasil 100-5型色谱柱（150 mm × 2.1 mm × 5.0 μm）分离，外标法定量。结果表明，16种合成着色剂呈现良好的线性关系（r2 = 0.9989 ～ 0.9998）,方法的测定低限为0.10或0.010 mg/kg，进行低、中、高3个浓度水平添加实验的平均回收率为86.5% ～ 97.3%，相对标准偏差＜4.9（n = 6）。该方法具有重现性好的优点，适合于多种食品中上述16种合成着色剂的检测。
关键字：合成着色剂；多种食品；液相色谱-串联质谱法
中图分类号：O657.63 文献标识码：A 文章编号：0258-3283（2017）
Determination of 16 Synthetic Colorants in Various Foods by LC-MS/MS Method ZHANG Xun1, ZHAO Yun-Hui1, HU Ting-Ting1, GAO Jie*2, LI Ting-ting2, XIONG Long3，ZHONG Wen-yan3, FU Yao1，XING Yan-Yan1 (1. Jilin Entry-exit Inspection and Quarantine Bureau, Changchun 130062, China; 2. Changchun University of Science and Technology, Changchun 130022, China; 3. Jiangsu Hanson Pharma, Lianyungang 222047, China), Huaxue Shiji, 2017, 39(3)
Abstract: A general analytical method based on liquid chromatography tandem mass spectrometry was established for 16 synthetic colorants in common food such as wine, soda, rice wine, vegetable protein beverage, milk beverages, peanut butter, sesame paste and cake, the applicable synthetic colorants include rouge red, bright blue, lure red, sunset yellow, indigo, tartrazine, acid red 1, acid red 4, acid red 8, acid red 14, acid red 88, acid red 97, Sudan Ⅰ, Sudan Ⅱ, Sudan Ⅲ and Sudan Ⅳ. Different methods for sample pre-treatment were also established depending on the difference of samples and contained ingredients. Mixed solvent of methanol and acetonitrile（V(methanol) : V(acetonitrile) = 2 : 3）was used for extraction analytes and showed much higher extraction efficiency than single solvent. Extraction liquid was separated by a Kromasil 100-5 column (150 mm × 2.1 mm × 5.0 μm) and quantified by external standard method. The calibration curves showed very good linearity for all 16 synthetic colorants with correlation coefficients of 0.9989 ～ 0.9998. The determination limits of 16 synthetic colorants were 0.10 mg/kg or even 0.010 mg/kg. The recoveries of analytes with low, middle and high concentrations were lying in 86.5% ～ 97.3% and the relative standard deviations was less than 4.9(n = 6). The method is reproducible and could be applied for the determination of above-mentioned 16 synthetic colorants in various kinds of foods.
Key words: synthetic colorants; food; liquid chromatography tandem mass spectrometry（LC-MS/MS）
双波长双指示剂褪色光度法测定大米中的痕量镉
郭振良*1，马岩1，王晓升1, 2
（1. 鲁东大学 化学与材料科学学院，山东 烟台 264025；
2. 山东省寿光市纪台镇第二初级中学，山东 潍坊 262723）
摘要：在盐酸介质中，痕量镉离子对双氧水氧化茜素红S和硫堇具有较强烈的催化作用，因此建立了一种测定痕量镉离子的双波长双指示剂褪色光度法。实验结果表明，溶液的最大吸收波长分别出现在420 nm和610 nm。6次空白实验的标准偏差S = 6.31 × 10-4，相对标准偏差为0.01%，检出限为4.878×10-2 μg/mL。
关键词：镉；茜素红S；硫堇；双氧水；双波长双指示剂褪色光度法
中图分类号：O657.3 文献标识码：A 文章编号：0258-3283（2017）
Determination of Trace Cadmium in Rice by Double Wavelength Double Width Indicatorwith Fading Reaction Spectrophotometry GUO Zhen-liang1, MA Yan1, WANG Xiao-sheng1,2 (1.School of Chemistry and Materials Science Ludong University, Yantai 264025, China; 2.Jitai No.2 Middle School of Shouguang, Weifang 262723, China), Huaxue Shiji, 2017, 39(4),
Abstract: The trace Cd2+ could strongly catalyze the fading oxidation reaction of alizarin red S and thionine by hydrogen peroxide in the medium of hydrochloric acid. A new catalytic fading spectrophotometric method by the double wavelength double width indicator had been established for the determination of trace Cd2+. The results showed that the maximum absorption wavelength of the solution were 420 nm and 610 nm, respectively. The standard deviation and the relative standard deviation of six blank experiments were 6.31×10-4 and 0.01%, the determination limit of the method was 4.878×10-2μg /mL. The method had been applied to the determination of Cd2+ in rice with satisfactory results.
Key words:Cadmium；alizarin red S；thionine；hydrogen peroxide ；double wavelength double indicator fading spectrophotometry
阳离子褐煤树脂的阳离子度测定方法研究
孟丽艳*，黄宁
（中石化中原石油工程有限公司 钻井工程技术研究院，河南 濮阳 457001）
摘要:采用四苯硼钠电位滴定法测定阳离子褐煤树脂的阳离子度。通过消除测定方法的离子干扰、优化四苯硼钠电位滴定法的测定条件两方面来提高测定方法的准确度。采用5%盐酸溶液提取阳离子腐植酸，去除钾离子和其它水溶性杂质；四苯硼钠电位滴定法过程中提纯后阳离子腐植酸加量0.5 g，用0.2%氢氧化钠溶液溶解阳离子腐植酸，在pH 10.0条件下，选用甘汞电极为参比电极，氟硼酸根离子选择性电极为指示电极，用十六烷基三甲基溴化铵标准溶液电位滴定四苯硼钠，电位突变约200 ～ 300 mV，加标回收率达95%，满足分析测试要求。实验结果表明，该方法选择性好、准确性高、易于操作，具有较高推广应用价值。
关键词:阳离子褐煤树脂；阳离子度；四苯硼钠电位滴定法
中图分类号：O655 文献识别码：A 文章编号：0258-3283（2017）
Cationic Degree Determination of Cationic Lignite MENG Li-yan*, HUANG Ning (Research Institute of Drilling Engineering Technology, Zhongyuan Petroleum Exploration Bureau,Sinopec, Puyang 457001, China), Huaxue Shiji, 2017, 39(4),
Abstract：The method of determining cationic degree of cationic lignite is tetraphenylboron sodium potentiometric method. By eliminating the ion disruption, optimizing the determination conditions of tetraphenylboron sodium potentiometric method , the two aspects improve the accuracy of the determination method of sodium. The results show that the cationic humic acid are extracted with 5% hydrochloric acid solution in order to remove the potassium and other soluble impurities. In the process of tetraphenylboron sodium potentiometric method, the purification of the cation humic acid added amount is 0.5 g, with 0.2% sodium hydroxide solution of cationic humic acid, in alkaline conditions pH10.0, selects the calomel is reference calomel, fluoboric acid root ion selective electrodes is indicating electrode, with hexadecyltrimethyl ammonium bromide standard solution potentiometric titration, tetraphenylboron sodium. The potential mutation is from 200mv~300mv.The standard addition recovery rate reaches 95% which analyzes the test requirements. The detecting results are verified and calculated by laboratory test which shows that the sodium tetraphenylborate method can satisfy the demand of product purchasing, checking and quality supervision with good reproducibility and high degree of accuracy．
Key words：cationic lignite; cationic degree; tetraphenylboron sodium potentiometric method
气相色谱法测定天然气组成的条件优化
孙秀
（湖南省长沙燃气燃具监督检测中心，湖南 长沙 410011）
摘要：气相色谱法是天然气检测常用的方法，在一定条件下可以快速准确地对天然气的气体组成成分进行测定，设定合适的色谱条件是保证测定准确、可靠的关键。以FID-TCD并联分析技术为基础，对气相色谱法测定天然气组成的条件进行了实验分析，对测定过程中使用的色谱柱、温度、柱流速、进样口温度、检测器温度、TCD参考气等测定条件进行了优化，找出了各条件的平衡点，使得测定出的各种气体分子浓度在实验中能够呈现出良好的线性关系。为FID-TCD并联检测的气相色谱技术在测定天然气成分中提供了参考，对提高测定的效率、灵敏度和准确性具有非常重要的意义。
关键词：气相色谱法；FID-TCD并联检测；天然气组成；成分测定
中图分类号：O657.7 文献标识码：A 文章编号：0258-3283（2017）
Conditions Optimization of Gas Chromatography for Determination of the Composition of Natural Gas SUN Xiu (Changsha Supervising and Test Center for Gas and Gas Appliances of Hunan Province, Changsha 410011, China), Huaxue Shiji, 2017, 39(3)
Abstract: Gas chromatography is a common method of natural gas detection. In certain conditions, it can quickly and accurately determine the gas composition of natural gas. The proper condition is the key to ensure the accurate and reliable measurement. In this work, based on the FID-TCD parallel analysis technique, the gas chromatographic conditions for the determination of the composition of natural gas were analyzed. The chromatographic column, temperature, column flow rate, inlet temperature, detector temperature and TCD reference gas were optimized and the equilibrium points of the different conditions were found. The determination of the molecular concentration of various gases in the experiment can show a good linear relationship. To provide reference for FID-TCD parallel detection technology of the gas chromatography in the determination of natural gas, it has very important significance to improve efficiency, sensitivity and accuracy of determination.
Key words: gas chromatography; FID-TCD parallel detection; gas composition; component measurement
儿童胶画颜料中邻苯二甲酸酯类化合物检测前处理方法的研究
何军*，朱亚伟，刘艇飞，王佳，林韫，张英
(台州出入境检验检疫局，浙江 台州 318000)
摘要：考察了12种不同种类的溶剂对儿童胶画颜料中邻苯二甲酸酯类化合物萃取效率的影响，发现乙酸乙酯作为溶剂时，萃取效率最高。比较了微波萃取、索氏提取、超声萃取、快速溶剂萃取这4种前处理方法对萃取效率的影响，发现微波萃取效率最高。进一步优化了微波萃取的方法，萃取效率随着微波萃取温度的升高而提高。但是，当萃取温度从100 ℃提高到120 ℃时，萃取结果增加不明显，说明在100 ℃的时候，萃取已经相对完全。该前处理方法简单快速、提取效率高、使用的试剂毒性小、对环境友好，能够满足儿童胶画颜料中邻苯二甲酸酯类化合物的检测要求。
关键词：儿童胶画颜料；邻苯二甲酸酯类化合物；前处理方法
中图分类号： 文献标识码：A 文章编号：0258-3283（2017）
Pretreatment Methods of Determination of Phthalte Acid Esters from Children Tempera Painting Pigments HE Jun*, ZHU Ya-wei, LIU Ting-fei, WANG Jia, LIN Yun, ZHANG Ying (Taizhou Entry-Exit Inspection and Quarantine Bureau, Taizhou 318000, China), Huaxue Shiji, 2017, 39(4)
Abstract：Compared the effect of 12 different kinds of solvents on the extraction efficiency of phthalic acid esters from children tempera painting pigments. The highest extraction efficiency was observed by using ethyl acetate as solvent. Also compared the different pre-treatment ways, there are microwave extraction, soxhlet extraction, ultrasonic extraction and fast solvent extraction. The results showed that the extraction efficiency was higher by using microwave extraction than other three extraction ways. The microwave extraction method has been optimized.With the increase of extraction temperature, the extraction efficiency improved. However, when the extraction temperature increased form 100 ℃to120 ℃, the extraction efficiency improved not obviously. So, the extraction relatively completed at 100 ℃.The pretreatment method observed in this work is simple and quick. Also, the extraction efficiency is high. Moreover, the solvent selected in this method is low toxicity and environmentally friendly. This pretreatment method is quiet suitable for the determination of phthalic acid esters from children tempera painting pigments.
Key words：children tempera painting pigments; phthalic acid esters; pre-treatment methods
基于4-氨基吖啶酮小分子传感器的设计、合成
及识别性能研究
田林a，盛风涛a，黄天姿b，颜金雷a，杨正茂a，李昭*a
（徐州工程学院 a. 化学化工学院；b. 食品（生物）工程学院，江苏 徐州 221018）
摘要：基于以往的研究进一步设计合成了一种Cu2+小分子传感器4-((3-甲氧基-4-羟基苄亚基)氨基)吖啶-9(10H)-酮（4-AAVS）。该化合物结构经过1HNMR、13CNMR和HR-MS确认。通过紫外-可见光谱法和荧光光谱法研究4-AAVS在水溶液中对金属离子的识别能力。实验结果表明，在pH 6.24 ～ 8.0的水溶液体系中，该化合物对Cu2+表现出优良的选择性识别作用。利用荧光滴定实验得到，该化合物和Cu2+的配位比为2 : 1，离子浓度在0.1 ～ 0.4 × 10-6 mol /L范围时，线性相关系数R = 0. 98889，最低检出限为1.8 × 10-9 mol/L。
关键词：4-氨基吖啶酮；水溶液；小分子传感器；Cu2+
中图分类号：O657.3 文献标识码：A 文章编号：0258-3283（2017）
Synthesis and Properties of Small Molecular Sensors for Recognition of Cu2+ Based 4-aminoacridone TIAN Lina, SHENG Feng-taoa, HUANG Tian-zib, YAN Jin-leia, YANG Zheng-maoa, LI Zhao*a ( a. School of Chemical Engineering and Technology; b. School of Food Science and Technology, Xuzhou Institute of Technlogy, Xuzhou 221018,China)
Abstract：The small molecule 4-(3-Methoxyl-4-hydroxylbenzylideneamino)acridin-9(10H)-one(4-AAVS) was synthesized for recognition of Cu2+ based on our previous studies. The structure of the compound was confirmed by 1HNMR, 13CNMR and HR-MS. The ability to recognize in aqueous solution was evaluated by ultraviolet-visible spectrometry and fluorescence spectroscopy. The results show that the 4-AAVS could selectivity recognition of Cu2+ in aqueous solution when the value of pH was between 6.24 and 8, and fluorescence titration experiment exhibited the complex of 4-AAVS and Cu2+ was 2 : 1,fluorescence intensity △F and the concentration of Cu2+ show a better linear relationship between 0.5 ～ 4 ×10-6 mol /L, the linear correlation coefficient was 0. 98889, the detection limit was 1.8 ×10-9 mol /L.
Key words: 4-aminoacridone; aqueous solution; small molecule sensor; Cu2+
二氢杨梅素及其氧钒配合物与DNA的相互作用研究
严高剑a, b，叶振锋b，柴栋a，唐敬b，陆家政*b
（广东药科大学 a. 中药学院，b. 药学院，广东 广州 510006）
摘要：二氢杨梅素是藤茶中重要药效物质。合成了一种二氢杨梅素的氧钒配合物，其结构经元素分析、IR、ESI-MS、1HNMR和13CNMR表征。采用紫外分光光度法、荧光淬灭和流体力学等方法分别测定二氢杨梅素及其氧钒配合物与DNA的键合能力。结果显示，这两种化合物都能以插入方式与CT-DNA结合，DNA断裂实验证实该新型配合物可较好地断裂pBR322 DNA。
关键词：二氢杨梅素；氧钒配合物；DNA键合
中图分类号：R284 文献标识码：A 文章编号：0258-3283（2017）
DNA-binding of Dihydromyricetin and its Oxovanadium(IV) Complex YAN Gao-jiana, b, YE Zhen-fengb, CHAI Donga, TANG Jingb, LU Jia-zheng*b (a. School of Traditional Chinese Medicine; b. School of Pharmacy, Guangdong Pharmaceutical University, Guangzhou 510006, China), Huaxue Shiji, 2017, 39(4),
Abstract: Dihydromyricetin is an important pharmacodynamic material in Tengcha. Its oxovanadium complex (VO-DMY) has been synthesized and confirmed by elemental analysis, IR, UV/vis, ESI-MS, 1HNMR and 13CNMR. The DNA-binding activity of DMY and VO-DMY with calf thymus CT-DNA have been investigated by using UV-vis absorption titration, fluorescence spectra and viscosity measurement. The results indicate that DMY and VO-DMY can bind to CT-DNA via an intercalative mode and can efficiently cleave pBR322 DNA after DNA photo cleavage experiment.
Key words: dihydromyricetin; oxovanadium(IV) complex; DNA binding
香豆素类席夫碱型Zn2+荧光探针的合成
万攀，张锦华，刘炜，彭明生*
(海南师范大学 化学与化工学院 热带药用植物化学教育部重点实验室，海南 海口 571158)
摘要：以4-二乙胺基水杨醛和丙二酸二乙酯为原料合成了7-二乙胺基-3-甲酰基香豆素，再与烟酸酰肼反应合成目标产物L。在乙腈溶液中，化合物L对Zn2+具有一定的荧光选择性，化合物L与Zn2+的配合比为1∶2。
关键字：荧光探针；香豆素；席夫碱；锌离子
中图分类号：O625 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of a Coumarin Schiff Base Fluorescent Probe for Zn2+WAN Pan , ZHANG jin-hua, LIU Wei, PENG Ming-sheng* (Key Laboratory of Tropical Medicinal Plant Chemistry of Ministry of Education, College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158, China), Huaxue Shiji, 2017, 39(3)
Abstract: The target compound L-a coumarin Schiff was synthesized through two-step reactions of 4-diethylaminosalicylaldehyde reacting with diethylmalonate to yield 7-diethylamino-coumarin-3-aldehyde, and 7-diethylaminocoumarin-3-aldehyde reacting with nicotinic hydrazide. This novel compound L showed very high fluorescent selectivity for Zn2+ in acetonitrile，and also experimental data revealed the complex ratio of compound L and Zn2+ to be 1 : 2.
Key words: fluorescent probe; coumarin; Schiff base; zinc ion
中心组合-响应面法优化中药钩藤总黄酮的提取条件
杨伟群*1，许晓芸2
（1. 宁波职业技术学院 化工学院，浙江 宁波 315800；
2. 台州职业技术学院 医学与制药工程学院，浙江 台州 318000）
摘要：为获取最佳的中药钩藤总黄酮提取条件，以提取量为响应值，在单因素实验研究的基础上，运用中心组合－响应面法考察了液固比、回流时间、乙醇浓度、提取温度及其交互作用对提取量的影响。研究结果表明，将液固比为1︰23的钩藤置于60%乙醇中并于80 ℃条件下提取2.0 h，总黄酮提取量最高，达1.2816 mg/g。经过验证，运用响应面分析法从钩藤中优选总黄酮工艺稳定、合理可行。
关键词：钩藤；总黄酮；中心组合设计；响应面法
中图分类号：R284.2 文献标识码：A 文章编号：0258-3283（2017）
Optimization of Extraction Conditions for Total Flavonoids in Traditional Chinese Medicine Uncaria Rhynchophylla by CCD-RSM YANG Wei-qun*1，XU Xiao-yun2（1. School of Chemical Engineering, Ningbo Polytechnic, Ningbo 315800, China；2. School of Medicine and Pharmaceutical Engineering, Taizhou Vocational & Technical College, Taizhou 318000, China), Huaxue Shiji, 2017, 39(3)
Abstract: In order to obtain the best extraction conditions for total flavonoids in traditional chinese medicine Uncaria rhynchophylla. Taking the extraction quantity as the response value and basing on single factor experiment, this work investigates the liquid-solid ratio, reflux time, ethanol concentration, extraction temperature and their interaction on the effect of extraction amount by CCD-RSM. The results show that the optimum conditions for the extraction of total flavonoids from Uncaria rhynchophylla are as follow: the liquid-solid ratio 1 : 23, 60% ethanol at 80 ℃ extracting for 2 hours, extraction amount of total flavonoids reached 1.2816 mg/g. The verification results show that the optimization process of total flavonoids from Uncaria is stable, reasonable and feasible by using the response surface analysis method.
Key words: Uncaria rhynchophylla; central composite design; total flavonoids; response surface method
合成3-甲氧基丙烯酸甲酯的新方法
吴清来*，鲁东飞
（长江大学 农学院 长江大学农药研究所，湖北 荆州 434025）
摘要：以乙烯基甲醚和三氯乙酰氯为原料，经加成消除、加成反应、卤仿反应及消除反应合成标题化合物，总收率为56.5%。该合成方法原料廉价且简单易得、反应条件温和、操作简单安全，有工业产业化应用的前景。
关键词：3-甲氧基丙烯酸甲酯；乙烯基甲醚；三氯乙酰氯；合成；
中图分类号：O626 文献标识码：A 文章编号：0258-3283（2017）
New Synthetic Method of Methyl 3-Methoxyacrylate WU Qing-lai*, LU Dong-fei（ ，School of Agricultural, Yangtze University, Jingzhou 434025, China），Huaxue Shiji，2017, 39（4），
Abstract: A new synthetic method of methyl 3-methoxyacrylate was established in this work. Methyl 3-methoxyacrylate was obtained from methyl vinyl ether and trichloroacetyl chloride as starting material via addition reaction, elimination reaction and haloform reaction. The total yield is 56.5%. In this method, material is cheap and easily available, reaction conditions are mild, the operation is simple and safe, and it has the prospect of industrial application.
Key words：methyl 3-methoxyacrylate; methyl vinyl ether; trichloroacetyl chloride; synthesis
N-(4-二苯胺苯甲基)-甘氨酰丝氨酸甲酯的合成
李志芬*，王君玲，乔俊，许琳，解海
（大同大学 化学与环境工程学院，山西 大同 037009）
摘要：主要以甘氨酸和4-二苯氨基苯甲醛为原料，通过还原氨化反应得到4-二苯胺-苯甲氨基乙酸，用叔丁氧羰基保护二级氨后，与丝氨酸甲酯脱水缩合生成N-(4-二苯胺苯甲基)-N-叔丁氧羰基-甘氨酰丝氨酸甲酯，脱去保护基后得到标题化合物。用1HNMR、13CNMR、IR、MASS、HRMS和HPLC对目标化合物的结构进行了表征。
关键词：4-二苯氨基苯甲醛；甘氨酸；丝氨酸
中图分类号：O622.5 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of N-(4-(Diphenylamino)benzyl)-glycyl-serine Methyl Ester LI Zhi-fen*, WANG Jun-lin, QIAO Jun, XU Lin, XIE hai (School of Chemical and Environmental Engineering, Datong University, Datong 037009, China), Huaxue Shiji, 2017, 39(3)
Abstract: In this paper, 2-(4-(diphenylamino)benzylamino)acetic acid was synthesized by using glycine and 4-diphenylamino-benzaldehyde as starting materials through the reductive amination. The secondary amine of 2-(4-(diphenylamino)benzylamino)acetic acidwas first protected by tert-butyloxycarbonyl, then was converted to N-(4-(diphenylamino)benzyl)-N-(tert-butoxycarbonyl)-glycylserine methyl ester through condensation with L-serine methyl ester hydrochloride. After deprotection, the target compound of N-(4-(dip-henylamino)benzyl)-glycylserine methyl ester was obtained. As-obtained compound was thoroughly characterized by1HNMR, 13CNMR, IR, MASS, HRMS and HPLC.
Key words：4-diphenylaminobenzaldehyde; glycine; serine
固体超强酸催化合成N-苯基吡咯烷酮的研究
张玲钰，王云川，吕慧敏，李修刚*
（铜仁学院 材料与化学工程学院，贵州 铜仁 554300）
摘要：采用固定床技术，以SO42-/MxOy型固体超强酸为催化剂，1, 4-丁内酯和苯胺反应合成了N-苯基吡咯烷酮(NPP)，研究固定床工艺条件对NPP转化率的影响。实验结果表明，以SO42-/MxOy型固体超强酸为催化剂固定床合成NPP的最佳实验条件为n([1], 4-丁内酯) : n(苯胺) = 1.2 : 1、反应温度为300 ˚C、进料速度为1.2 mL/min，NPP的转化率最高为98.7%。
关键词：固定床；1-苯基-2-吡咯烷酮；1, 4 -丁内酯；苯胺
中图分类号：TQ252.3 文献标识码：B 文章编号：0258-3283（2017）
Synthesis of N-Phenyl Pyrrolidone Catalyzed by Solid Superacid ZHANG Ling-yu, WANG Yu-chuan, LV Hui-ming, LI Xiu-gang*(College of Material and Chemical Engineering, Tongren University, Tongren 554300, China), Huaxue Shiji, 2017, 39(3)
Abstract: N-Phenyl pyrrolidone (NPP) was synthesized from 1, 4-butyrolactone and aniline in fixed bed with the catalysis of solid super acid, and the processing parameters of fixed bed on production of NPP was investigated. The results showed that the optimal ratio between 1, 4-butyrolactone and aniline was 1.2 : 1 at 300 ºC, and the feeding rate of reacting material was 1.2 mL/min. NPP was obtained with the highest conversion rate of 98.7%.
Key words: fixed bed; 1-phenyl-2-pyrrolidone; 1, 4-butyl ester; aniline
1-(溴甲基)-4-环丙基苯的合成研究
杨露a，刘力b，赵春深b, c，宋方祥a，李焱*b
(贵州大学 a. 化学与化工学院，b. 药学院，c.贵州省发酵工程与生物制药重点实验室，贵州 贵阳 550003)
摘要：标题化合物是一种非常重要的化工中间体，广泛应用于医药领域。以对溴苯甲醛为起始原料，经Suzuki偶联、还原和溴代反应制得目标产物。本方法成本较低、操作简单且反应条件较为温和，总收率达62.8%。目标化合物的结构经1HNMR和MS确证。
关键词：1-(溴甲基)-4-环丙基苯；对溴苯甲醛；合成
中图分类号： 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of 1-(Bromomethyl)-4-cyclopropylbenzene YANG Lua，LIU Lib，ZHAO Chun-shenb, c, SONG Fang-xianga，LI Yan*b (a. College of Chemistry and Chemical Engineering; b. School of Pharmaceutical Sciences; c. Guizhou key Laboratory of Fermentation engineering and Biopharmaceutical, Guizhou University, Guiyang 550003, China), Huaxue Shiji, 2017, 39(4),
Abstract: 1-(bromomethyl)-4-cyclopropylbenzene, an important intermediate of ROR-gamma inhibitors, sodium-dependent glucose co-transporter 2 inhibitors and 5-HT2C agonists, was synthesized by steps of Suzuki coupling reaction, reduction reaction and bromination reaction. And its structure was confirmed by MS and 1HNMR. The total product yield was 62.8%.
Key words: 1-(bromomethyl)-4-cyclopropylbenzene; bromobenzaldehyde; synthesis
6-甲基-2-苯基咪唑[2, 1-b]并-1,3,4-噻二唑-5-N′-取代苯基亚甲基碳酰肼的设计与合成
杨娜*1，鲁源2
（1. 内蒙古医科大学附属医院 药剂部，内蒙古 呼和浩特 010050；
2. 内蒙古医科大学 药学院，内蒙古 呼和浩特 010059）
摘要：根据已有的具有抗肿瘤活性的咪唑[2, 1-b]并-1, 3, 4-噻二唑类化合物的结构及其构效关系，以2-氨基-5-苯基-1, 3, 4-噻二唑和溴代乙酰乙酸乙酯为原料设计并合成了8个6-甲基-2-苯基咪唑[2,1-b]并-1, 3, 4-噻二唑-5-碳酰肼的腙类衍生物。通过1HNMR、LC-MS、IR等方法对其结构进行了确证。
关键词：杂环化合物；咪唑[2, 1-b]并-1, 3, 4-噻二唑；合成；抗肿瘤活性
中图分类号：O626 文献标识码：A 文章编号：0258-3283（2017）
Design and Synthesis of 6-methyl-2-phenylimidazo[2, 1-b][1, 3, 4]thiadiazole-5-N′-substituted pheny-lmethylene carbohydrazides YANG Na*1, LU Yuan2 (1.Department of Pharmacy,The Affiliated Hospital of Inner Mon-golia Medical University, Hohhot 010050, China; 2. College of Pharmacology, Inner Mongolia Medical University, Hohhot 010059, China), Huaxue Shiji, 2017, 39(4):
Abstract: According to the structure and the structure-activity relationship of imidazo[2, 1-b][1, 3, 4]thiadiazole with antitu-mor activity,eight kinds novel hydrazone derivatives of 6-methyl-2-phenylimidazo[2, 1-b][1, 3,4]thiadiazole-5-carbohydrazi-de were synthesized in the basis of 2-amino-5-phenyl-1,3,4-thiadiazole and bromination ethyl acetoacetate. The structures of the compounds were confirmed by 1HNMR, LC-MS and IR.
Key words：heterocyclic compounds; imidazo[2, 1-b][1, 3, 4]thiadiazole; synthesis; anti-tumor activity
5-咪唑甲基-二氢吡咯-3-甲酸甲酯的合成
张晴晴，滕大为*
（青岛科技大学 化工学院，山东 青岛 266042）
摘要：以组氨酸为原料，经选择性咪唑环氮的保护、氨基的迈克尔加成、甲基化、关环、还原和消除等反应合成了5-咪唑甲基-二氢吡咯-3-甲酸甲酯。对其中关键步骤氨基迈克尔加成反应和分子内关环反应进行了研究，获得了较优的工艺条件：在迈克尔加成反应中以甲醇钠为碱，甲醇为溶剂；在分子内环化反应中选择以叔丁醇钾为碱，四氢呋喃为溶剂。目标产物的总产率为28.3%。目标化合物的结构经1HNMR和MS进行了确定。
关键词：迈克尔加成；吡咯衍生物；组氨酸；环合
中图分类号：O626.1 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of Methyl 5-((1H-imidazol-4-yl)methyl)-1-methyl-2,5-dihydro-1H-pyrrole-3-carboxylate ZHANG Qing-qing, TENG Da-wei* (College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China), Huaxue Shiji, 2017, 39(4),
Abstract:Methyl5-((1H-imidazol-4-yl)methyl)-1-methyl-2,5-dihydro-1H-pyrrole-3-carboxylate was synthesized from histidine by selective protection of the imidazole ring nitrogen, amino Michael addition, methylation, cyclization, reduction and elimination reactions. The optimum conditions of Michael addition reaction and intramolecular cyclization were obtained. For Michael addition reaction: sodium methylate as base, methanol as solvent. For intramolecular cyclization: potassium t-butoxide as base, tetrahydrofuran as the solvent. The overall yield of target product is 28.3%. The structure was confirmed by 1HNMR and MS.
Key word: Michael addition; pyrrolidine derivatives; histidine; cyclization
3，3-二氯-2-羟基-4-羰基-4-对甲苯基丁酸异丙酯的合成及晶体结构
王月梅，徐泽刚，王伦，李秉擘，宁斌科，刘康云，陈涛，卫天琪，杨翠凤*
（西安近代化学研究所 氟氮化工资源高效开发与利用国家重点实验室，陕西 西安 710065）
摘要: 通过ɑ, ɑ-二氯-4’-甲基苯乙酮与乙醛酸异丙酯反应合成标题化合物，收率61.5%，产物结构经核磁、IR、X -射线单晶衍射确定。晶体结构数据表明晶体属单斜系，P2(1) /c 空间群，晶胞参数为a =11.3367(19) Å，b = 10.8311(17) Å，c = 12.437(2) Å，α = 90. 00°，β = 101.285 °，γ＝90°，V = 1497.6(4) Å3，Dc = 1.416 g /cm3 ，μ = 0.443 cm-1 ，F(000) = 664，Z = 4，R1 =0.0473，wR2 = 0.0967。
关键词: ɑ, ɑ-二氯羰基化合物；乙醛酸异丙酯；合成；X-单晶衍射；晶体结构
中图分类号：O621.3 文献标识码：A 文章编号：0258-3283（2017）
Synthesis and Crystal Structure of Isopropyl 3, 3-dichloro-2-hydroxy-4-oxo-4-（p-tolyl）Butanoate WANG Yue-mei，XU Ze-gang，WANG Lun，LI Bing-bo，NING Bin-ke，LIU Kang-yun，CHEN Tao，WEI Tian-qi，YANG Cui-feng*（State Key Laboratory of Fluorine & Nitrogen Chemicals，Xi’an Modern Research Institute，Xi’an 710065，China），Huaxue Shiji，2017，39（4），
Abstract：Isopropyl 3, 3-dichloro-2-hydroxy-4-oxo-4-（p-tolyl）butanoate was synthesized by ɑ, ɑ-dichloro-1-（p-tolyl）ethanone and isopropyl 2-oxoacetate. The yield was 61.5% and the structure of the product was confirmed by 1HNMR, 13CNMR, IR, X-ray diffractometer. Crystal data are: monoclinic, P2 ( 1) /c space group, a =11.3367(19) Å，b = 10.8311(17)) Å，c = 12.437(2) Å，α =90. 00°，β = 101.285 °，γ＝90°，V = 1497.6(4) Å3，Dc = 1.416 g /cm3，μ = 0.443 cm-1，F( 000) = 664，Z = 4，R1 =0.0473，wR2 =0.0967.
Key words：ɑ, ɑ-dichlorocarbonyl；isopropyl 2-oxoacetate；synthesis；X-ray diffraction；crystal structure
间三氟甲基苯乙酮的合成新方法
张学慧*，王丹丹
（赤峰工业职业技术学院，内蒙古 赤峰市 024000）
摘要：肟菌酯作为重要的一类甲氧基丙烯酸酯类杀菌剂，市场应用前景广阔。标题化合物是合成肟菌酯的关键中间体，考察了以三氟甲苯与乙酰氯为原料，通过与丁基锂反应，在路易斯酸的催化作用下得到该化合物的方法。通过反应条件优化，实验确定的最佳反应条件是四氢呋喃为格氏反应溶剂，丁基锂的反应温度为0.09 eq，滴加乙酰氯的温度为-10 oC，乙酰化反应保温时间为8 h，催化反应的路易斯酸用量为10%氯化亚铜。标题化合物总产率91%，含量96%。
关键词：间三氟甲基苯乙酮；乙酰氯；三氟甲苯
中图分类号：TQ 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of 3-Trifluoromethyl-phenylethanone ZHANG Xue-hui*，WANG Dan-dan （The Chifeng Industry Vocational Technology College, Chifeng 024000, China）, Huaxue Shiji, 2017, 39(4),
Abstract:Trifloxystrobin is an important strobilurin fungicide with a good impetus and vast potential development. 3-Trifluoromethyl-phenylethanone is the key intermediate to synthesize trifloxystrobin. In this work, the intermediate was obtained by taking benzotrifluoride and acetyl chloride as the reactants, butyl lithium as the strong base and catalyzed by Lewis acid. With the optimal reaction conditions, 3-trifluoromethyl-phenylethanone was synthesized by taking THF as the Grignard reaction solvent and 0.09eq amount of butyl lithium. Acetylation was furnished under 10% CuCl catalyzed by adding acetylchloride under -10oC and keeping for 8 h. The yield of 3-trifluoromethyl-phenylethanone was reached 91%.The purity of the product was 96%.
Key words: 3-trifluoromethyl-phenylethanone; acetylchloride; benzotrifluorid
