Schiff碱链接的双菲并咪唑Fe3+荧光探针的合成及识别性能研究
赵冰*，刘婷，王丽艳，邓启刚
(齐齐哈尔大学 化学与化学工程学院，黑龙江 齐齐哈尔 161006)
摘要：以2-(2-氨基苯基)-1-苯基-1H-菲并[9,10-d]咪唑和对苯二甲醛为原料，合成了以Schiff碱链接的双菲并咪唑衍生物(BPII)，并通过并采用红外和核磁对所合成的化合物进行了结构表征和确认。通过紫外和荧光光谱实验表明，主体化合物BPII在DMF/HEPES的混合溶液中 (V（DMF） ︰ V（HEPES） = 7 ︰ 3)对Fe3+具有选择性识别性能，且不受其他共存金属离子的干扰；荧光滴定实验表明，主体化合物BPII对Fe3+的检出限为2.08 μmol/L, 可用于真实水样中Fe3+浓度的检测；Job’s曲线确定了主体化合物BPII与Fe3+之间形成物质的量比为1:1的金属络合物。
关键词：Schiff碱；双菲并咪唑；荧光探针；Fe3+；合成；识别
中图分类号：0621.2 文献标识码：A 文章编号：0258-3283(2017)
Synthesis and Recognition Properties of Bis-phenanthro[9,10-d]imidazole Linked by Schiff Base Group for Fe3+ ZHAO Bing*, LIU Ting, WANG Li-yan, DENG Qi-gang (Chemistry and Chemical Engineering Institute, Qiqihar University, Qiqihar 161006, China)，Huaxue Shiji，2017, 39（1），
Abstract：Bis-phenanthro[9,10-d]imidazole BPII linked by Schiff base group was synthesized by the reaction of 2-(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)aniline with terephthalaldehyde and the structure was confirmed by IR and NMR. The experiments of UV-Vis and fluorescent spectra showed that compound BPII could selectively recognize the Fe3+ in DMF/HEPES solution (V（DMF） ︰ V（HEPES） = 7 ︰ 3) without interference by other ions. The detection limit of compound BPII to Fe3+ was 2.08 μmol/L by the method of the fluorescence titration, which had been successfully used to detect the concentration of Fe3+ in the real water samples. The 1 : 1 stoichiometry of the binding mode of BPII to Fe3+ was confirmed by the Job’s method.
Key words：Schiff base; bis-phenanthro[9,10-d]imidazole; fluorescent sensor; synthesis; recognition
可见光响应Fe掺杂ZnO/凹凸棒石复合材料的制备和光催化性能
王芳*，侯建华，马小华，张正国，李慧，敏世雄
（北方民族大学 化学与化学工程学院，宁夏 银川 750021）
摘要: 采用直接沉淀法制备了Fe掺杂ZnO/凹凸棒石（Fe-ZnO/ATP）复合材料，评价了其在可见光条件下（>400 nm）光催化降解高浓度亚甲基蓝（MB）溶液的性能，并系统研究了ZnO负载量、Fe掺杂量和焙烧温度等对复合材料吸附性能和光催化性能的影响。结果表明，ATP的复合增强了复合材料对MB的吸附能力，MB在最佳条件下制备的Fe(0.3%)-ZnO(50%)/ATP复合材料上降解的表观反应速率常数（kapp）为4.2×10-3 min-1，反应3.5 h后的降解率可达65.40%，与ZnO相比较，kapp和MB的降解率提高了2.6倍。XRD、TEM和UV-Vis-DRS的结果表明，复合材料中ATP的结构在热处理过程中基本保持不变，复合材料中ZnO的粒径明显减小，暴露了更多的活性位点。另外，Fe的掺杂可明显增强复合光催化剂对可见光的吸收，增强了对光的利用效率，从而使复合材料显示出优异的光催化活性。
关键词：Fe-ZnO/ATP复合材料；可见光；亚甲基蓝；光催化降解
中图分类号：O643；O644 文献标识码：A 文章编号：0258-3283（2017）
Preparation and Photocatalytic Performances of Visible Light-responsive Fe-doped ZnO/Attapulgite Composites WANG Fang*, HOU Jian-hua, MA Xiao-hua, ZHANG Zheng-guo, LI Hui, MIN Shi-xiong (School of Chemistry and Chemical Engineering, Beifang University of Nationalities, Yinchuan 750021, China), Huaxue Shiji, 2017, 39(1),
Abstract: Fedoped ZnO/Attapulgite (Fe-ZnO/ATP) photocatalysts were prepared by direct precipitation method and the photocatalytic activities were investigated by degrading concentrated methylene blue (MB) solution under visible light irradiation (> 400 nm). The effect of loading amount of ZnO, doping amount of Fe, and calcination temperature were investigated. The results showed that the presence of ATP can greatly enhance adsorption capability of Fe-ZnO/ATP towards MB and the Fe(0.3%)-ZnO(50%)/ATP prepared at optimal conditions showed enhanced activity for MB degradation with an apparent reaction rate constant (kapp) of 4.2×10-3 min-1 and a degradation rate of 65.40% after 3.5 h of visible light irradiation, respectively, which are 2.6 times higher than that of pristine ZnO. XRD, TEM and UV-vis-DRS analyses revealed that the crystalline structure of ATP in the composite was found thermally stable after calcination and the particle size of ZnO in composite is smaller than pristine ZnO with more exposed active sites. Moreover, Fe doping could improve the light response of the composite to maximize the utilization of incident light, which in turn enhances the photocatalytic performance of Fe-ZnO/ATP.
Key words: Fe-ZnO/ATP composites; visible light; methylene blue; photocatalytic degradation
香豆素噻唑类化合物的合成及其抗菌活性研究
何典雄，刘文超，彭知云，王广成*
（吉首大学 化学化工学院，湖南 吉首 416000）
摘要：以水杨醛为原料，经5步反应合成了一系列新型香豆素噻唑类化合物，其结构经1HNMR、13CNMR和元素分析证实。体外考察了所得化合物对大肠杆菌、金黄色葡萄球菌和枯草芽孢杆菌的抑制活性。结果表明，大部分化合物都具有较强的抗菌活性。其中，化合物(E)-N′-(3-氟-4-羟基苯基亚甲基)-4-(2-氧代-2H-苯并吡喃-3-基)噻唑-2-酰肼活性最好，对大肠杆菌、金黄色葡萄球菌和枯草芽孢杆菌的最低抑制浓度分别为0.39、1.56和1.56 μg/mL。
关键词：香豆素；噻唑；抗菌活性
中图分类号：O626.23 文献标识码：A 文章编号：0258-3283（2017）
Synthesis and Antibacterial Activity of Coumarin Thiazole Derivatives HE Dian-xiong, LIU Wen-chao, PENG Zhi-yun, WANG Guang-cheng*(College of Chemistry and Chemical Engineering, Jishou University, Jishou 416000, China), Huaxue Shiji, 39(1)
Abstract: A series of novel coumarin thiazole derivatives were successfully synthesized via five steps, by using salicylaldehyde as raw material. The structures of the synthesized compounds were confirmed by 1HNMR, 13CNMR and elemental analysis. The antibacterial activities against Escherichia coli, Staphylococcus aureus and Bacillus subtilis were tested. The majority of the screened compounds displayed potent antibacterial activity. Among them, compound 5f showed the most potent antibacterial activity against Escherichia coli, Staphylococcus aureus and Bacillus subtilis with minimum inhibitory concentration (MIC) of 0.39, 1.56, 1.56 μg/mL, respectively.
Key words: coumarin; thiazole; antibacterial activity
新型光催化剂BiOI的制备及其光催化性能
郑立允，王书岭*
（河北工程大学 机电工程学院，河北 邯郸 056038）
摘要：采用水热法和溶剂热法制备了两种不同的结构光催化剂BiOI，通过X-射线粉末衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)等技术对其晶相结构、微观形貌进行了表征，并模拟太阳光下降解甲基橙（MO）评价所制备样品的催化性能。光催化实验表明，可见光下，溶剂热法所制备的光催化剂明显优于水热法合成的催化剂以及商品光催化剂P25，在80 min内对甲基橙溶液的催化降解率达90%以上，同时在紫外光下依然具有很高的活性。分析其降解机理可知，光催化降解过程是光生电子与空穴同时作用的结果。
关键词：光催化；BiOI；结构；催化降解；光降解反应
中图分类号：O614.53 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of New Type BiOI Photocatalyst and Enhanced Photocatalytic Activities ZHENG Li-yun, WANG Shu-ling* (Mechanical and Electrical Engineering Institute, Hebei University of Engineering, Handan 056038，China), Huaxue Shiji, 2017, 39(1),
Abstract: Two different structures of BiOI photocatalysts were synthesized using hydrothermal method and solvent-thermal method. Several technologies including X-ray powder diffraction (XRD), scanning electron microscope (SEM) and scanning electron microscopy (TEM) were employed to investigate the phase structures, morphologies. The photocatalytic properties of BiOI were evaluated by degrading methylene orange (MO) in simulate solar light, and the absorption capacity of solvent-thermal method-prepared samples were better than the solvent-thermal method-prepared and commercial photocatalyst P25 obviously. The absorption rate of methyl orange (MO) maintains more than 90% in 80 minutes. At the same time, it still has very high activity under UV light. In the process of photocatalytic reaction，exited electrons and the photo generated holes led to the photodegradation of MO aqueous by analyzing of the degradation mechanism
Key words: photocatalysis; BiOI; structure; catalytic degradation
新型吡咯酰胺催化剂的设计合成及催化Knoevenagel反应
黄克俊，裴学海，尹晓刚，杜莹，陈治明*
（贵州师范大学 化学与材料科学学院，贵州 贵阳 550001）
摘要：合成了5种未见报道的手性吡咯酰胺类有机小分子催化剂，并催化Knoevenagel反应。生成的烯腈产率高达80%以上，有机小分子催化剂回收率高达85％以上，可以重复使用，其催化活性并未降低。
关键词：吡咯酰胺；有机催化；Knoevenagel
中图分类号：O621.3 文献标识码：A 文献标识码：0258-3283（2017）
Synthesis of Novel Pyrrolidine-amide Catalysis for Knoevenagel Reaction HUANG Ke-jun, PEI Xue-hai, YIN Xiao-gang, DU Ying, CHEN Zhi-ming*(School of Chemistry and Materials Science, Guizhou Normal University, Guiyang 550001, China), Huaxue Shiji, 2017, 39(1)，
Abstract: Five kinds of new pyrrolidine-amide organocatalysts were synthesized and the Knoevenagel reaction is catalyzed by new pyrrolidine-amide catalysts in this work. The yied of the ethyreal are more than 80%，and the recovery rate of the organic small molecule catalyst is over 85% and can be reused, and catalytic activity is not reduced.
Key words：pyrrolidine-amide; organic catalyst; Knoevenagel
山楂酸衍生物的生物活性研究进展
张磊，张泽国，陈凡，林娅，朱心玲，王京*
(遵义医学院 药学院，贵州 遵义 563003)
摘要：山楂酸是一种天然植物中含有的五环三萜类产物，具有多种潜在的药理活性。但是其仍然存在五环三萜类共同的缺点，如水溶性差、生物活性水平较弱等。因此，人们对山楂酸的结构开展了一系列修饰与改造探索，得到了一些潜在的先导化合物。本文对近年来山楂酸衍生物的生物活性研究进展进行了综述，希望对山楂酸的进一步研究提供一些帮助。
关键词：山楂酸；衍生物；生物活性
中图分类号：R914 文献标识码：A 文章编号：0258-3283(2017)
Progress in Biological Activities of Maslinic Acid Derivatives ZHANG Lei, ZHANG Ze-guo, CHEN Fan, LIN Ya, ZHU Xin-ling, WANG Jing* (School of Pharmacy, Zunyi Medical College, Zunyi 563003, China), Huaxue Shiji, 2017, 39(1),
Abstract：Maslinic acid, a pentacyclictriterpene acid from many natural plants, has diverse potential pharmacological activities. However, it has some common disadvantages of pentacyclictriterpene, such aspoor solubility and low biological activity. Hence, the structure modifications of maslinic acid have been carried out for decades, discovering several potential lead compounds. This worker views the progress in biological activities of maslinic acid derivatives in recent years.
Key words：maslinic acid; derivative; biological activity
电化学氧化还原法降解卤代有机污染物的研究进展
黄金鑫，杨海，李海峰，林能，令狐文生*
（绍兴文理学院 化学化工学院，浙江 绍兴 312000）
摘要：卤代有机污染物的降解是水污染控制的一项重要课题。在诸多的降解技术中，电化学降解法具备反应条件温和、反应器简单、设备及其运行成本低、毒性副产物少等优点，因而成为了一项极具发展前景的环境友好型应用技术。综述了电化学氧化还原降解的反应机理以及目前国内外学者对该技术的研究进展，同时指出该技术研究在实际应用中所存在的问题和不足，并对未来电化学氧化降解卤代有机污染物的技术研究进行了展望。
关键词：卤代有机污染物；电化学氧化；电化学还原；电化学催化降解
中图分类号： 文献标识码：A 文章编号：0258-3283（2017）
Progress of Electrochemical Oxidation-reduction Method for Degradation of Halogenated Organic Pollutants HUANG Jin-xin, YANG Hai, LI Hai-feng, LIN Neng, LINGHU Wen-sheng（School of Chemistry and Chemical Engineering, Shaoxing University, Shaoxing, Zhejiang 312000）, Huaxue Shiji, 2017, 39(1),
Abstract：The degradation of halogenated organic pollutants is an important subject of water pollution. Rather than other various decomposing technologies of halogenated organic pollutants, the technique of electrochemical degradation has many advantages, such as mild reaction conditions, simple reactor, low cost of equipment and its operation, less toxic by-products, etc. So the technique of electrochemical degradation is environmentally friendly, which has a vast potential for future development. In this work, the reaction mechanism degradation of halogenated organic pollutants and the progress of its current research were reviewed. At the end, the problems and defects of this method in practical application and the outlook of in the future have been pointed out.
Key words: halogenated organic pollutants; electrochemical oxidation; electrochemical reduction; electrochemical catalytic degradation
原油及其馏分油中硫化物测定与形态分析
李佳1,2，周如金*1，郎春燕2
(1. 广东石油化工学院 化学工程学院，广东 茂名 525000；
成都理工大学 材料与化学工程学院，四川 成都 610059)
摘要：综述了原油及其馏分油中各类型硫化物的测定方法以及硫化物形态分析的方法，重点分析了重质馏分油中硫化物分离富集的3种方法：配位交换色谱法、氧化-还原法以及甲基化-去甲基化法，最后展望了硫化物形态分析方法的发展趋势。
关键词：硫化物；重质馏分油；形态分析；分离富集
中图分类号：TE624 文献标志码：A 文章编号：0258-3283（2017）
Determination of Sulfur Compounds and Analytical Methods of Sulfur Speciation in the Crude Oil and Distillation LI Jia1,2，ZHOU Ru-jin*1，LANG Chun-yan2 (1. College of Chemical Engineering, Guangdong University of Petrochemical Technology, Maoming 525000, China; 2.College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu 610059, China)，Huaxue Shiji，2017，39(1)，
Abstract: Determination of sulfur compounds and analytical methods of sulfur speciation in the crude oil and distillation were briefly reviewed and methods of separation and enrichment of sulfur compounds including ligand exchange chromatography method, oxidation-reduction method and methylation-demethylation method were mainly summarized and discussed. At last, the development trends of analytical methods were prospected.
Key words: sulfur compounds; heavy distillation; speciation analysis; separation and enrichment
气相色谱-串联质谱法同时测定可食用动物猪、牛和羊及淡水鱼中12种拟除虫菊酯类农药的残留量
李婷婷1，张勋2，付瑶2，高杰1，熊龙3，李丹4，刘先德5，马玉芹*1
（1. 长春理工大学，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 130022；5. 敦化市市场和质量监督管理局，吉林 敦化 133799）
摘要：建立12种拟除虫菊酯类农药在活体猪、牛和羊的尿液及其血液，淡水鱼中的多残留分析方法。样品经乙腈提取，弗罗里硅土柱层析净化，对气相色谱串联质谱法测定。同时对质谱条件进行了优化，从而得到了一种准确快速、灵敏度较高的农残检测方法。方法在0.002、0.005和0.01 mg/kg 3个添加水平下，拟除虫菊酯的添加回收率均在84.3% ～ 102.5%之间，相对标准偏差小于5.7%。12种菊酯类农药在10.0 ～ 200 µg/L的范围内具有良好的线性关系，相关系数为0.9993 ～ 0.9998；检出限均在10 μg/kg以下。
关键词：固相萃取；气相色谱-质谱法；菊酯类农药；食用动物
中图分类号：TQ450.7 文献标识码：A 文章编号：0258-3283(2017)
Determination of 12 Pyrethroid Pesticides in Livestock and Freshwater Fish of Edible Living Animals by Gas Chromatography-Mass Spectrometry LI Ting-ting1, ZHANG Xun2, FU Yao2, GAO Jie1, XIONG Long3, LI Dan4, LIU Xian-de5, MA Yu-qin* 1 (1.Changchun University of Science and Technology, Changchun 130022, China; 2.Jilin Entry-Exit Inspection and Quarantine Bureau, Changchun 130062, China; 3.Hanson Pharma Group Co., Ltd, Lianyungang 222047, China; 4.Anxin Technology Services Limited Liability Company, Changchun 130022, China; 5.The Administration of Market and Quality Supervision, Dunhua 133799, China), Huaxue Shiji, 2017, 39(1),
Abstract：A method was developed for the determination of 12 pyrethroid pesticides in edible living animals by gas chromatography-mass spectrometry. The edible living animals including the blood and urine of pig, cattle and sheep. Samples were extracted with acetonitrile and cleaned up on a florisil column before GC-MS analysis. This technique simultaneously provided with the function of extraction and purification. The recoveries were between 82.3% ～ 99.5% with the relative standard derivation(RSD) of less than 5.7% at the spiking levels of 0.002, 0.005 and 0.01 mg/kg. A good linear relationship was obtained in the range of 10.0 ～ 200 µg/L of the analysts with the correlation of 0.9993 ～ 0.9998. And the detection limit of the method was less than 10 μg/kg.
Key words：solid-phase extraction (SPE); gas chromatography-mass spectrometry (GC-MS); pyrethroid pesticides; edible living animals
电除尘汞平衡方法可靠性的研究
王雪1，江新权2，邬琦斌2，刘寅2，闫靖2，马萍2，陈平*1
（1.新疆师范大学 化学化工学院 污染监测与控制重点实验室，新疆 乌鲁木齐 830011；
2. 新疆电力科学研究院，新疆 乌鲁木齐 830011）
摘要：质量平衡率一般用来判断测试样品的准确性与可靠性。为了确定安大略法、EPA-30B法的准确性及可靠性，利用电除尘烟气中总汞监测结果等数据进行电厂汞平衡分析。汞在烟气及煤中的含量较低，汞的质量平衡率在70% ～ 130%范围内可接受。本实验锅炉+除尘器安大略法、EPA-30B法总汞平衡率为72.62% ～ 99.58%，均在参考范围之内，说明本次测试燃煤烟气中的汞取样操作可靠、测试数据准确、可信度较好。
关键词：烟气汞；平衡率；总汞监测；汞形态
中图分类号： TQ534.9 文献标识码：A 文章编号：0258-3283（2017）
Mercury BalanceMethod Based on the Reliability forthe Electric Dedust WANG Xue1，JIANG Xin-quan2，WU Qi-bin2，LIU Yin2，YAN Jing2，MA Ping2，CHEN Ping*1（1. Key Laboratory on Pollution Monitoring and Control, College of Chemistry and Chemical Engineering, Xinjiang Normal University, Urumqi 830011, China; 2. Xinjiang Electric Power Research Institute，Urumqi 830011, China），Huaxue Shiji, 2017, 39(1),
Abstract: Mass balance rate is generally used to judge the accuracy and reliability of the test samples. The mercury balance of power plant was analyzed by monitoring results of total mercury in ESP-flue gas. In order to determine the accuracy and operation reliability of the Ontario method and the EPA-30B method. The content of mercury in flue gas and coal is low, the mass balance rate of mercury is acceptable in the range of 70% ～ 130%. In this work, the boiler dust remover + Ontario method and the EPA-30B method of total mercury balance at a rate of 72.62% to 99.58%, were in the range of literature. The results show clearly that the test sample of mercury in coal-fired flue gas is reliable to operate. Accurate test data and high reliability can be obtained.
Key words: flue gas of mercury; balancerate; total mercury monitoring; forms of mercury
基于CdSe/ZnS量子点荧光猝灭法测定硫胺素
申晨凡，张直峰，郭瑜桉，闫桂琴*
（山西师范大学 生命科学学院，山西 临汾 041000）
摘要：以 CdSe/ZnS 量子点为荧光探针，基于硫胺素（VB1）与 CdSe/ZnS 量子点间通过静电作用而有效猝灭 CdSe/ZnS 量子点荧光强度的机制，建立了一种可快速测定 VB1的荧光检测方法。在最优实验条件下（pH 7.4，反应时间25 min），硫胺素（VB1）浓度在0.01 ～ 1 μmol/L之间时，CdSe/ZnS 量子点荧光猝灭变化强度与硫胺素（VB1）浓度呈良好的线性关系：F0/F=0.67CVB1+1.05（R=0.9992），方法检出限为5.1×10-3 μmol/L，相对标准偏差为1.09%。该方法可用于人体尿样中VB1的快速测定。
关键词：CdSe/ZnS量子点；硫胺素(VB1)；荧光猝灭；测定
中图分类号： O657. 3；Q563+.1 文献标识码：A 文章编号：0258-3283（2017）
Fluorescence Quenching Determination of Thiamin Based on Cdse/Zns Quantum Dots SHEN Chen-fan, ZHANG Zhi-feng, GUO Yu-an, YAN Gui-qin*( College of Life Science, Shanxi Normal University, Linfen 041000, China)，Huaxue Shiji，2017，39(1)，
Abstract：A new fluorescent probe analysis method for determination of thiamine (VB1) was developed based on fluorescent quenching function of thiamine (VB1) for CdSe/ZnS quantum dots.The fluorescence quenching was caused by the electrostatic inter-action from thiamine (VB1) to CdSe/ZnS QDS. Under the optimal conditions (pH 7.4, reaction time of 25 min), when the concentration of thiamine (VB1) is in the range of 0.01 ～ 1 μmol/L, the fluorescence quenching change strength of CdSe/ZnS quantum dots has a good linear relationship with concentration of thiamine (VB1): F0/F=0.67CVB1+1.05（R=0.9992）. The detection limit and relative standard deviation were 5.1×10-3 μmol/L and 1.09%, respectively. Finally,this method was successfully used to detect thiamine (VB1) in human urine.
Key words: CdSe/ZnS quantum dots; thiamine(VB1); fluorescence quenching; determination
置换液液分散微萃取测定水样中的痕量镉
朱晓敏*，王博，任云，王胜利
（邯郸学院 化学化工与材料学院 邯郸市有机小分子材料重点实验室，河北 邯郸 056005）
摘要：首次采用置换液液分散微萃取法分离富集环境水样中痕量镉。在实验中，分别对萃取剂、分散剂、被置换剂的种类、配合剂二乙基二硫代氨基甲酸钠（DDTC）的浓度、水-分散剂-有机萃取剂三者的体积比，以及溶液的酸度进行了优化。得到的最佳实验条件为：在pH 6左右时，四氯化碳、丙酮、Zn2+分别为萃取剂、分散剂和被置换剂，DDTC配合浓度为0.003%，水相、丙酮和四氯化碳的体积分别为5.00、0.50 mL和90 μL。在上述确定的实验条件下，成功测定了复杂水样中痕量镉，方法的检出限为0.005 μg/L，回收率为92.5% ～ 109%。
关键词：置换液液分散微萃取；复杂基质；被置换剂；镉
中图分类号：0652.6 文献标识码：A 文章编号：0258-3283（2017）
Application of Novel Dispersive Liquid-liquid Microextraction for Trace Cadmium in Environmental Water Samples ZHU Xiao-min*，WANG Bo，REN Yun，WANG Sheng-li （ ），Huaxue Shiji, 2017, 39(1),
Abstract：In this work, displacement dispersive liquid-liquid micro extraction (D-DLLME) has been developed for the analysis of cadmium in complex matrix for the first time. Extracting agent, dispersant, displacement agent were selected, and the concentration of sodium diethyldithiocarbamate（DDTC）, the volume ratio of water, dispersant, organic phase, and solution acidity were optimized. The optimal experimental conditions were obtained. pH 6, the extracting agent, dispersant, displacement agent was selected the carbon tetrachloride, acetone and Zn2+. 0.003%DDTC, the volume of water, dispersant , organic phase was 5.00 mL, 0.50 mL, 90 μL. The method was developed in Complex matrix, and the detection limit was 0.005 μg/L．The recovery rate was from 92.5% to 109%.
Key words：displacement dispersive liquid-liquid microextraction；complex matrix；displacement agent；cadmium
柱前衍生化-高效液相色谱法测定叔丁基肼盐酸盐的含量
刘立业*，丁元生，史晋宜
（吉林化工学院 化学与制药工程学院，吉林 吉林 132022）
摘要：建立了柱前衍生化高效液相色谱法测定叔丁基肼盐酸盐含量的方法。以苯甲醛为衍生化试剂，色谱柱为HypersilTM BDS C18，柱温为25 ℃，流动相为甲醇，流速为1.0 mL/min，检测波长为298 nm。叔丁基肼盐酸盐在3.0 ～ 7.0 mg范围内与其衍生物峰面积呈良好的线性关系，回归方程为Y = 179361X - 112865，R2= 0.999，RSD = 0.68%，平均回收率为100.40%。本方法简便易行、样品前处理简单，具有较高的精密度与准确度。
关键词：叔丁基肼盐酸盐；高效液相色谱法；含量测定；柱前衍生化法
中图分类号：R917 文献标识码：A 文章编号：0258-3283（2017）
Determination of Tert-butyl Hydrazine Hydrochloride by Pre-column Derivatization with HPLC LIU Li-ye*, DING Yuan-sheng, SHI Jin-yi（College of Chemistry and Pharmaceutical Engineering, Jilin Institute of Chemical Technology, Jilin 132022，China）, Huaxue Shiji, 2017, 39(1),
Abstract：A pre-column derivatization with HPLC method was established for the determination of tert-butyl hydrazine hydrochloride. Benzaldehyde was used as the derivatizing reagent. The HypersilTM BDS C18 column was used with the column temperature of 25 ℃. Methanol was used as the mobile phase with the flow rate of 1.0 mL/min at the detection wavelength of 298 nm. It was linear for the tert-butyl hydrazine hydrochloride in the range of 3.0 ～ 7.0 mg. The regression equation was Y=179361X-112865, R2=0.999.The average recovery was 100.40% with RSD of 0.68%.This method was simply with higher precision and accuracy.
Key words: tert-butyl hydrazine hydrochloride; HPLC; content determination; pre-column derivatization
冷聚焦-GC-MS法测定22种氯代烃气体标准样品
杜健1，李宁2，王帅斌2，钱萌2，王倩*1
（1.环境保护部标准样品研究所，北京 100029
2.国家环境保护污染物计量和标准样品研究重点实验室(筹)，北京 100029）
摘要：采用冷聚焦-GC-MS联用测定浓度水平为1 μmol/mol的22种氯代烃混合气体标准样品，在保证各组分能够实现良好分离效果的前提下，对相关分析条件进行了优化以实现样品分析测定的重复性最佳。采用优化后的分析条件对两瓶同一浓度水平的样品进行量值比对，结果表明该方法准确、可靠，可为相关气体标准样品的研制提供技术支持。
关键词：冷聚焦-GC-MS；氯代烃；标准样品；优化
中图分类号：O659 文献标识码：A 文章编号：0258-3283（2017）
Measurement of Standard Gas Mixture of 22 Chlorinated Hydrocarbons by Method of Cryofocus-GC-MS DU Jian1，LI Ning2，WANG Shuai-bin2，QIAN Meng2，WANG Qian* 1 (1. Institute for Environmental Reference Materials，Beijing 100029，China；2. State Environmental Protection Key Laboratory of Environmental Pollutant Metrology and Reference Materials，Beijing 100029，China)，Huaxue Shiji，2017，39(1)，
Abstract: Standard gas mixture of 22 chlorinated hydrocarbons by the level of 1 μmol/mol was determined by cryofocus-GC- MS. Under the premise of ensuring good separation effect, the relevant analysis conditions were optimized to achieve the best repeatability of sample analysis and determination. The results show that the method is accurate and reliable by using the optimized analytical condition to compares two samples in the same concentration level. Therefore, the method can provide technical support for the research of relevant standard gas.
Key words: cryofocus-GC-MS; halogenated hydrocarbon; standard gas; optimized
荧光“502”显现潜在手印研究
刘哲，王聪，罗亚平*
(中国人民公安大学 刑事科学技术学院，北京 100038）
摘要：探究一种新型的荧光“502”用于显现潜在手印的方法。实验对该荧光“502”显现常见客体上潜在手印的效果以及显现手印的灵敏度进行了研究，并比较了这种同步熏显染色的方法与罗丹明6G、Ardrox荧光液、基础黄40二次染色方法显现手印的效果。结果表明这种荧光“502”显现潜在手印效果较好，用Coherent Tracer激光器激发后，在橙红色护目镜下可以到观察强烈的黄色或橙黄色荧光，显出的手印纹线清晰，与背景反差明显，可以观察到手印纹线上的汗孔。荧光“502”显现潜在手印的方法操作简便，没有后续二次染色的过程，因此不会破坏手印，可以确保纹线及其细节特征的完整性。
关键词：法庭科学；荧光“502”；同步熏显染色；潜在手印显现
中图分类号： DF794.1 文献标识码：A 文章编号：0258-3283（2017）
Fluorescent Cyanoacrylate for Latent Fingerprints Development LIU Zhe, WANG Cong, LUO Ya-ping* ( ，People’ s Public Security University of China, Beijing 100038，China)，Huaxue Shiji，2017，39(1)，
Abstract: To develope the method of a new luminescent cyanoacrylate which allows one-step development for fingerprints. This work investigated the effect of latent fingerprints detected by using new luminescent cyanoacrylate, sensitivity of its development and compares the one-step development to Rhodamine 6G solution, Ardrox and BasicYellow40solution staining methods. The results indicate that luminescent cyanoacrylate detects fingerprints with good ridge details. In green laser wavelengths of excitation. It can be observed strong yellow or orange fluorescent fingerprints with clear fingerprint ridges and sweat pores under the orange goggles. Detecting fingerprints by luminescent cyanoacrylate is easy to accomplish, moreover, the integrity of fingerprint ridges and details could be ensured without the subsequent dyeing process.
Key words: forensic science; fluorescent cyanoacrylate; one-step development; latent fingerprints
基于联苯甲酰衍生物新型荧光探针的设计、合成及其性质研究
田林a，岳玮a，盛风涛a，黄天姿b，张青青a，刘冬妮a，朱凤娟a，于浩a，堵锡华*a
（徐州工程学院 a. 化学化工学院；b.食品工程学院，江苏 徐州 221018）
摘要：以1-(2-氯苯基)-2-（2,3-二甲氧基苯基）-乙二酮、水杨酰肼为原料合成了一种新型的离子荧光探针苯甲酰双腙类衍生物BDH，化合物结构通过红外、氢谱、碳谱以及高分辨质谱进行确认。选择性实验表明，当以乙腈为溶液时，化合物BDH能够选择性的识别Cr3+。竞争性实验表明，当其他金属离子与Cr3+形成共存离子时，不影响BDH对Cr3+的检测作用，说明配体具有较强的抗干扰能力。荧光滴定实验表明，当Cr3+的浓度范围在8 × 10-7 ～ 5 × 10-6 mol/L时，Cr3+的浓度与△F呈现较好的线性关系，线性拟合系数为0.99695，检测限为1.19 × 10-11 mol/L。Job’s Plot实验表明，BDH和Cr3+以1:1的形式配位。
关键字：合成；Cr3+ 专一识别；强抗干扰能力
中图分类号: 0641 文献标识码:A 文章编号：0258-3283（2017）
Synthesis and Property of Novel Fluorescent Probe Based Dibenzoyl Derivatives TIAN lina, YUE weia, HUANG Tian-zib, ZHANG Qing-qinga, LIU Dong-nia, ZHU Feng-juana, YU Haoa, DU Xi-hua*a (a. School of Chemical Engineering and Technology；b. Food Engineering College, Xuzhou Institute of Technlogy，Xuzhou 221018, China)，Huaxue Shiji，2017, 39（1）
Abstract: A novel Cr3+ fluorescent probe benzildihydrazone dericatives BDH for Cr3+ was synthesized via1-(2-chlorophenyl)-2-(2, 3- dimethoxyphenylethane-1, 2- dione, salicylhydrazide as raw materials. The structures were confirmed by IR, 1HNMR,13CNMR, HR-MS. The compound BDH had an excellent special identification capacity for Cr3+ in acetonitrile, competiting experiment showed that it does not affect on the detection Cr3+, while another metal ions coexist with Cr3+，and this work indicates ligand BDH had a strong anti-interference ability, and fluorescence titration experiment exhibited the fluorescence intensity △F and the concentration of Cr3+ show a better linear relationship and the linear correlation coefficient was 0.97488, when the concentration range of Cr3+ was 0.1 × 10-5 ～ 0.5×10-5 mol/L. The detection limit was 1.19 × 10-11 mol/L. The Job’s plot experiment showed that the complex of BDH and Cr3+ was 1:1.
Key word: synthesis; Cr3+; special identification；stronger anti-interference ability
新型手性β-氨基醇的合成及其催化性质
白冰，惠志铮，杨静，张改红，毛多斌*
(郑州轻工业学院 食品与生物工程学院，河南 郑州 450000)
摘要：以色氨酸和多环芳醛为原料，经过酯化、格氏加成、还原氨化反应，合成了一系列具有大体积基团的手性β-氨基醇催化剂。利用核磁、红外、质谱（1HNMR、13CNMR、IR、MS）等对化合物结构进行了表征，并对其催化二乙基锌对醛的加成作用进行了研究。
关键词：β-氨基醇；二乙基锌；加成
中图分类号：O621.3 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of β-Amino Alcohols and Application in Enantioselective Reaction BAI Bing, HUI Zhi-zheng, YANG Jing, ZHANG Gai-hong, MAO Duo-bin*(School of Food & Biological Engineering, Zhengzhou University of Light Industry, Zhengzhou 450000, China), Huaxue Shiji, 2017, 39(1),
Abstract：Several chiral β-amino alcohols possessing bulky substituents were synthesized from L-tryptopha. The structures were confirmed by 1HNMR, 13CNMR, IR, MS. They were used as chiral catalysts in the asymmetric addition of diethylzinc to aldehydes．
Key words：β-amino alcohol; diethylzinc; addition
固体超强酸SO42-/Fe2O3的制备及其对甲缩醛合成反应的催化性能
颜康*，贺新，李树白
（常州工程职业技术学院 ，江苏 常州 213164）
摘要：以Fe(NO3)3、NH3·H2O和H2SO4为原料，采用直接沉淀法制备了固体超强酸SO42-/Fe2O3催化剂，用于甲醇与甲醛催化合成甲缩醛。围绕焙烧温度对催化剂催化活性的影响进行了考察，得到了最佳焙烧温度。用X-射线衍射（XRD）、红外光谱（IR）、比表面积（BET）、pH测试等方法对催化剂进行了表征，得到了催化剂比表面积、晶型、活性中心结构等性能参数，使用优化条件下制备的催化剂，反应可得甲缩醛质量分数为59%的馏出液。
关键词：固体超强酸；甲缩醛；SO42-/Fe2O3；催化
Preparation of Solid Superacid SO42-/Fe2O3 and Catalytic Performance for Synthesis of Methylal YAN Kang*, HE Xin, LI Shu-bai (College of Material and Chemical Engineering, Changzhou Institute of Engineering Technology, Changzhou 213164,China), Huaxue Shiji, 2017, 39(1)
Abstract: A solid super acid catalyst was prepared from Fe(NO3)3, NH3·H2O and H2SO4 by direct precipitation in the synthesis of dimethoxymethane(DMM) from methanol and formaldehyde. The influence of roast temperature on the activity of the catalyst was investigated and an optimum temperature was obtained. By use of X-ray diffraction (XRD), infrared spectroscopy (IR), specific surface area test (BET) and pH value test, SO42-/Fe2O3 catalyst was characterized, specific surface area and structure of active center of the catalyst were obtained. The distillate (with 59% mass fraction of methylal) can be produced by reaction, in which the catalyst was prepared in optimized condition.
Key words: solid super acid; methylal; SO42-/Fe2O3; catalysis
萃取蒸馏法提升乙酸乙酯的品质
朱彩芳，凌芳*，郑琦，顾小焱，刘征宙
（国药集团化学试剂有限公司，上海 200002）
摘要：本论文公开了一种提升乙酸乙酯品质的方法。以工业乙酸乙酯为原料，加入混合萃取剂，大孔分子筛，在萃取精馏装置内进行蒸馏，全回流1 ～ 2 h后弃去前馏分，收集76.8 ～ 77.5 ℃的馏分，再经0.10 ～ 0.22 μm醋酸纤维素酯膜的过滤后得到提升品质的乙酸乙酯，混合萃取剂与分子筛可以循环使用。用本方法得到的乙酸乙酯纯度＞99.9%，水分＜0.01%，符合LC-MS分析乙酸乙酯的标准。本方法操作简单，同时萃取剂及分子筛可重复利用，符合绿色化工的要求，产品质量稳定，适于工业化生产。
关键词：乙酸乙酯; 混合萃取剂; 大孔分子筛; 蒸馏; 0.10 ～ 0.22 μm醋酸纤维素酯膜; 过滤
中图分类号：TQ225.2 文献标识码：A 文章编号：0258-3283（2017）
Improving the Quality of Ethyl Acetate- Extractive Distillation ZHU Cai-fang, LING Fang*, ZHENG Qi, GU Xiao-yan, LIU Zheng-zhou（Sinopharm Chemical Reagent Co., Ltd，Shanghai 200002, China）, Huaxue Shiji, 2017, 39(1),
Abstract: The dissertation discloses a method to improve the quality of ethyl acetate. Using ethylacetate as raw material, adding a mixture of extraction agent, a large pore molecular sieve, and distilling in the extraction and distillation unit. Full reflux 1 ～ 2 h before discarding the former fraction, then collecting the fraction of 76.8 ～ 77.5. The improved quality of ethyl acetate was obtained by the filtration of 0.10 ～ 0.22 μm cellulose acetate membrane. Mixed extraction agent and molecular sieve can be recycled. The purity of ethyl acetate obtained is greater than 99.9%, and the water content is less than 0.01%, which conforms to the standard of LC-MS analysis. The method has the advantages of simple operation, simultaneous extraction and molecular sieve recycling, which meets the requirements of the green chemical industry, and the product quality is stable, and the product is suitable for industrial production.
Key words: ethylacetate; mixed extraction agent; a large pore molecular sieve; distillation; 0.10 ～ 0.22 μm cellulose acetate membrane; filter
新型立体位阻的叔丁基芳基N-磺酰亚胺的合成
王玉麟1，李飞龙1，刘雨风1，赵敏*1，陈建中*2
(1.华东理工大学 ，上海 200237；2.上海交通大学 ，上海 200240)
摘要：以芳基溴和氯代叔丁烷为原料，经格式反应得到相应叔丁基芳基酮，接着在四氯化钛、三乙胺存在下，与磺酰胺加成得到了10个新型的叔丁基芳基N-磺酰亚胺化合物，其结构经1HNMR、13CNMR、ESI-MS、IR和熔点等表征。并通过单晶X-ray衍射确定代表化合物的绝对构型是Z构型。该产物可以应用于生物活性物质的合成中。
关键词：叔丁基芳基酮；叔丁基N-磺酰亚胺；合成；立体位阻
中图分类号：O625; O622.6 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of Sterically Hindered tert-Butyl Aryl N-Tosylimines WANG Yu-lin1, LI Fei-long1, LIU Yu-feng1, ZHAO Min*1, CHEN Jian-zhong *2 (1. ，East China University of Science and Technology, Shanghai 200237, China; 2. ，Shanghai Jiao Tong University, Shanghai 200240, China)，Huaxue Shiji, 2017, 39(1),
Abstract： The t-butyl aryl ketones were prepared via Grignard reaction of aryl bromides and t-butylchloride. The corresponding ketones readily coupled in the presence of TiCl4 and Et3N with sulfamide. A series of t-butyl aryl N-tosylimines were obtained with good yields. The structures were confirmed by 1HNMR, 13CNMR, ESI-MS, IR and melting point measurement. X-ray crystal analysis of 1a showed that the products could be assigned with the Z configuration. The reduced products could subsequently be used in the synthesis of bioactive compounds.
Key words：t-butyl aryl ketones；t-butyl N-tosylimines；synthesis；sterically hindered
DMAc促进乙酰苯胺的合成
罗年华*a，郑大贵a，钟瑜红b，王勇a，余维洁a，曾春a
(上饶师范学院 a. 化学化工学院；b.教育技术与实验中心，江西 上饶 334001)
摘要:在N,N-二甲基乙酰胺(DMAc)和CH2Cl2体系中，乙酸与SOCl2在0 ℃下反应20 min，制得的乙酰氯不经提纯直接与加入的苯胺在25 ℃下反应5 h，得到了一系列取代乙酰苯胺化合物。优化条件下，反应产率为83 % ～ 97 %。目标化合物的结构经1HNMR、13CNMR、IR和MS确证，提出了DMAc协同促进乙酰苯胺合成反应的可能机理。
关键词：DMAc；乙酸；苯胺；乙酰苯胺
中图分类号：O625.52 文献标识码：A 文章编号：0258-3283（2017）
Dimethylacetamide-promoted Synthesis of N-acetyl Anilines LUO Nian-hua*a, ZHENG Da-guia, ZHONG Yu-hongb, WANG Yonga, YU Wei-jiea, ZENG Chuna (a. ; b. Educational Technology&Expenimental Center, Shangrao Normal University, Shangrao 334001, China), Huaxue Shiji, 2017, 39(1),
Abstract: A series of N-acetyl anilines were synthesized by the chlorination of acetic acid with thionyl chloride in dimethylacetamide-dichloromethane at 0 ℃ for 20 min，followed by amidationin situ withanilines at 25 ℃ for 5 h in 83 %～97 % yields under the optimal conditions. The structures of target compounds were confirmed by 1HNMR, 13CNMR, IR and MS. The proposed mechanism for the promotion of dimethylacetamid on the synthesis was suggested.
Key words: dimethylacetamide; acetic acid; anilines; N-acetyl anilines
新型四唑并[1, 5-a]哌嗪类螺环化合物的合成研究
李飞飞，滕大为*
(青岛科技大学 化工学院，山东 青岛 266042）
摘要：以取代苄胺、1-叔丁氧羰基-4-哌啶酮、叠氮基三甲基硅烷（TMSN3）和异腈化合物为原料，经四组分“一锅煮”反应，得到新型四唑并[1, 5-a]哌嗪类螺环化合物。研究了温度和溶剂对反应的影响，得到最佳反应条件，以甲醇为溶剂，65 ℃回流条件下反应48 h。所有产物结构经1HNMR和MS进行了表征。
关键词：四唑；螺环化合物；四组分反应；合成
中图分类号：O626 文献标识码：A 文章编号：0258-3283（2017）
Synthesis and Characterization of Novel Spirotetrazoles LI Fei-fei ,TENG Da-wei* (College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China), Huaxue Shiji, 2017, 39(1),
Abstract: An efficient one-pot synthesis of spirotetrazole [1,5-a] piperazine-piperidines by the four-component condensation of benzylamine, 1-Boc-4-piperidinone, TMSN3 and isocyanides derivatives was reported. The effects of solvent and temperature on the reaction were elucidated and the optimal reaction conditions were obtained. The structures of products were confirmed by 1HNMR and MS.
Key words: tetrazole; spiro compounds; four-component reaction; synthesis
叶菌唑戊酮的合成研究
李海涛1, 2，张皓3，张传好1，纪招君1，詹家荣*1，田伟生*4
(1. 上海化学试剂研究所有限公司，上海 200333；2. 华东理工大学 化工学院，上海 200237；3. 上海试四赫维化工有限公司，上海 200940；4. 中国科学院上海有机化学研究所，上海 200032)
摘要：标题化合物是合成杀菌剂叶菌唑的关键中间体。以异丁酸甲酯为原料，经过碳链增长、分子内Friedel-Crafts酰化、Baylis-Hillman反应、催化氢化、琼斯氧化等反应，摒弃了传统高毒性甲基化步骤，成功合成了叶菌唑戊酮，以初始原料异丁酸甲酯计算，总收率47.5%，中间体及产物用1HNMR及ESI-MS进行了表征。
关键词：叶菌唑戊酮；叶菌唑；异丁酸甲酯
中图分类号：O626 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of Metconazole-pentone LI Hai-tao1,2, ZHANG Chuan-hao1, JI Zhao-jun1, ZHAN Jia-rong*1 (1.Shanghai Chemical Reagent Research Institute Co., Ltd, shanghai 200333,
Abstract: Metconazole-pentone is a key intermediate for the synthesis of metconazole. Methyl isobutyratewas treated by carbon chain growth, intramolecular Friedel-Crafts acylation, Baylis-Hillman reaction, catalytic hydrogenation and Jones oxidation etal to synthesize metconazole-pentone without the traditional highly toxic methylation step. This method was successful and the total yield was 47.5%. Important intermediates and products were confirmed with 1HNMR and ESI-MS.
Key words: metconazole-pentone; metconazole; methyl isobutyrate
艾氟康唑相关物质的合成
李晓坤*，张灵帅，孟迪
(河南中医药大学 药学院，河南 郑州 450046)
摘要：为控制抗真菌药艾氟康唑的产品质量，合成了(2S,3R)-2-(2,4-二氟苯基)-3-(4-亚甲基哌啶-1-基)-1-(1H-1,2,4-三唑-1-基)-2-丁醇)(艾氟康唑非对映异构体)。首先以L-乳酸甲酯为原料合成了中间体 (2S)-2’,4’-二氟苯基-2-(3,4,5,6-四氢-2H-吡喃-2-氧)丙基酮，然后经脱保护、哌啶烷基化得中间体，经科里-柴可夫斯基环氧化、三氮唑烷基化后得目标化合物。该合成路线未见报道，所有化合物经1HNMR和ESI-MS确证结构。该相关化合物可作为艾氟康唑质量控制中的杂质对照，用于准确定量、定性分析相关杂质。
关键词：抗真菌药；艾氟康唑；相关物质；合成
中图分类号： R914.5 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of Related Substance of Efinaconazole LI Xiao-kun*，ZHANG Ling-shuai，MENG Di ( School of Pharmcy, Henan University of Traditional Chinese Medicine, Zhengzhou 450046，China), Huaxue Shiji, 2017, 39(1),
Abstract：To perform the quality control of the antifungal drug efinaconazole, the diastereoisomer of efinaconazole (2S,3R)-2-(2,4-difluorophenyl)-3-(4-methylenepiperidin-1-yl)-1-(1H-1,2,4- triazol-1-yl)butan- 2-ol was prepared. Intermediate (2S)-2’,4’-difluoro-2-(3,4,5,6-tetrahydro-2H-pyran-2-yloxy)propiophenone was first prepared from L-methyl lactate based on the reference, then the ketone (2R)-2’,4’- difluoro-2-(4-methylenepiperidin-1-yl)propan-1-one was offered via the deprotection and alkylation reaction, finally the product was obtained after the subsequent Corey–Chaykovsky epoxidation and triazole alkylation. It is the first time to report this route for synthesis of the product. The structures were comfirmed by 1HNMR and ESI-MS. This substance can be used as the reference substance of the impurity in the quality control of efinaconazole.
Key words：antifungal drug; efinaconazole; related substance; synthesis
三聚茚可控分步氧化制备三聚茚酮衍生物
李继超，刘亚东，宋新潮，张倩，郭旺军，安忠维*
（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：报道了一种三聚茚通过可控氧化分步制备三聚茚酮衍生物的方法，采用的氧化剂体系是三氧化铬和冰乙酸。通过控制氧化剂的用量和反应温度，三聚茚可以69% ～ 78%的收率被分步氧化为三聚茚单酮、双酮或三酮。本方法步骤短、操作简单、产物易分离纯化，有望用于构建复杂的非C3对称型三聚茚基功能分子。
关键词：三聚茚；三聚茚酮；氧化
中图分类号：O626 文献标识码：A 文章编号：0258-3283（2017）
Controllable Stepwise Oxidation of Truxene to Truxenone Derivatives LI Ji-chao, LIU Ya-dong, SONG Xin-chao, ZHANG Qian, GUO Wang-jun, AN Zhong-wei* (State Key Laboratory of Fluorine＆Nitrogen Chemicals, Xi'an Modern Chemistry Research Institute, Xi'an 710065, China), Huaxue Shiji, 2017, 39(1)
Abstract：A stepwise oxidation method of 10, 15-dihydro-5H-diindeno[1, 2-a : 1', 2'-c]fluorine (truxene) derivatives to 5H-diindeno[1, 2-a : 1', 2'-c]fluorene-5,10,15-trione (truxenone) derivatives by chromium trioxide and glacial acetic acid system was reported. Truxene could be converted to mono-, di- or tri-ketone derivatives with 69% ～ 78% yield by controlling the amount of oxidant and reaction temperature. Short step, simple operation, easy separation were the advantages of this method, which was expected for the construction of complicated non-C3 symmetrical truxene based functional molecules.
Key words：truxene; truxenone; oxidation
新型喹诺酮类衍生物的合成
李文燕*1，刘洪涛2，任炳楠2，徐辰1
(1. 河北师范大学 化学与材料科学学院，河北 石家庄 050024；
2. 河北省人民医院 药学部，河北 石家庄 050051)
摘要：以4-硝基愈创木酚、乙氧甲叉基丙二酸二乙酯、2-巯基苯并噻唑等为原料，经烃化、还原、缩合、环合、水解、缩合酰化等反应合成了两个喹诺酮-3-甲酰胺类衍生物、两个喹诺酮-3-甲酸硫酯类衍生物，化合物结构经核磁氢谱、质谱确证，结构未见文献报道，为新型喹诺酮类小分子药物的研究提供了化合物基础。
关键词：喹诺酮-3-甲酰胺类；喹诺酮-3-甲酸硫酯类；合成
中图分类号：O626 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of Novel Quinolone Derivatives LI Wen-yan*1, LIU Hong-tao2, REN Bing-nan2, XU Chen1 (1. College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang 050024, China; 2. Department of Pharmacy, Hebei General Hospital, Shijiazhuang 050051, China), Huaxue Shiji, 2017, 39(1)
Abstract：Two novel quinolone-3-carboxamides and two novel quinoline-3-carbothioates were synthesized form 2-methoxy-4-nitrophenol, ethoxy methylene diethyl malonate and 2-mercapto benzothiazole via alkylation, reduction, condensation, cyclization, hydrolyzation and acylation etc. The structures were confirmed by 1HNMR and MS. This work provides a compound foundation on the development of novel quinolones drug.
Key words：quinolone-3-carboxamides; quinoline-3-carbothioates; synthesis
