稳定同位素氘标记苯脲类除草剂的合成
冯玉冰，李晶，杨顺风，邵星，倪澜荪*
（湖北出入境检验检疫局检验检疫技术中心，湖北 武汉430050）
摘要：为制备HPLC-MS/MS农药残留分析中使用的苯脲类除草剂同位素内标物，以取代苯胺为原料，与三光气反应制得取代的苯基异氰酸酯，再与二甲胺-D6盐酸盐亲核加成，合成了9种苯脲类除草剂的氘取代物，分别是敌草隆-D6、灭草隆-D6、2，3-敌草隆-D6、绿麦隆-D6、甲氧隆-D6、秀草隆-D6、非草隆-D6、伏草隆-D6和异丙隆-D6。结构通过NMR，MS和UV确证，化学纯度均大于98%，同位素丰度大于99.5%，完全满足质谱分析对内标物的要求，可作为HPLC-MS/MS分析的同位素内标物。
关键词：同位素内标；氘取代物；苯脲类化合物；除草剂；合成
中图分类号：O628.1 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of Stable Isotope Deuterium Substituted Phenylurea Hebicides FENG Yu-bing, LI Jin, YANG Shun-feng, SHAO Xing, NI Lan-sun*(Technology Center, Hubei Entry-Exit Inspection and Quarantine Bureau, Wuhan430050,China)
Abstract：In order to prepare isotope internal standards of phenylurea hebicides for pesticide residue HPLC-MS/MS analysis, the N,N-dimethyl-deuterated forms of nine ingredients were synthesized form substituted phenylamine in two simple steps via the reaction with triphosgene, and nucleophilic addition with dimethyl-D6-amine hydrochloride, the deuterium substituted compounds include Diuron-D6, Monuron-D6, 2,3-Diuron-D6, Chlorotoluron-D6, Metoxuron-D6, Bromuron-D6, Fenuron-D6, Fluometuron-D6 and Isoproturon-D6. The structures were confirmed by NMR, MS and UV. The purities of all chemicals are more than 98%, meanwhile, all the isotope purities are more than 99.5%. These deuterium substituted compounds could be used an isotope internal standards in quantitation of herbicide residue in water, soil and agricultural products by HPLC-MS/MS.
Key words: isotope internal standard; deuterium substituted compounds; phenylurea compounds; herbicide; synthesis
TiO2 纳米管阵列光电催化降解抗生素
缪应纯，王宁宏，徐晓林
(曲靖师范学院 化学与环境科学学院 资源与环境化学重点实验室，云南 曲靖 655011
摘要：阳极氧化制备的TiO2比表面积大且形貌尺寸可控，比其他形式的纳米二氧化钛具备更加优异的性能。本文研究了氧化时间、氧化电压以及烘烤温度对TiO2光电流的影响，更重要的是采用制备的TiO2在光电催化下降解环境中的新型污染物抗生素（盐酸四环素、头孢唑啉钠、头孢噻肟钠）。结果表明：氧化时间为6 h 、氧化电压20 V、烘烤温度为 500 oC时制备的TiO2具有优异的光电催化活性，其降解率是光催化条件下的3倍，明显优于电催化。
关键词：TiO2；阳极氧化法；光电催化；降解率
中图分类号：X382 文献标志码：A
Photoelectrocatalytic Degradation of Antibiotics by TiO2 Nanotubes Array MIAO Ying-chun, WANG Ning-hong, Xu Xiao-lin (Faculty of Chemical and Environment Sciences, Key Laboratory of Environment Chemistry for Natural Resource, Qujing Normal University, Qujing 655011, )
Abstract：The surface area, morphology and size of TiO2 by anodic oxidation method could be controlled. It has more excellent performance than other TiO2. The effect of oxidation time, temperature and voltage was discussed on the photocurrent, and the optimization of anodic oxidation method was found. The as-prepared TiO2 used for photoelectrocatalytic degradation of antibiotics (tetracycline hydrochloride, cefazolin, cefotaxime sodium ). The results shows that degradation exhibited higher activity under photoelectrocatalytisis than photocatalysis and electrocatalysis, and then the photoelectrocatalytic degradation rate was 3 times of the photocatalytic degradation rate,when oxidation time of 6 h, oxidation voltage 20 V, calcination temperature of 500 OC prepared TiO2.
Key words：TiO2; anodic oxidation; photoelectrocatalysis; degradation rate
N-((吡咯-2-)甲基)-3-羟基萘-2-甲酰胺催化的吲哚与硝基烯烃的Friedel-Crafts烷基化反应
王文琛，黄克俊，裴学海，杨志翔，王金娟，陈治明*
（贵州师范大学 化学与材料科学学院 贵州省功能材料重点实验室，贵州 贵阳 550001）
摘要：探讨廉价易得、环境友好的N-((吡咯-2-)甲基)-3-羟基-萘-2-甲酰胺催化的吲哚与硝基烯烃不对称Friedel-Crafts烷基化反应。研究表明，在35 ℃条件下，CH2Cl2为溶剂，10 mmol% 催化剂，反应11 h，吲哚及1-位或2-位被取代的吲哚与硝基烯烃能有效的进行Friedel-Crafts烷基化反应，可以获得较好的产率。该反应具有催化剂经济易得及用量少、反应条件温和、环境友好和操作简单等优点。
关键词：吲哚；硝基烯烃；Friedel-Crafts烷基化反应
中图分类号：O626 文献标识码：A 文章编号：0258-3283（2017）
3-hydroxy-N-((pyrrolidin-2-yl)methyl)naphthalene-2-carboxamide catalyzed Fiedel-Crafts Alkylation of indole with nitrostyrene Wang Wen-cheng,, Huang Ke-jun, Pei xue-hai, Yang Zhi-xiang, Wang jing-juan, Cheng Zhi-ming*(Key Laboratory of Functional Materials chemistry of Guizhou province, School of chemistry and Materials Science,Guizhou Normal University, Guiyang 550001)
Abstract：An inexpensive and enironmentally friendly 3-hydroxy-N-((pyrrolidin-2-ly)methy)naphthalene-2-carboxamide asymmetric Friedel-Crafts alkylation of indole with β- nitrostyrenes including free-NH indoles and N or C2-substituted indoles has been developed .The reaction was 11 hours efficiently performed in the presence of (10 mmol%) at 35 ℃ in CH2Cl2, obtained in excellent yield. The procedure was characterized by lower amount of inexpensive catalyst mild reaction condition envronmentally benign and similicity.
Key words：ndoles; nitrocellulose; Friedel-crafts alkylation
Ag/TiO2空心微球的制备及光催化杀菌性能的研究
李君建，李巧玲*，李艳，蔚青，石凯
(中北大学 理学院，山西 太原 030051)
摘要：采用一步水热法，以NH4HF2作为形貌控制剂、反应温度为200 ℃、反应时间为12 h，制备锐钛矿型TiO2空心微球，并通过紫外光还原法在TiO2表面沉积单质银。采用SEM、TEM、XRD以及EDS对样品进行表征。以罗丹明B作为模拟污染物表征样品的催化性能。锐钛矿型TiO2空心微球在40 min时降解率达93%，载银二氧化钛复合材料的光催化性能优于纯二氧化钛，当载银量达到2.5%时，光催化活性最佳；在30 min时降解率为98%，采用抑菌圈法表征其杀菌性能，其抑菌圈的直径达16 mm。
关键词：二氧化钛；空心微球；水热法；光催化；载银
中图分类号：O643.3 文献标识码：A 文章编号：0258-3283（2017）
Fabrication of TiO2 Hollow Microspheres Modificated by Ag Nanoparticles：Application in Photocatalysis and Antibacterial LI Jun-jian，LI Qiao-ling*，LI Yan，YU Qing，SHI Kai (College of Science, North University of China, Taiyuan 030051, China)，Huaxue Shiji, 2017, 39(4),
Abstract：TiO2 hollow microspheres were prepared by a one-step hydrothermal strategy using ammonium bifluoride (NH4HF2) as a morphology controlling agent. The hydrothermal synthesis was conducted at 200℃ for 12 h in a vacuum oven. The surface of TiO2 has been modified with Ag nanoparticles induced byultraviolet radiolysis. The prepared samples were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction,energy dispersive spectroscopy. The photocatalytic activity were evaluated by photocatalytic decolorization of Rhodamine B aqueous solution. The best result indicated that the degradation rate of TiO2 had achieved 93% at forty minutes. The photocatalytic activity of Ag-modified TiO2 exceeds that of TiO2，and the degradation rate of Ag-modified TiO2 had achieved 98% at thirty minutes when the mass fraction of silver was 2.5%. Bacteriostatic circle method was introduced to characterize the bactericidal performance and the antibacterial circle diameter had achieved 16 mm.
Key words：titanium dioxide; hollow microspheres; hydrothermal method; photocatalysis; loading sliver
杯[4]芳烃咪唑盐的微波合成
及在氟化反应中的应用
王丹丹，吕早生*，徐珍，唐月娇，王茂志
（武汉科技大学化学工程与技术学院，湖北武汉 430081）
摘要：以杯[4]芳烃为起始原料，首先制得中间体杯[4]芳烃双溴代烷基衍生物，然后经微波辐射和阴离子交换，共得到9种杯[4]芳烃咪唑盐衍生物。化合物的结构与构象经元素分析、IR、1HNMR、19FNMR、31PNMR表征。研究它们在对氯硝基苯的氟化反应中的催化性能以及对K+的萃取性能，结果表明，这9种化合物在氟化反应中的催化效果良好，对氟硝基苯的收率在80.89%~92.67%之间；同时对K+具有较好的萃取效果，其中以化合物25, 27-二[4-(3-甲基咪唑)乙氧基]-26, 28-二羟基-5, 11, 17, 23-四叔丁基杯[4]芳烃六氟磷酸盐的萃取效果最好，萃取率可达75.45%。
关键词：微波辐射；杯[4]芳烃咪唑盐衍生物；氟化反应；阴离子交换
中图分类号：O644.2；O626.23文献标识码：A 文章编号：0258-3283（2017）
Microwave-assisted Synthesis of Calix[4]areneImidazolium Salts and Application in Fluoridation WANG Dan-dan, LV Zao-sheng*, XU Zhen, TANG Yue-jiao, WANG Mao-zhi(College of Chemical Engineering and Technology, Wuhan University of Science and Technology, Wuhan 430081, China)
Abstract: O-alkylated calix [4] arene derivatives were synthesized by using calix[4] arene as a starting material. Nine calix[4]areneimidazolium salts were obtained by microwave-assisted synthesis and anion complexation. The structures were confirmed by elemental analyses, IR, 1HNMR, 19FNMR, 31PNMR.The compounds were used as phase transfer catalysis in the fluoridation of p-chloronitrobenzene. And their extraction properties of K+ was evaluated. The results showed that nine compounds possessed excellent catalytic properties forthe fluoridation.The yields of p-fluoronitrobenzene were between 80.89%~92.67%. And thesecompoundshave good extraction efficiency of K+.25,27-bis[4-(3-methylimidazolium)ethoxy]-26,28-dihydroxy-5,11,17,23-tetra-tert-butylcalix[4]a- -renehexafluorophosphate has the bestextraction performance. The extracted percentage was as high as 75.45%.
Keywords: microwave irradiation; calix[4]areneimidazolium salts; fluoridation; anion complexation
双（三甲基硅基）二亚胺的合成研究
丁可伟，许诚，汪伟，纪晓唐，葛忠学，李陶琦*
（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：以双（三甲基硅基）氨基锂为起始原料，分别与氯化亚砜、三溴化磷反应，合成了双（三甲基硅基）硫二亚胺和双（三甲基）硅胺基-三甲基硅亚氨基磷，然后通过二者间的硫原子迁移反应，合成了标题化合物。通过梯度温度下的减压冷凝，实现了目标产物的分离和纯化，并采用核磁共振、紫外-可见吸收光谱进行了结构表征，根据最大吸收波长计算得其跃迁能为2.53×10-19 J。
关键词：双（三甲基硅基）硫二亚胺；双（三甲基）硅胺基-三甲基硅亚氨基磷；双（三甲基硅基）二亚胺；合成
中图分类号：TJ55；O61 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of Bis(trimethylsilyl)diimine DING Ke-wei, XU Cheng, WANG Wei, JI Xiao-tang, GE Zhong-xue, LI Tao-qi*(State Key Laboratory of Fluorine & Nitrogen Chemicals, Xi’an Modern Chemistry Research Institute, Xi’an 710065, China)
Abstract：Bis(trimethylsilyl)diimine was synthesized by sulfur atom migration between bis(trimethylsilyl)sulfurdiimide and bis(trimethylsilyl)amino-(trimethylsilylimino)phosphin, which were synthesized via reaction of lithium bis(trimethylsilyl)amide with sulfinyl chloride and phosphorus tribromide, respectively. Bis(trimethylsilyl)diimine was separated from the reaction mixture by condensation at high vacuum, the structure of which was characterized by HNMR and UV-Vis absorption spectra. The energy gap of bis(trimethylsilyl)diimine was calculated to be 2.53×10-19 J based on the maximum absorption wavelength.
Key words: bis(trimethylsilyl) sulfurdiimide; bis(trimethylsilyl) amino- (trimethylsilylimino) phosphin; bis(trimethylsilyl) diimine; synthesis
基于卟啉的药物活性化合物的合成研究进展
周勇a,b，黄一波b
（常州工程职业技术学院 a. 科技处，b. 制药学院 江苏省应用酶工程技术开发中心 江苏 常州 213164）
摘要：综述了十几年来基于卟啉的药物活性物质的设计思路和合成方法，重点介绍了基于卟啉的光敏剂及二元活性化合物的合成。同时，展望了卟啉类药物活性化合物合成领域的未来发展趋势。
关键词：卟啉；合成；活性化合物
中图分类号：O62 文献标识码：A 文章编号：0258-3283（2017）
Progress on Synthesis of Active Drug Compounds Based on Porphyrin ZHOU Yonga, HUANG Yi-bob（a. Scientific and Technical Department; b. School of Pharmaceutical and Environmental Engineering, Changzhou Vocational Institute of Engineering, Jiangsu Provincial Applied Enzymatic Engineering Technology Development Center, Changzhou 213164）
Abstract: Design idea and synthesis method have been summarized about the active drug compounds, especially on the synthesis of dual active compounds. In the meanwhile, the development trends on synthesis field of active compounds also have been looked forward in future.
Key word: porphyrin; synthesis; active compounds
G-四联体结构在生物传感器中的应用进展
杨华林*，吴庆华，苏东晓，王允，李利
(长江大学 生命科学学院，湖北 荆州 434025)
摘要：G-四联体结构是由多聚鸟嘌呤序列通过Hoogsteen氢键配对形成的笼式结构。该结构具有独特的化学性质，如可以特异性地和N-甲基卟啉二丙酸 IX (NMM)化合物结合，产生荧光以及具有过氧化物酶活性等。这些性质被科学家用来开发生物传感器，并取得了丰硕的成果。此类传感器大多是通过被检物质引起DNA结构的变化，进而引起荧光信号和过氧化物酶活性变化，最终达到检测的目的。对基于G-四联体结构开发生物传感器检测金属离子、有机大分子、核酸和生物酶等物质的研究进展进行了综述。
关键词：G-四联体结构；生物传感器；N-甲基卟啉二丙酸 IX
中图分类号：O657 文献标识码：A 文章编号：0258-3283（2017）
Progress of G-quadruplexes Application in Biosensors YHANG Hua-lin*, WU Qin-hua, SU Dong-xiao, WANG Yun, LI Li ( College of Life Science, Yangtze University, Hubei 434025,China)
Abstract：G-quadruplexes are formed by the stacking of guanine-rich sequences of DNA composed of four guanines paired by Hoogsteen hydrogen bonding. The structure has the unique chemical properties, such as producing fluorescence by binding with N-methyl mesoporphyrin IX(NMM) and peroxidase activity. These properties are used to develop biosensors and a lot of biosensors are developed. Principles of G-quadruplex-based detection methods involve DNA conformational change caused by the presence of analyte which leads to a decrease or an increase in fluorescence and peroxidase activity of the used probe. It is a potential method in analysis and detection. This work mainly reviewed the technology and advances of G-quadruplexes used in development of biosensors to detect metal ion, organic macromolecule, nucleic acid and biological enzyme.
Key words：G-quadruplexes; biosensors; N-methyl mesoporphyrin IX
白桦酸衍生物的抗肿瘤活性研究进展
张磊，刘来，郑诚月，王杨，王京*
(遵义医学院 药学院，贵州 遵义 563003)
摘要：白桦酸是一种来源于天然植物的羽扇豆烷型五环三萜类产物，具有一定的抗肿瘤活性。近年来，为了增强白桦酸的水溶性以及抗肿瘤活性，研究人员对其结构进行了大量的结构修饰与改造，获得了一些具有潜在抗肿瘤研究价值的白桦酸衍生物。综述了近3年来白桦酸衍生物的抗癌研究进展，以期为白桦酸的结构修饰改造提供有益的帮助。
关键词：白桦酸；衍生物；抗肿瘤活性；研究进展
中图分类号：R284.3 文献标识码：A 文章编号：0258-3283（2017）
Progress in Anticancer Activities of Betulinic Acid Derivatives ZHANG Lei, LIU Lai, ZHENG Cheng-yue, WANG Yang, WANG Jing* (School of Pharmacy, Zunyi Medical College, Zunyi 563003, China)
Abstract：Betulinic acid, a lupine-type triterpene from natural plants, holds potential antineoplastic property. In recent years, to enhance the solubility and anti-proliferative activities of betulinic acid, numerous derivatives with potential anticancer property have been prepared via structure modifications of betulinic acid. In this work, the progress in anticancer activities of betulinic acid derivatives was reviewed, which is helpful for the further modification of betulinic acid.
Key words：betulinic acid; derivative; anticancer activity; research progress
动态反应池-电感耦合等离子体质谱法
分析菊芋中的铬、砷、镉和铅
王丽娟1, 2, 3，孙姗1, 2, 3，吕元琦*3，姚庆强2
（1.济南大学-山东省医学科学院 医学与生命科学学院，山东 济南 250062； 2.山东省医学科学院药物研究所， 山东 济南 250062；3. 德州学院分析测试中心，山东 德州 253023）
摘要：建立了一种动态反应池-电感耦合等离子体质谱法测定菊芋中铬、砷、镉和铅4种有害元素的分析方法。利用该方法分析GBW 07604国家杨树叶标准物质，分析结果与标准值一致。实际样品分析回收率在89% ～ 110%范围内。该方法准确、快速，可用于菊芋及其产品中铬、砷、镉和铅4种元素的分析。
关键词：动态反应池；电感耦合等离子体质谱；菊芋
中图分类号：O657.63 文献标识码：A 文章编号：0258-3283（2017）
Analysis of Chromium, Arsenic, Cadmium and Lead in Jerusalem Artichoke by InductivelyCoupled Plasma Mass Spectrometry with Dynamic Reaction Cell WANG Li-juan1,2,3, SUN Shan1,2,3, LU Yuan-qi*3, YAO Qing-qiang2（1. School of Medical and Life Sciences, University of Jinan-Shandong Academy of Medical Sciences, Jinan 250062; 2. Institute of Materia Medical, Shandong Academy of Medical Sciences, Jinan 250062; 3. Analysis and Testing Centre, Dezhou University, Dezhou 253023)
Abstract: A method was established to determine chromium, arsenic, cadmium and lead in Jerusalem Artichoke by inductively coupled plasma mass spectrometry with dynamic reaction cell. The developed method was applied to analyze GBW 07604 national standard reference material of poplar leaves and the found values were agreeable to those certified. In real sample analysis, the recoveries were in the 89~110% range. This method is correct and fast and can be utilized to the above four harmful elements analysis in Jerusalem Artichoke and its products.
Key words: dynamic reaction cell(DRC); ICP-MS; Jerusalem Artichoke
2, 2′-联吡啶分光光度法测定烟气中二氧化硫
刘彩1a, 2，马卫兴*1b，路源2
(1. 淮海工学院 a. 化学工程学院，b. 药学院，江苏 连云港 222005；
2. 江苏中国科学院能源动力研究中心，江苏 连云港 222005）
摘要：在HAc-NaAc缓冲液中基于亚硫酸根将三价铁离子还原为亚铁离子，后者与2, 2′-联吡啶形成红色配合物，提出了分光光度法测定工业燃煤锅炉排烟中二氧化硫的新方法。在体系最大吸收波长520 nm处二氧化硫浓度在3.2 ～ 40 mg/L范围内符合比尔定律，其回归方程为A = 0.00322c (μg/10 mL)－0.10516，相关系数r为0.9983，表观摩尔吸光系数ε为2.576×103 L/(mol·cm)。将该法用于工业燃煤锅炉排烟中二氧化硫的检测，回收率在95.80% ～ 100.55%之间。该法所用仪器简单，且操作简便快速。
关键词：2, 2′-联吡啶；分光光度法；燃煤锅炉；二氧化硫
中图分类号：O657. 32 文献标识码：A 文章编号：0258-3283（2017）
Determination of Sulfur Dioxide in Flue Gas by 2, 2´-Bipyridyl Spectrophotometry LIU cai1a,2, MA Wei-xing＊1b, LU Yuan2(1. Huaihai Institute of Techology, a. College of Chemical Engineering, b. College of Pharmacy, Lianyungang 222005, China; 2. Energy Research Center, Institute of Engineering Thermophysics, Chinese Academy of Sciences, Lianyungang 222005,China), Huaxue Shiji, 2017, 39(3)
Abstract: A new spectrophotometric method for the determination of sulfur dioxide in flue gas from industrial coal-fired boiler was proposed, based on which ferric ions can be reduced to ferrous ions by sulfite, ferrous ions reacts with 2, 2´-bipyridyl to form a red complex in a medium of HAc-NaAc buffer solution. Beer´s law is obeyed in the concentration range of 3.2 ~ 40 mg/L of sulfur dioxide with its maximum absorption wavelength at 520 nm. The linear regression equation of the calibration was A = 0.00322c (μg/10 mL)-0.10516, with a regression correlation coefficient 0.9983 and the apparent molar absorption coefficient of absorptivity 2.576 × 103 L/(mol·cm). The method was simple, easy to operate, fast and used sulfur dioxide in flue gas from industrial coal-fired boiler, and the coveries were between 95.80% ~ 100.55%.
Key words: 2, 2´-bipyridyl; spectrophotometry; coal-fired boiler; sulfur dioxide
注射称量法配气中的称量线性研究及不确定度评定
周鑫，李志昂，董了瑜，方正*
(中国测试技术研究院，成都 四川 610021)
摘要：采用称量法制备混合气体，当加入的原料组分为微量的液体时，需要使用气密性良好的注射器进行液体组分的转移。通过准确称量注射器转移前后的质量差来计算加入液体组分的质量，因此需要使用高灵敏度、低载荷的天平。选用称量重复性好的质量比较器，使用标准砝码研究了质量比较器的称量线性，建立了注射法加入液体质量的数学模型，评定了该方法的不确定度。使用该方法制备了两瓶氮中苯的混合气体，通过气相色谱进行了一致性分析，对称量过程中引入的不确定度进行了验证。
关键词：液体组分；注射器；称量；不确定度；线性
中图分类号： 文献标识码：A 文章编号：0258-3283（2017）
Weighing Linearity and Uncertainty Evaluation forGravimetric Preparation of Reference Gas Mixture Using Injection Method ZHOU Xin, LI Zhi-ang, DONG Liao-y1, FANG Zheng*(National Institute of Measurement and Testing Technology, Chengdu 610021, China), Huaxue Shiji, 2017, 39(4),
Abstract：As the gas mixtures are prepared gravimetrically and the mass of liquid is normally small, using a gas-tight syringe to inject liquid components into gas mixtures is considered to be a delicate introduction method. The mass difference between the syringe with and without liquid is the introduced liquid mass, so a highly sensitive and low capacity balance is required. In this work, a mass-comparator with brilliant repeatability was chosen to do the weighing process, the weighing linearity was checked using standard mass pieces, and a mathematical description of the injection method was established and its uncertainty was evaluated. Then two binary gas mixture of benzene in nitrogen were prepared and verification was done by GC analyzing.
Keywords：liquid components; syringe; weighing; uncertainty; linearity
QuChERS在线凝胶色谱-气相色谱质谱联用测定水果蔬菜中氟虫腈农药残留
胡贵祥*，夏祥，朱惠芳
（南昌市疾病预防控制中心，江西 南昌 330038）
摘要：建立了在线凝胶色谱-气相色谱-负化学源质谱(GPC-GC/MS)联用法测定水果蔬菜中氟虫腈的残留。采用QuEChERS法对样品净化处理，即乙腈为提取液、无水硫酸钠和N-丙基乙二胺(PSA)为净化剂去除基质干扰，以在线GPC-GC/MS系统进样分析，采用负化学源电离，SIM方式定量检测。回收率为86.0% ～ 108.1%，相对标准偏差(RSD)＜10%，方法的检出限(LOD)和定量限(LOQ)分别为1.5 μg/kg和4.5 μg/kg，已用于水果、蔬菜共220件样品的检测。该方法前处理简单快速、灵敏度高，适应于水果蔬菜中氟虫腈的检测。
关键词：氟虫腈；QuEChERS；凝胶色谱气质联用；负化学电离
中图分类号：O657.63 文献标识码：A 文章编号：0258-3283（2017）
Determination of Fipronil in Vegetables and Fruits by QuEChERS-online Gel Permeation Chromatography Coupled with Gas Chromatography-mass Spectrometry HU Gui-xiang, XIA Xiang, ZHU Hui-fang (Nanchang Center for Disease Control and Prevention, Nanchang 330038)
Abstract: Fipronil residues in vegetables and fruits were determined by online GPC- GC-NCI/ MS. The sample was cleaned up by QuEChERS, extracted with acetonitrile, removed chromatographic interferences by Na2SO4 and PSA, then analyzed by online GPC- GC/ MS with NCI, quantitated by SIM. The recovery rate was 86.0% ~ 108.1%, and the relative standard deviation was less than 10%, the limits of detection ( LOD) was 1.5 μg/kg, while the limits of quantification ( LOQ) was 4.5 μg/kg. The method is simple, convenient, highly sensitive and satisfied for detection of fipronil residues in vegetables and fruits.
Key words: fipronil; QuEChERS; GPC -GC/MS; NCI
比值导数光谱法同时测定食品中山梨酸、苯甲酸和糖精钠的含量
梁奇峰*，侯敬杨，梁文
（嘉应学院 化学与环境学院，广东 梅州 514015）
摘要：利用比值导数光谱法，不经分离同时测定山梨酸、苯甲酸和糖精钠的含量。确定山梨酸、苯甲酸和糖精钠的测定波长分别为237.5、208.5和204.5 nm，测定的线性范围分别为0.50 ~ 4.50、1.60 ~ 14.40和10.00 ~ 90.00 μg/mL，线性相关系数分别为0.9997、0.9996和0.9986，测定的相对标准偏差＜3.3 %（n = 11），加标回收率介于96.4% ～ 104.1%之间。
关键词：比值导数光谱；山梨酸；苯甲酸；糖精钠
中图分类号：O657.3 文献标识码：A 文章编号： 0258-3283（2017）
Determination of Sorbic Acid, Benzoic Acid and Saccharin Sodium in Food by Ratio Derivative Spectrophotometry LIANG Qi-feng*, HOU Jing-yang, LIANG Wen (School of Chemistry and Environmen, Jiaying University , Meizhou 514015, China)
Abstract:A method of determination of sorbic acid , benzoic acid and saccharin sodium in food by ratio derivative spectrophotometry was proposed. The determination wavelengths were selected as 237.5 nm, 208.5 nm and 204.5 nm for sorbic acid, benzoic acid and saccharin sodium, respectively. The linear ranges of determination were 0.50 ~ 4.50 μg/mL, 1.60 ~ 14.40 μg/mL and 10.00 ~ 90.00 μg/mL.The correlative coefficients were 0.9997,0.9996 and 0.9986. The relative standard derivations was less than 3.3% (n =11), the recoveries were in the range of 96.4% ～ 104.1%.
Key words: ratio derivative spectrophotometry; sorbic acid ; benzoic acid ;saccharin sodium
气相色谱-质谱联用测定纺织品及皮革禁用偶氮染料中2,4-二甲基苯胺和2,6-二甲基苯胺
许峰*，李丹
（大加利（太仓）质量技术检测中心有限公司，江苏 苏州 215400）
摘要:采用气相色谱质谱法对纺织品、皮革禁用偶氮染料检测中致癌芳香胺2,4-二甲基苯胺和2,6-二甲基苯胺的测定进行了研究。结果表明，采用DB-35MS中等极性色谱柱，优化气相色谱条件后，能够实现二甲基苯胺的分离。通过保留时间和特征离子丰度比进行定性分析，排除了同分异构体的干扰。该方法简便、快捷，具有良好的准确性和重现性，可有效解决二甲基苯胺的假阳性问题。
关键词:气相色谱质谱；禁用偶氮染料；二甲基苯胺；同分异构体；纺织品；皮革；假阳性；高效液相
中图分类号： 文献标识码：A 文章编号：0258-3283（2017）
Determination of 2,4-Xylidine and 2,6-Xylidine in Banned Azo Colourants Testing of Textiles and Leathers by Gas Chromatography-Mass Spectrometry XU Feng, LI Dan (Dajiali(Taicang)Quality Technology Testing Center, Suzhou 215400, China), Huaxue Shiji, 2017, 39(4),
Abstract: The determination of 2,4-xylidine and 2,6-xylidine in banned azo dyes testing of textiles and leathers was performed by gas chromatography-mass spectrometry. The results showed that the separation of compounds, which was carried out on a medium polarity column DB-35MS,wascompleted by improving the chromatographic conditions. The retention time of quantitative ions and the abundance ratio of characteristic ions were applied to identify each compound so as to prevent the influence of isomers. The method is simple and rapid, which can be validated with respect to high accuracy and good reproducibility, and it also solves the false positive problem in the analysis of xylidine effectively.
Key words: GC-MS; banned azo dyes; xylidine; isomers; textile; leather; false positive; HPLC
利用四氮杂大环配合物催化的Briggs-Rauscher振荡反应测定2,6-二叔丁基-4-甲基苯酚
孙璇璇1，Waqar Uddin1，宋继梅1，胡刚*1，胡林2
(1.安徽大学 化学化工学院，安徽 合肥 230601；
2.华东交通大学 应用化学研究所，江西 南昌 330013)
摘要：报道了一种利用四氮杂大环配合物催化的Briggs-Rauscher(BR)振荡反应测定2,6-二叔丁基-4-甲基苯酚（BHT）的方法，所涉及的体系为H2SO4-KIO3-[NiL](ClO4)2-MA-H2O2，其中L为四氮杂大环5，7，7，12，14，14-六甲基- 1，4，8，11-四氮环杂十四-4，11-二烯，MA表示丙二酸。通过研究发现，在该体系中加入一定浓度的BHT会使得振荡体系的周期、振幅等都发生改变，同时体系会产生抑制时间。当浓度在1.95 × 10-7 ～6.25× 10-6 mol/L范围内，抑制时间与加入的BHT浓度呈很好的二次函数关系;当浓度在6.25× 10-6 ～ 1.56 × 10-5 mol/L范围内，抑制时间与加入的BHT浓度呈很好的线性关系。为了达到更好的定量检测效果，对各组分的浓度进行了优化，使得检测效果达到最佳，最后对反应机理进行了探讨。
关键词：2,6-二叔丁基-4-甲基苯酚；Briggs-Rauscher(BR) reaction；化学振荡；抑制时间
中图分类号：O657.15 文献标识码：A 文章编号：0258-3283（2017）
A New method for Determination of 2,6-Di-tert-butyl-4-methylphenol by Using a Briggs - Rauscher Reaction Catalyzed by a Macrocyclic Nickel (II) Complex SUN Xuan-xuan1, Waqar Uddin1, SONG Ji-mei1, HU Gang*1, HU Lin2 (1.College of Chemistry and Chemical Engineering, Anhui University, Hefei 230601,China; 2. Institute of Applied Chemistry, East China Jiaotong University, Nanchang 330013,China)
Abstract：A new method for the determination of 2,6-di-tert-butyl-4-methylphenol (BHT) was reported. The method relies on the perturbation effect which is caused by different amounts of BHT on the macrocyclic Ni(II) complex -catalyzed Briggs-Rauscher (BR) oscillating reaction. The macrocyclic Ni(II) complex is [NiL](ClO4)2, where L is 5,7,7,12,14,14-hexemethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene. Perturbation of the BHT on the BR system resulted in changes in the oscillation amplitude and period of oscillation, being accompanied by an inhibition time. This method relies on the relationship between inhibition time (tin) and the concentration of BHT. The calibration curve fits a second-order polynomial equation very well when the concentration of BHT is over the range of 1.95× 10-7-6.25 × 10-6 mol/L (r = 0.99905). When the concentration of BHT is over the range of 6.25 × 10-6-1.56 ×10-5 mol/L (r=0.98666), the calibration curve obeys linear equation. The effects of the concentration of components were elucidated. Some aspects of the BHT perturbation mechanism were discussed in detail.
Key words：2,6-di-tert-butyl-4-methylphenol; Briggs-Rauscher(BR) reaction; chemical oscillation; inhibition time
2-取代硫醚-5-[5-(4-氯苯基)吡唑-3-基]-1,3,4-噁二唑类化合物的合成及其荧光性质
王俊岭*，汪小伟，吴峰敏，马军营
（河南科技大学 化工与制药学院，河南 洛阳 471003）
摘要: 以5-(4-氯苯基)-3-吡唑甲酰肼为起始原料，经关环和硫醚化合成了6个新型的标题化合物，其结构经元素分析、IR、1HNMR表征。利用UV以及单光子液体荧光光谱探讨了其光学性质，结果表明目标产物具有良好的荧光性质，最大发射波长在342 ～ 345 nm。
关键词：吡唑；1,3,4-噁二唑；合成； 荧光光谱； 紫外光谱
中图分类号：O626.2 文献标识码：A 文章编号：0285-3283（2017）
Syntheses and Fluorescent Properties of 2-Alkylthio-5-[5- (4-chlorophenyl) pyrazole-3-yl] -1,3,4-oxadiazole Derivatives WANG Jun-ling*, WANG Xiao-wei, WU Feng-min, MA Jun-ying (Chemical Engineering and Pharmaceutics College，Henan University of Science and Technology，Luoyang 471003，China)
Abstract: Six novel 2-alkylthio-5-[5- (4-chlorophenyl)pyrazole-3-yl]-1,3,4-oxadiazole derivatives were synthesized based on the starting material 5-(4-chlorophenyl)pyrazole-3- carbohydrazide by cyclization and thioetherification. The structures of the title compounds were confirmed by elemental analysis, IR,1HNMR. The optical property of these compounds were investigated by UV, single-photon liquid fluorescence spectra. The results indicated the target compounds have good fluorescent properties，and the maximum emission wavelength is in 342 ～ 345 nm range.
Key words: pyrazole; 1,3,4-oxadiazole; synthesis; fluorescent; UV-Vis
1, 3-二氯-2 ,4 ,6-三硝基苯的合成及其硝酯化
孙玲，曹端林*，马文兵，李永祥，王建龙
（中北大学 化工与环境学院，山西 太原 030051）
摘要：以间二氯苯为原料，发烟硫酸和硝酸钾为硝化剂，制备得到标题化合物（DCTNB），以硝酸银为亲核试剂与DCTNB进行亲核取代反应，合成一种新型的含能化合物2, 4, 6-三硝基苯-1, 3-二硝酸酯（TNPDN）。考察了硝化剂用量，反应温度和反应时间等工艺条件对DCTNB 产率的影响。结果表明，较佳的工艺条件为100 mL发烟硫酸，35.5 g硝酸钾，反应温度为160 ℃，反应时间为4 h，产率为75.4%。DCTNB与硝酸银在50 ℃下反应2 h，收率可得32.4%。经红外光谱、核磁共振、元素分析对产物进行结构表征。
关键词：硝化；1, 3-二氯-2, 4, 6-三硝基苯（DCTNB）；2, 4, 6-三硝基苯-1, 3-二硝酸酯（TNPDN）；硝酸盐酯化
中图分类号：O625.6 文献标识码：A 文章编号：0258-3283（2017）
Synthesis and Nitrate Esterification of 1, 3-Dichloro-2, 4, 6-trinitrobenzene SUN Ling, CAO Duan-lin*, MA Wen-bing, LI Yong-xiang, Wang Jian-long（School of Chemical and Environment Engineering, North University of China, Taiyuan 030051, China）
Abstract: 1, 3-Dichloro-2, 4, 6-trinitrobenzene (DCTNB) was prepared with m-dichlorobenzene as the raw material, and fuming sulfuric acid and potassium nitrate as the nitrating agent. Based on DCTNB, a new energetic compound 2, 4, 6-trinitro-1, 3-phenylene dinitrate (TNPDN) was then synthesized via nucleophilic substitution reaction. The effects of nitrating agent, reaction temperature and reaction time on the yield of DCTNB were investigated and the optimal condition was obtained. The results showed that the better synthesis conditions of DCTNB were as follows: fuming sulfuric acid of 100 mL, and potassium nitrate of 35.5 g, DCTNB got the highest yield of 75.4%, under the reaction temperature of 160 ℃and the reaction time of 4 h. The TNPDN can be obtained by mixing DCTNB with silver nitrate, and the yield can reach up to 32.4% at 50 ℃ for 2 h. The structure of product was confirmed by FT-IR, NMR and elemental analysis.
Key words: nitration; 1,3-dichloro-2,4,6-trinitrobenzene(DCTNB); 2,4,6-trinitro-1,3-phenylene dinitrate(TNPDN); nitrate esterification.
Pd@SnO2催化剂的制备及其应用
田园*1，成晟2
（1.绍兴贝斯美化工股份有限公司，浙江 上虞 312369；2.浙江省诸暨中学，浙江 诸暨 311800）
摘要：首先合成了一种具有多孔结构的SnO2，进而以此为金属钯的载体，制备了一种非均相钯催化剂Pd@SnO2，并将其应用于Suzuki偶联反应。研究结果表明，所合成的Pd@SnO2非均相催化剂在Suzuki反应后容易回收，并可被多次使用，同时Pd@SnO2催化剂在Suzuki反应中具有很好的底物普适性。
关键词：非均相Pd催化；Suzuki偶联反应；二氧化锡
中图分类号：0643.32 文献标识码：A 文章编号：0258-3283（2017）
Preparation of Pd@SnO2 Catalyst and Applications TIAN Yuan*1, CHENG Cheng2 (1. Shaoxing BSM Chemical Co., Lit., Shang Yu 312000, China; 2. Zhuji Middle School, Zhuji 311800 )
Abstract：In this work, SnO2 with porous structure was firstly prepared. It was then used as a support for palladium catalyst to achieve a new heterogeneous Pd catalyst Pd@SnO2. Finally, application of Pd@SnO2 in Suzuki cross-coupling reaction was carried out. The results indicated that the present Pd@SnO2 could be easily recovered and exhibited good reusability. Moreover, heterogeneous Pd@SnO2 catalyst possess good substrate scope in Suzuki reaction.
Key words：heterogeneous Pd catalysis; Suzuki cross coupling; tin dioxide
高镁锂比盐湖卤水锂镁沉淀法分离研究
刘凯，梁渠*，庞莎莎，蔡静
（成都理工大学 材料与化学化工学院 化学系，四川 成都 610059）
摘要：采用改进的沉淀法进行锂镁分离，来解决我国青海高镁锂比盐湖卤水中提锂的工艺难题。配制镁锂比为44的模拟卤水（含110 g/L Mg2+、2.5 g/L Li+），以氢氧化钠为主沉淀剂，以吐温-80、聚丙烯酰胺及晶种为辅助沉淀剂，来改进氢氧化镁沉淀的颗粒大小及其形态，使生成的氢氧化镁易于过滤，锂离子吸附损失减小。取10 mL模拟卤水，以50 mL（2 mol/L）的氢氧化钠、0.5 mL吐温-80、0.03 g聚丙烯酰胺、0.03 g晶种构成复合沉淀剂，反应温度为60 ℃，溶液pH 12 ～ 13，则沉淀除镁率达99.9%，锂离子吸附损失率低于2%，过滤速度大大提高。采用扫描电镜、XRD、粒度分布仪、热分析对氢氧化镁晶体的形貌和结构进行了分析，结果表明，辅助沉淀剂的加入能有效地改变氢氧化镁沉淀的颗粒大小及其形态。
关键词：锂；镁；盐湖卤水；沉淀法
中图分类号：TQ131.11 文献标识码：A 文章编号：0258-3283（2017）
Separation of Lithium and Magnesium in Salt Lake Brine with High Ratio of Magnesium to Lithium LIU Kai, LIANG Qu*, PANG Sha-sha, CAI Jing（Department of Chemistry, College of Materials, Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu 610059, China）
Abstract: The improved precipitation is used to solve the problems that lithium is extracted by means of the high ratio of magnesium lithium from brine in Qinghai Salt Lake. In order to improve the size and morphology of magnesium hydroxide precipitate particle, Mg-Li ratio of 44 simulation brine (containing Mg2+ 110g / L; Li+ 2.5g / L) is prepared , and precipitation reaction for magnesium hydroxide was proceeded by using sodium hydroxide as the main precipitating agent , and Tween -80, polyacrylamide regard as auxiliary precipitant，the resulting precipitate of magnesium hydroxide was got with large granular , easy to filter, and lithium ion adsorption loss decreased. The magnesium ion was precipitated with rate of 99.9 % , lithium-ion adsorption loss rate of less than 2%, and the filtration rate is greatly improved when using the simulation brine 10 mL, and the compound precipitation agents which being made up of 50mL 2 mol/L of sodium hydroxide,0.5 mL Twain-80, 0.03g polyacrylamide,0.03g crystal seed , and the reaction conditions such as reaction temperature 60℃, the solution pH 12 ～ 13 .The morphology and structure of magnesium hydroxide crystals were analyzed via SEM, XRD, particle size distribution and thermal analysis. The results show that precipitate particle size and morphology of the magnesium hydroxide could be changed effectively by the addition of an auxiliary precipitant.
Key words: lithium; magnesium; salt lake brine; precipitation
微波下氯化镍催化纤维素制备五羟甲基糠醛
李林，张强，喻蓬秋，乐治平*
(南昌大学 化学学院，江西 南昌 330031)
摘要:以氯化镍为催化剂，氯化锌溶液为溶剂，在微波作用下直接将纤维素转化生成5-羟甲基糠醛（5-HMF）。考察了微波反应功率、微波反应时间、氯化锌浓度、纤维素用量及催化剂与纤维素物质的量比对5-HMF产率的影响。实验结果表明，在微波功率为350 W，微波反应时间为4 min，20 mL 69 wt%氯化锌溶液中，纤维素加入量为0.25 g，n (氯化镍)︰n (纤维素) = 6.42∶1的最佳工艺条件下，5-HMF的产率达22%。
关键词：纤维素；微波；5-羟甲基糠醛；氯化镍；氯化锌
中图分类号：O643 文献标识码：A 文章编号：0258-3283（2017）
Preparation of 5-Hydroxymethylfurfural from Cellulose Catalyzed by NiCl2 under Microwave LI Lin，ZHANG Qiang, YU Peng-Qiu, LE Zhi-Ping*(College of Chemistry, Nanchang University, Nanchang 330031, China)
Abstract: Direct conversion of cellulose into 5-hydroxymethylfurfural (5-HMF) catalyzed by NiCl2 in ZnCl2 solution under microwave was investigated. The effects of microwave power, microwave times, concentrations of ZnCl2, cellulose contents, the molar ratio of NiCl2 to cellulose on the yields of 5-HMF were investigated. The results showed that under the optimum reaction conditions: microwave power was 350w, reaction time was 4 min, 0.25g cellulose resolved in 20 ml 69wt% ZnCl2 solution, n (NiCl2)︰n (cellulose) = 6.42∶1, the yields of 5- HMF was 22%.
Key words: cellulose; microwave; 5-hydroxymethylfurfural; NiCl2; ZnCl2
一种合成氟喹诺酮DW286的新方法
徐志1，黄国成1，张姝2，强敏1，吕早生*1，冯连顺*1,3
(1. 武汉科技大学 化学工程与技术学院，湖北 武汉 430081；2. 武汉谱尼测试有限公司，湖北 武汉 430034；
3. 武汉药明康德新药开发有限公司，湖北 武汉 430411)
摘要：DW286是吉米沙星的甲基衍生物，该品的体内、外抗多种革兰阳性致病菌的活性普遍优于第三代氟喹诺酮。但是，目前对其合成工艺的研究较少，且普遍存在合成步骤较多、污染严重等缺点。本文采用常规方法(甲基化、还原、保护、氧化、肟化、脱保护等)得到了侧链化合物3-甲基-3-(氨甲基)-4-(甲氧亚胺基)吡咯烷盐酸盐，然后将其与萘啶酸母核缩合制备DW286，成功地得到了目标化合物。该合成方法简单易行，具有进一步的研究价值。
关键词：氟喹诺酮；DW286；合成
中图分类号:O629.12 文献标识码:A 文章编号:0258-3283(2017)
A New Method to Synthesize DW286-a Novel Fluoroquinolone Antibacterial Agent XU Zhi1, HUANG Guo-cheng1, ZHANG Shu2, QIANG Min1, LV Zao-sheng*1, FENG Lian-shun*1,3 (1. , Wuhan University of Science and Technology, Wuhan 430081, China; 2.Pony Testing International Group, Wuhan 430034, China; 3.WuXi App Tec, Wuhan 430411, China), Huaxue Shiji, 2017, 39(4),
Abstract: DW286, a methyl analog of gemifloxacin, which shows better in vitro and in vivo activity than the typical third generation fluoroquinolones against commonly pathogens in clinic. However, the current synthetic process of DW286 is rather complex and environmental pollution. From the cyano ketone, DW286 was easily obtained via methylation, reduction, protection, oxidation, oximation, deprotection and condensation. This route is much simpler and valuable.
Key words: fluoroquinolone; DW286; synthesis
6-((2R, 6S)-2, 6-二甲基吗啉代)吡啶-3-胺盐酸盐的合成
刘卓a,b，周志旭a,b，黄筑艳a,b，闫沛沛b ，赵春深*a,b
(贵州大学 a.药学院; b.化学与化工学院 贵州省发酵工程与生物制药重点实验室, 贵州 贵阳 550003)
摘要：标题化合物是一个重要的医药中间体，以(2S, 6R)-2, 6-二甲基-4-(5-硝基吡啶-2-基)吗啉为起始原料，经与Pd/C、氢气和二碳酸二叔丁酯体系反应和氯化氢乙醇脱BOC保护两步反应制备。该合成方法成本低廉、反应条件温和、操作简便、副反应少、目标产物稳定、适合工业化生产，反应总收率为78.45%。
关键词：(2S, 6R)-2,6-二甲基-4-(5-硝基吡啶-2-基)吗啉；6-((2R, 6S)-2,6-二甲基吗啉代)吡啶-3-胺盐酸盐；合成
中图分类号：O626.3 文献标识码：A 文章编号：0258-3283(2017)
Synthesis of 6-((2R,6S)-2,6-dimethylmorpholino)pyridin-3-amine Hydrochloride LIU Zhuoa,c, ZHOU Zhixua,c，HUANG Zhuyana,c，YAN Peipeib,c，ZHAO Chunshen*a,c (a. School of Pharmaceutical Sciences; b.School of Chemistry and Chemical Engineering, Key Laboratory of Guizhou for Fermentation Engineering and Biomedicine, Gui yang 550003, China）
Abstract:6-((2R,6S)-2,6-dimethylmorpholino)pyridin-3-amine hydrochloride, an important pharmaceutical intermediate, was synthesized from (2R,6S)-2,6-dimethyl-4-(5-nitropyridin-2-yl)morpholine which was the main starting material.The synthesis method has the advantages of low cost, mild reaction condition, simple operation, less side reaction, stable product of target product, suitable for industrial production.The total yield was 78.45%.
Key words：(2R,6S)-2,6-dimethyl-4-(5-nitropyridin-2-yl)morpholine; 6-((2R,6S)-2,6- dimethylmorpholino) pyridine -3-amine hydrochloride; synthesis
异海松酰肼系列衍生物的合成与表征
刘娟娟1, 赵振东*1,2, 卢言菊1,2, 王婧1,2
（1. 中国林业科学研究院 林产化学工业研究所 生物质化学利用国家工程实验室 国家林业局林产化学工程重点开放性实验室 江苏省生物质能源与材料重点实验室，江苏 南京 210042；
2. 中国林业科学研究院 林业新技术研究所，北京 100091）
摘要：以异海松酸（IPA）为原料，经过酰氯化和肼解两步合成了中间体异海松酰肼，该化合物进一步衍生化合成了异海松酰胺基（2,5-二甲基）吡咯、异海松酰胺基硫脲、异海松酰胺基苯基硫脲和异海松酰胺基苯磺酰胺（Ⅵ）等4种新型异海松酰肼衍生物，收率53.67 ～ 76.46 %。所得产物经光谱和波谱分析得到确证。
关键词：异海松酸；酰肼；吡咯；硫脲；磺酰胺
中图分类号：O626.9 文献标识码：A 文章编号：0258-3283（2017）
Synthesis and Characterization of Isopimaric Hydrazide Derivatives LIU Juan-juan1, ZHAO Zhen-dong*1,2, LU Yan-ju1,2, WANG Jing1,2（1. National Engineering Lab for Biomass Chemical Utilization, Key and Open Lab on Forest Chemical Engineering SFA, Key Lab of Biomass Energy and Material, Institute of Chemical Industry of Forest Product, CAF,Nanjing 210042 ; 2. Research Institute of Forestry New Technology, CAF, Beijing 100091）
Abstract: Intermediate hydrazine was synthesized via two steps of chloridization and hydrazinolysis from isopimaric acid. Derivatization of intermediate obtained four new hydrazine derivatives of pyrrole, thiourea and sulfonamide, with yields of 53.67 ～ 76.46 %. The synthesized compounds were confirmed by microcopy and spectral studies.
Key words:isopimaric acid; acylhydrazine; pyrrole; sulfourea; sulfonamide
(S)-1-苄基吡咯烷-3-醇的合成新方法
张永创1，王丽丽2a，彭金刚2b，张吉泉*2b，汤磊*2a
（1. 武警贵州省总队医院 药剂科，贵州 贵阳 550005；
（2. 贵州医科大学 a. 医药卫生管理学院，b. 药学院，贵州 贵阳 550004）
摘要：以廉价易得的反式L-羟基脯氨酸为原料，经脱羧、苄基化、甲磺酰化、构型翻转及水解等5步反应得到标题化合物，总收率41.72%，手性纯度大于99%。目标产物经高分辨质谱、核磁氢谱等确证。整条路线收率高、成本低且操作简便，适用于放大生产。
关键词：L-羟基脯氨酸；构型翻转；中间体；合成
中图分类号：R914 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of (S)-1-Benzylpyrrolidin-3-ol ZHANG Yong-chuang1, WANG Li-li2a, PENG Jin-gang2b, ZHANG Ji-quan*2b, TANG Lei*2a (1. Department of Pharmacy, General Hospital of Police in Guizhou province, Guiyang 550005, China; 2. a. School of Medicine and Health Management, b. College of Pharmacy, Guizhou Medical University,Guiyang 550004, China)
Abstract: Using cheap and easily achieved L-hydroxyproline as starting material, the important medicinal intermediate (S)-1-Benzylpyrrolidin-3-ol was prepared via decarboxylation, benzylation, mesylation, configuration reversed and hydrolyzation with a total yield of 41.72% and chiral purity of more than 99%. The compound was confirmed by HR-MS, 1HNMR. This protocol featured by high yield, low cost and easy to operate, and thus suitable for its scale up preparation.
Key words: L-hydroxyproline; configuration reversed; intermediate; synthesis
酰胺类三嗪衍生物的合成
张丽慧*，田秋月，杨颖，刘杰，夏俊丽，朱小勇
（铜仁职业技术学院药学院，贵州 铜仁 554300）
摘要：以氯乙酸乙酯和二甲双胍盐酸盐为原料，经环合反应得到1, 3, 5-三嗪衍生物的母环部分，将所合成的三嗪类似物母核与乙醇胺反应，得到1, 3, 5-三嗪类中间体。再以合成的乙醇胺取代的三嗪类似物为母核，分别与丙磺舒、对位取代四氢吡喃苯甲酸、3, 4, 5-三甲氧基苯甲酸、对甲氧基苯甲酸、3-甲氧基苯乙酸反应，首次得到5个合成的酰胺类三嗪目标化合物。
关键词：三嗪衍生物；合成；结构表征
中图分类号:O626.43 文献标识码:A 文章编号:0258-3283(2017)
Synthesis of Amide Triazine Analogs ZHANG Li-hui*,TIAN Qiu-yue, LIU-Ji, XIA Jun-li, ZHU Xiao-yong ( Shool of Pharmacy , Tongren Polytechnic College, Tongren 554300, China)
Abstract: The intermediate 6-chloromethyl-1,3,5-triazine was synthesized from dimethybiguanide hydrochlorid and ethyl chloroacetate. The desired Intermediate of 1,3,5-triazine analogue was prepared respectively by the reaction of 6-chloromethyl-1,3,5-triazine with 2-aminoethanol. And then five 1,3,5-triazine analogues were prepared by the reactions of acylation, with substituted 1,3,5-triazine and probenecid, para substituted pyran four hydrogen 3,4,5- trimethoxy benzoic acid, benzoic acid, p-methoxybenzoic acid, 3- methoxy phenyl acetic acid.
Key words : triazine; synthesis; structure determination
