肼类推进剂环境检测技术的研究进展
钟秋*，毛亚南，李俊，张学军
(北京航天试验技术研究所，北京 100074)
摘要：环境中的痕量肼、偏二甲肼和甲基肼等肼类推进剂的准确测定是一项重要又较为艰难的工作。综述了国内外在肼类推进剂环境分析检测技术方面的研究进展，如色谱分析法、光度分析法、毛细管电泳法、传感器法等，列举了各种分析技术的方法学特征及在实际样品测定中的应用实例。
关键词：肼类推进剂；环境检测；研究进展
中图分类号： O656.31 文献标识码：A 文章编号：0258-3283（2017）
Progress in Environmental Detection Techniques of Hydrazines Propellant ZHONG Qiu*, MAO Ya-nan, LI Jun, ZHANG Xue-jun (Beijing Institute of Aerospace Testing Technology, Beijing 100074, China), Huaxue Shiji, 2017, 39(3)
Abstract: The accurate determination of trace hydrazine, methylhydrazine and unsymmetrical dimethylhydrazine in environmental samples is an important and difficult task. This review shows the progress in environment detection techniques of hydrazines propellant home and abroad, such as chromatographic analysis, photometric analysis, capillary electrophoretic analysis, sensor and probe method, with illustrates methodological aspects of these separation and detection methods and the application in the determination of real environmental samples.
Key words：hydrazines propellant; environmental detection; research progress
菲并咪唑类席夫碱双核卟啉的合成及性能
邹丽，张卓强，张晓，张学俊*
(中北大学 理学院，山西 太原 030051)
摘要：以9, 10-菲醌、对苯二甲醛、对氟苯甲醛、对甲氧基苯甲醛、对硝基苯甲醛及吡咯等为主要原料，设计合成了双核卟啉（P2-PPI）。通过FTIR光谱、1HNMR和13CNMR表征了其结构，利用UV-Vis光谱、荧光光谱测试了其光谱特征。UV-Vis光谱测试表明，双核卟啉（P2-PPI）Soret带的摩尔消光系数是对应单核卟啉（P1）的2.85倍，光谱吸收范围显著变宽；在浓度测试范围内，双核卟啉P2-PPI的聚集形态未改变。同浓度下，荧光光谱测试表明，双核卟啉P2-PPI中菲并咪唑部分的荧光强度仅为菲并咪唑前驱体的1/3，卟啉单元的荧光强度是单体卟啉的2倍。通过循环伏安法测试并比较了P2-PPI和P1的电化学性质，并结合光化学带隙计算了ELUMO和EHOMO值，分别与TiO2和I-/I3-氧化还原电对能级匹配。
关键词：双核卟啉；菲并咪唑；聚集性；荧光
中图分类号：O626 文献标识码：A 文章编号：0258-3283（2017）
Synthesis and Properties of Phenanthroimidazole Schiff Base Derivatives of Binuclear PorphyrinZOU Li, ZHANG Zhuo-qiang, ZHANG Xiao, ZHANG Xue-jun*(College of Science, North University of China, Taiyuan 030051, China), Huaxue Shiji, 2017, 39(3)
Abstract：The target binuclear porphyrin P2-PPI was synthesized by raw materials of 9, 10-phenanthrenequinone, 4-fluorobenzaldehyde, 1, 4-phthalaldehyde, anisic aldehyde, 4-nitrobenzaldehyde, and pyrrole. The structures of all compounds were characterized by IR and 1HNMR, and the spectral characteristics of P2-PPI is studied by UV-Vis and fluorescence spectra. Results showed that molar extinction coefficient of the target binuclear porphyrin P2-PPI was 2.85 times as high as the mononuclear porphyrin P1, and occupied broader spectral absorption range than P1. And in the range of concentration test, the aggregation behaviors of P2-PPI remained unchanged. Fluorescence spectrum indicated that the intensity of the phenanthrenequinone unit of P2-PPI was only two-third smaller than phenanthrenequinone precursor, and the intensity of theporphyin unit of P2-PPI was 2 times as high as mononuclear porphyrin. The electrochemical properties of P2-PPI and P1were tested and compared with cyclic voltammetry. Also, the LUMO and HOMO energy levels were calculated combined with photochemical band gap, matching with the conductive band of TiO2 and the redox energy level of I-/I3-, respectively.
Key words：binuclearporphyrin; phenanthroimidazole; aggregation behaviors; fluorescence
中氮茚并喹啉二酮衍生物的合成、表征及抗菌活性
胡翥，巫锡伟，李龙，陈芸芸，安林坤*
(中山大学 药学院，广东 广州 510006)
摘要：以自制的6, 7-二氯喹啉-5, 8-二酮为原料，经一步反应合成了目标化合物9-氯-5, 12-二酮-5, 12-二氢中氮茚并[2, 3-g]喹啉-6-甲酸乙酯，并通过1HNMR、HRMS以及X-射线单晶衍射对其结构进行表征。活性测试结果表明，该化合物对革兰氏阳性菌具有选择性抑制作用，对耐甲氧西林金黄色葡萄球菌（MRSA）的最小抑菌浓度（MIC）为1 μg/mL，优于阳性对照药物万古霉素。通过化合物与DNA促旋酶的分子对接实验进一步说明了化合物可能的作用机理。
关键词：中氮茚并喹啉二酮；合成；表征；抗菌
中图分类号：R914.5 文献标识码：A 文章编号：0258-3283(2017)
Synthesis, Characterization and Antimicrobial Activity of Indolizinoquinoline-5, 12-dione Derivatives HU Zhu, WU Xi-wei, LI Long, CHEN Yun-yun, AN Lin-kun* (School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, China), Huaxue Shiji, 2017, 39(3)
Abstract：Target compound of ethyl 9-chloro-5, 12-dioxo-5, 12-dihydroindolizino[2, 3-g]quinoline-6-carboxylate was one-step synthesized from the homemade 6, 7-dichloroquinoline-5, 8-dione. The atomic structure was characterized using 1HNMR, HRMS, and X-ray single crystal analysis. Antimicrobial activity assessment indicates that the compound exhibits selective inhibition against gram-positive bacterial strains. Meanwhile, its minimum inhibition concentration (MIC) against methicillin-resistant Staphylococcus aureus (MRSA) is 1.0 μg/mL, which is superior to that of positive control: vancomycin. Furthermore, we proposed the inhibition mechanism via docking the compound to DNA gyrase.
Key words：indolizinoquinoline-5, 12-dione; synthesis; characterization; antimicrobial
水相中非催化芳胺的高选择性双苄基化
王锐，魏小红，杜正银*
（西北师范大学 化学化工学院，甘肃 兰州 730070）
摘要：在无添加催化剂、乙醇和水作混合溶剂的碱性体系中，苯胺类化合物和苄基卤化物经过反应，高选择性地得到了双苄基化产物。苯胺类化合物转化为各类叔胺且产率高达99%。该反应具有无需添加催化剂、反应时间短、产率高、绿色经济以及底物范围广等优点。同时根据反应结果提出了该反应可能的反应机理。
关键词：苯胺；苄基卤化物；双苄基化反应；水相反应；绿色化学
中图分类号：O625.6 文献标识码：A 文章编号：0258-3283（2017）
Catalyst-free and Highly Selective N, N-Dibenzylation of Anilines in Aqueous Phase WANG Rui, WEI Xiao-hong, DU Zheng-yin*(College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, China), Huaxue Shiji, 2017, 39(3)
Abstract: A highly selective dialkylation reaction of anilines with benzyl halides was developed in aqueous alkaline alcohol solution without catalysts. Various symmetrical tertiary amines could be obtained using the above-mentioned synthetic strategy with yields up to 99.0%. The advantages of this protocol include short reaction duration, high yields of targeted products, safe aqueous medium, no use of catalysts, and wide acceptance of reactants. A rational mechanism was also proposed based on the facts of experimental observations.
Key words: aniline; benzyl halides; dibenzyl reaction; aqueous reaction; green chemistry
含苯并噻唑环的硫脲类化合物的合成、晶体结构及抑菌活性
曾振芳*，黄秋萍，韦友欢，黄秋婵，王强
(广西民族师范学院 化学与生物工程系 广西高校桂西南特色植物资源化学重点实验室培育基地，广西 崇左 532200)
摘要：以取代苯甲酸为原料合成了一系列含苯并噻唑环的硫脲类化合物，其中有8个为新型化合物，化合物结构经元素分析、IR、1HNMR表征。采用X-射线单晶衍射测定了N-(2-溴苯甲酰基)-N′-(4-甲基苯并噻唑-2-基)硫脲的晶体结构，该晶体属于三斜晶系，P
空间群，晶胞参数a = 0.74168(7) nm，b = 1.08871(10) nm，c = 1.20682(11) nm，α = 103.504(8)°，β = 106.632(8)°，γ = 108.278(8)°，V = 0.82874(13) nm3，Dc=1.628 Mg/m3，μ = 2.738 mm-1，Z = 2，F(000) = 408，最终偏差因子R1 = 0.0304，wR2 = 0.0756 [I＞2 σ(I)]，S = 1.048，CCDC号为1471387。选择广西主要经济作物(水稻、甘蔗、番茄、木薯、龙眼、荔枝)中常见的病原菌，对目标化合物进行室内抑菌活性测试，实验结果发现该类化合物具有一定的抑菌活性。
关键词：2-氨基-4-甲基苯并噻唑；合成；晶体；抑菌活性
中图分类号： O641.4 文献标识码：A 文章编号：0258-3283（2017）
Synthesis, Crystal Structure and Antibacterial Activity of Thiourea Derivatives with Benzothiazole-ring ZENG Zhen-fang*, HUANG Qiu-ping, WEI You-huan, HUANG Qiu-chan, WANG Qiang (Guangxi Colleges and Universities Key Laboratory Breeding Base of Chemistry of Guangxi Southwest Plant Resources, Department of Chemistry and Biological Science, Guangxi Normal University for Nationalities, Chongzuo 532200, China), Huaxue Shiji, 2017, 39(3)
Abstract: In this work, a series of thiourea derivatives with benzothiazole-ring were synthesized from substituted benzoic acid, eight of them are new compounds. The structures had been confirmed by elemental analysis, IR and 1HNMR. The crystal structure of the compound 1 was determined by X-ray diffraction analysis, the crystal belongs to the triclinic system, space group P, unit cell dimensions with a = 0.74168(7) nm, b = 1.08871(10) nm, c = 1.20682(11) nm, α = 103.504(8)°, β = 106.632(8)°, γ = 108.278(8)°, V = 0.82874(13) nm3, Dc = 1.628 Mg/m3, μ = 2.738 mm-1, Z = 2, F(000) = 408, the final R1 = 0.0304, wR2 = 0.0756 [I＞2σ(I)], S = 1.048, CCDC: 1471387. The common pathogenic bacterias on the main economic crops (rice, sugarcane, tomatoes, manioc, longan, litchi) in Guangxi province was choosed to proceed antibacterial activity test, the result showed that the compounds exhibited certainly antibacterial activity.
Key words: 2-amino-4-methylbenzothiazole; synthesis; crystal; antibacterial activity
活性白土/壳聚糖吸附剂对果汁的澄清作用研究
徐启杰a, 孙楠*b, 李伟a, 潘庆才a, 李晓玉a
（ 黄淮学院 a. 化学化工系；b. 生物工程系, 河南 驻马店 463000）
摘要：利用简便的方法制备了活性白土/壳聚糖吸附剂，并通过红外光谱(FTIR)、热重(TG)、X-射线衍射(XRD)和透射电镜对所制备的吸附剂进行表征。结果表明，壳聚糖嵌入到活性白土的片层结构中，形成了稳定的复合结构，进而增大了活性白土的片层间距，有利于提高活性白土的吸附性能。活性白土/壳聚糖吸附剂作为吸附剂，可以对草莓汁、西瓜汁、橙汁均具有较好的澄清效果。对草莓汁的澄清的条件为：吸附剂用量为0.02 g，35 ℃、吸附时间3 h、pH 5，澄清度为69.36%；对西瓜汁的澄清条件为：吸附剂用量0.02 g，25 ℃、吸附时间1 h，pH 6，澄清度达到98.42%；对橙汁的澄清条件为：吸附剂用量为0.02 g，30 ℃、吸附时间0.5 h，pH 5.6，澄清度为61.08%。
关键词：活性白土；壳聚糖；复合吸附剂；澄清；果汁
中图分类号：O611.6 文献标识码：A
Clarified Effect of Activated Clay/Chitosan Composite on Juice XU Qi-jie a, SUN Nan *b, LI Wei a, PAN Qing-cai a, LI Xiao-yu a (a. The Department of Chemistry and Chemical Engineering; b. The Department of Biological Engineering, Huanghuai university, Zhu madian 463000, China)
Abstract: Activated clay/chitosan composite was prepared readily. As-obtained composite was characterized by infrared spectrometer (FTIR), thermogravimetric analyzer (TG), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The results showed that chitosan successfully embedded in the lamellar structure of activated clay thereby increasing the lamellar distance, which is beneficial to form stable composite structure between activated clay and chitosan. Activated clay/chitosan composites indicated perfect adsorption rate on the strawberry juice, watermelon juice, orange juice. Besides, the adsorption rate was 69.36% for strawberry juice in the condition of 0.02 g activated clay/chitosan composites, 35 ℃, 3 h, and pH 5. Watermelon juice was adsorbed by activated clay/chitosan complex, founding that the best adsorption conditions were that the dosage of activated clay/chitosan composites was 0.02 g, 25 ℃, the adsorption time of 1 h and pH 6, and the maximum adsorption rate reached to 98.42%. Moreover, for adsorption of orange juice, the condition contained that activated clay/chitosan composites of 0.02 g, 30 ℃, 0.5 h, pH 5.6, the adsorption rate was 61.08%.
Key words: activated clay; chitosan; composite adsorbent; clarify; juice
异靛蓝衍生物生物活性的研究进展
张磊，陈凡，张泽国，林娅，朱心玲，王京*
(遵义医学院 药学院，贵州 遵义 563003)
摘要:异靛蓝是一种重要的双吲哚类天然产物，具有多种生物活性。为了增强异靛蓝的生物活性和水溶性，近年来人们对其结构进行了大量的修饰和改造，合成了一些活性较强的衍生物。对近年来异靛蓝衍生物的生物活性及构效关系研究进行了综述。
关键词:异靛蓝；衍生物；生物活性
中图分类号：R284.3 文献标识码：A 文章编号：0258-3283（2017）
Progress in Biological Activities of Isoindigo Derivatives ZHANG Lei, CHEN Fan, ZHANG Ze-guo, LIN Ya, ZHU Xin-ling, WANG Jing* (School of Pharmacy, Zunyi Medical College, Zunyi 563003, China)
Abstract: Isoindigo is an important natural bisindoles with many biological activities. To enhance its activity and water solubility, numerous modifications of isoindigo have been carried out in recent years, and some isoindigo derivatives with better bioactivities have been prepared. This work will review the progress in biological activities and structure-activity relationships of isoindigo derivatives.
Key words：isoindigo; derivatives; biological activities
绿原酸提取纯化方法的研究进展
孙阳a，黄和b，胡燚*a
(南京工业大学 a. 生物与制药工程学院，b. 药学院 材料化学工程国家重点实验室，江苏 南京 210009)
摘要：绿原酸是植物体内一种重要的次生代谢产物，作为一种活性物质广泛存在于高等双子叶植物和蕨类植物中。由于其具有抑菌消毒、活血降压、抗氧化、防衰老等功效，因而成为生物活性物质研究的热点之一。从绿原酸的提取和分离纯化两方面进行综述，并就传统提取法、物理场提取法和生物酶解法3种方法进行重点阐述，旨在为绿原酸的应用提供参考和依据。
关键词：绿原酸；提取方法；分离纯化
中图分类号：TS202 文献标识码：A 文章编号：0258-3283（2017）
Progress on Extraction and Purification of Chlorogenic Acid SUN Yanga, HUANG Heb, HU Yi*a (a. College of Biological and Pharmaceutical Engineering, b. State Key Laboratory of Chemical Engineering Material, College of Pharmacy, Nanjin Technology University, Nanjin 210009, China), Huaxue Shiji, 2017, 39(3)
Abstract: Chlorogenic acid is an important secondary metabolic product in plant, it is wide existed in dicotyledonous plants and ferns as a kind of biological active substance. Due to it′s antibacterial disinfection, blood pressure lowering, anti-oxidation, anti-aging and so on, it has become one of popular topics in the study of bioactive substances. This work describes extraction, separation and purification methods of chlorogenic acid, focuses on traditional extraction, the physical field extraction, enzyme hydrolysis and aims to provide reference and basis for the utilization of chlorogenic acid.
Key words: chlorogenic acid; extraction; separation and purification
固相萃取-气相色谱法水果、蔬菜中氯丹的测定
郑俊旦，朱杰丽
（浙江省林产品质量检测站 国家林业局林产品检验检测中心（杭州），浙江 杭州 310023）
摘要：建立一种简单、灵敏的水果、蔬菜中氯丹残留量的气相色谱检测方法。样品用乙腈提取，经Florisil（弗罗里硅土）SPE小柱净化，由配有ECD检测器气相色谱（GC-ECD）进行测定。该方法中水果、蔬菜氯丹检出限为0.0002 mg/kg，工作曲线在0.001 ～0.08 ug/mL范围内呈良好的线性关系。在该线性范围内，苹果、柿子、西红柿和鲜笋中回收率为82.6% ～ 93.1%。
关键词：固相萃取；氯丹；残留分析；气相色谱
中图分类号：O657.7 文献标识码：A
Determination of Chlordane in Fruit and Vegetable via Solid Phase Extraction and Gas Chromatography ZHENG Jun-dan1, ZHU Jie-li2（Zhejiang Forestry Product Quality Testing Station, Hangzhou 310023, China）
Abstract:The establishment of the amount of gas chromatography detection method is simple sensitive chlordane residues in fruit, vegetables. Samples were extracted with acetonitrile, then Florisil (Florisil) and purified with SPE column. Gas chromatography equipped with ECD detector (GC-ECD) were measured. The detection limit of chlordane in the fruit and vegetables was 0.0002 mg/kg. A good linear relationship was obtainedat 0.001 ~ 0.08 ug/mL range. The recovery was 82.6% ~ 93.1% in the linear range.
Key words: solid phase extraction; chlordane; residue analysis; gas chromatography
高效液相色谱法测定人参提取物中的苯并(α)芘
田芳洁*，康明芹，曹海微，李荣荣，刘泽朋，陈明岩
（吉林出入境检验检疫局，吉林 长春 130062）
摘要：建立了人参提取物中苯并(α)芘残留量的高效液相色谱分析方法。样品加水浸泡，用正己烷液液萃取，提取液减压蒸干，C18色谱柱分离，以乙腈-水为流动相，外标法定量。结果表明，苯并(α)芘在1.0 ~ 100.0 µg/L范围内线性良好，相关系数R为0.9999，平均加标回收率为85.2% ~ 96.7%，相对标准偏差为7.1% ~ 11.2%。方法的定量限为1.0 μg/kg。该方法简单快速、灵敏度高、重现性好，能满足人参提取物中苯并(α)芘残留量定量分析的要求。
关键词：液液萃取；高效液相色谱；苯并(α)芘；人参提取物
中图分类号：O657.72 文献标识码：A 文章编号：0258-3283（2017）
Determination of Benzo(a) Pyrene in Ginseng Extract via High Performance Liquid Chromatography TIAN Fang-jie*，KANG Ming-qin，CAO Hai-wei，LI Rong-rong, LIU Ze-peng, CHEN Ming-yan（Jilin Entry-Exit Inspection and Quarantine Bureau,Changchun 130062,China）
Abstract：A method for the determination of benzo(α) pyrene in ginseng extract was developed using high performance liquid chromatography. The samples were soaked with water, extracted with n-hexane, evaporated in vacuum, separated by C18 column with acetonitrile and water as mobile phase and quantitative by external standard method. The results showed that benzo(α) pyrene had a good linear relationship in the range of 1.0 ~ 100.0 μg/L and the relative coefficient was 0.9999．The spiked recoveries was 85.2% ~ 96.7 % and the relative standard deviations was 7.1% ~ 11.2%.The limit of quantitation of the method was 1.0 μg/kg. The simple and rapid method with good reproducibility can be used for the determination of benzo(α) pyrene in ginseng extract．
Key words: liquid-liquid extraction; HPLC; benzo(α) pyrene; ginseng extract
离子色谱法测定甲基亚磺酸钠中的氯离子和硫酸根离子
闫春辉a，徐凌云*a，马泓冰 a，张勇a，孙宏枚b
（苏州大学 a. 分析测试中心，b. 材料与化学化工学部，江苏 苏州 215123）
摘要：建立了抑制电导检测离子色谱法同时测定甲基亚磺酸钠中氯离子和硫酸根离子的方法。Cl－和SO42－分别在0.2 ～ 25 mg/L(r = 0.9999)和0.1 ～ 10 mg/L (r = 0.9996)浓度范围内线性关系良好，甲基亚磺酸钠中Cl－和SO42－的方法平均回收率分别为102% (RSD为0.36%)和101% (RSD为0.61%)，检出限分别为0.011和0.014 mg/L。该方法具有良好的线性、检出限低、操作简便、可靠，可作为甲基亚磺酸钠中的Cl－和SO42－质量控制方法。
关键词：离子色谱法；甲基亚磺酸钠；Cl－；SO42－
中图分类号： 文献标识码：A 文章编号：0258-3283（2017）
Determination of Cl- and SO42- in Sodium Methanesulfinate by Ion Chromatography YAN Chun-huia，XU Ling-yun *a，MA Hong-bing a，ZHANG Yonga，SUN Hong-meib ( a. Analysis and Test Center ; b. Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China )
Abstract: To establish a method for the simultaneous determination of Cl- and SO42- in sodium methanesulfinate by ion chromatography with suppression conductivity detector. The calibration curve was linear in the range of 0.2～25 mg/L(r = 0.9999) and 0.1～10 mg/L (r = 0.9996) for Cl- and SO42- rspectively. The mean recovery of Cl- and SO42- were 102% (RSD of 0.36%) and 101% (RSD of 0.61 %) respectively. Detection limits for Cl- and SO42- were 0.011 mg/L and 0.014 mg/L respectively. This method has the benefits of good linear range, low detection limit, easy operation and reliable. It can be used as the quality control method of Cl- and SO42- in sodium methanesulfinate.
Key words: ion chromatography; sodium methanesulfinate; Cl-; SO42-
新疆不同产地沙枣叶微量元素测定及主成分分析
巴依尔太，余志银，郭童童，孙芸*
（新疆医科大学 中医学院，新疆 乌鲁木齐 830011）
摘要：为了测定新疆不同产地沙枣叶中Li、Na、Mg、K、Al、Ca、Fe、Cr、Mn、Cu、Zn、As、Se、Sr、Ag、Cd、Hg和Pb 18种微量元素的含量。利用微波消解法对沙枣叶样品进行前处理，采用ICP-MS测定沙枣叶中18种微量元素的含量，运用主成分分析法并结合SPSS软件对测定结果进行综合分析。结果显示，检测到新疆不同产地沙枣叶中Na、Mg、K、Ca、Fe、Mn、Zn、Sr、Se的含量相对较高，未检测到重金属元素Hg、Ag，这18种元素的加标回收率为95.8% ～ 102.3%，相对标准偏差＜3.3%。最终主成分分析选出9个主因子，得出沙枣叶的特征元素为Mg、Al、Fe、Cu、Cd、K、Se。喀什地区沙枣叶品质总体高于其他7个产区。本方法能够准确、可靠地测定沙枣叶中微量元素的含量，具有较高灵敏度，可用于沙枣叶中微量元素的测定，为沙枣叶的深度开发利用以及产区考核提供参考依据。
关键词：新疆沙枣叶；ICP-MS；微量元素；主成分分析
中图分类号：R284.2 文献标识码：A 文章编号：0258-3283（2017）
Determination of Trace Elements and Principal Components Analysis in Elaeagnus angustifolia L. Leaves from Different Growing Areas of Xinjiang Bayiertai, YU Zhi-yin, GUO Tong-tong, SUN Yun*（College of TCM, Xinjiang Medical University, Urumqi 830011, China）
Abstract: The contents of eighteen kinds of trace elements, Li, Na, K, Mg, Al, Ca, Fe, Cr, Mn, Cu ,Zn, As, Se, Sr, Ag, Cd, Hg and Pb, in Elaeagnus angustifolia L. leaves in different regions of Xinjiang, were determined by inductively coupled plasma mass spectrometry (ICP-MS) . Elaeagnus angustifolia L. leaves were dealt with microwave digestion and 18 trace elements was analyzed by ICP-MS. The data were analyzed by the principal components analysis in combination with SPSS statistical software．The results showed that the contents of Na，Mg，K，Ca，Fe，Mn，Zn，Sr，and Se were abundant, and the contents of Hg,Ag and other harmful element are not detected. The recovery is 95.8% ～ 102.3%, and the RSD is less than 3.3%. Nine principal components were extracted from the original data. The principal component analysis results showed that Mg, Al, Fe, Cu, Cd, K, and Se may be the characteristics elements of Elaeagnus angustifolia L. leaves, especially, the kashi region Elaeagnus angustifolia L. leaf quality is outstanding. This is a simple and rapid method with good accuracy and sensibility. So, it is suitable for the determination of trace elements in Elaeagnus angustifolia L. leaves and can provide some theoretical basis for better development and utilization of the resource．
Key words: Elaeagnus angustifolia L. leaf；ICP-MS；trace elements；principal component analysis
胶体磷[32P]酸铬注射液无菌检查及核纯度检查方法研究
张云*，孙祥敏，张文在，王晓静，张先
(原子高科股份有限公司，北京 102413)
摘要：对胶体磷[32P]酸铬注射液的无菌检查方法和核纯度检查方法进行研究，以对其无菌检查方法进行验证并建立核纯度检查方法。结果表明，可采用直接接种法，接种0.2 mL供试品至7.5 mL培养基管进行该产品的无菌检查；在核纯度检查方法方面，对放射性吸收套进行设计加工，改变了主核素和杂质核素测量比，用高纯锗γ谱仪测量出γ杂质的活度，用活度计测量出32P活度，根据32P和杂质核素的活度计算出32P核纯度。检查方法经验证准确可靠，简单易行，为产品的质量控制提供保证。
关键词：胶体磷[32P]酸铬注射液；无菌检查；核纯度检查
中图分类号： 文献标识码：A 文章编号：0258-3283（2017）
Sterility and Radionuclide Purity Examination Methods of Colloidal Chromium Phosphate[32P] Injection ZHANG Yun*1, SUN Xiang-min, ZHANG Wen-zai,WANG Xiao-jing, ZHANG Xian (HTA CO.LTD, Beijing 102413, China)
Abstract：The sterility and radionuclide purity analytical methods of colloidal chromium phosphate [32P] injection were investigated to validate the sterility examination and establish the radionuclide purity analytical method. It was indicated that the direct inoculation method can be used with 0.2 mL samples inoculated into 7.5 mL medium to conduct the sterility analysis. Regarding the radionuclide purity test, radioactive absorbing sleeve was designed and processed, which changed the measurement ratio of main nuclide and impure nuclide. In the work, the activity of γ impurities was measured by the highly purified germanium gamma spectrometer, followed by the analysis of the 32P activity using the activity meter. The radionuclide purity of 32P was eventually calculated based on the activity of 32P and impure nuclide. The analytical method is revealed to be conducted to ensure good quality control of the product.
Key words：colloidal chromium phosphate [32P] injection; sterility examination; radionuclide purity test
苯氧乙醇标准物质的纯度分析方法及不确定度评定
顾玲玲*，田玉平，吴建军，朱丽娜，刘悦
（上海市计量测试技术研究院，上海 201203）
摘要：采用质谱（MS）和核磁共振谱（NMR）对原料苯氧乙醇进行定性分析，优化并建立了液相色谱法及气相色谱法测定苯氧乙醇纯度为99.3%。以甲醇为基体溶液，采用重量-容量法制备苯氧乙醇标准物质。以液相色谱（紫外法、示差法）两种方法进行定值，并做了均匀性检验和稳定性跟踪。建立不确定度评定方法，标准物质特性值为99.3（±1.1）μg/mL（k = 2）。苯氧乙醇标准物质具有溯源性和准确性，对于化妆品中防腐剂苯氧乙醇含量的准确测定及监控具有重要意义。
关键词：苯氧乙醇；标准物质；均匀性；稳定性；不确定度
中图分类号：O625.34 文献标识码：A 文章编号：0258-3283（2017）
Certification and Uncertainty Evaluation of Phenoxyethanol Purity Certified Reference Material GU Ling-ling, TIAN Yu-ping, WU Jian-jun, ZHU Li-na, LIU-Yue (Shanghai Institute of Measurement and Testing Technology, Shanghai 201203, China), Huaxue Shiji, 2017, 39(3)
Abstract: GC-MS and NMR were used to confirm the structure of phenoxyethanol. HPLC and GC were used to determine the purity of phenoxyethanol, and the purity was revealed to be 99.3%. Phenoxyethanol reference was prepared in methanol according to weight-capacity method. Ultraviolet and differential spectrophotometry were used for certificating the value, the homogeneity and stability. The uncertainty of this evaluation method was established. The property value of phenoxyethanol was 99.3(±1.1) μg/mL (k = 2). The standard phenoxyethanol reference prepared in this study was traceable and accurate, and it can be used as a standard reference for preservative analysis of cosmetics.
Key words: phenoxyethanol; reference material; homogeneity; stability; uncertainty
监测水质用多组分挥发性有机物标准样品的研究
杨刚1，姜洋2，鲁炳闻1，王伟1，田文1，房丽萍*1
(1. 环境保护部标准样品研究所 国家环境保护污染物计量和标准样品研究重点实验室，北京 100029；
2. 北京化工大学 理学院，北京 100029)
摘要：研制了配套国家标准、适合我国水质环境监测需要的多组分挥发性有机物标准样品。经纯度验证后，采用称量法制备、分层随机抽样法抽样，单因素方差分析法评价样品均匀性。在室温、4 ℃冷藏和-18 ℃冷冻3种保存条件下观察样品稳定性，线性模型进行稳定性评价。结果表明，制备的多组分挥发性有机物标准样品具有良好的均匀性和稳定性，量值准确可靠，可用于环境监测中绘制标准曲线等相关工作。
关键词：挥发性有机物；标准样品；制备；不确定度
中图分类号： X832 文献标识码：A 文章编号：
Development of Reference Material for Analysis and Calibration ofr Volatile Organic Compounds YANG Gang1, JIANG Yang2, LU Bing-wen1, WANG Wei1, TIAN Wen1, FANG Li-ping*1(1. State Environmental Protection Key Laboratory of Environmental Pollutant Metrology and Reference Materials, Institute for Environmental Reference Materials, Ministry of Environmental Protection, Beijing 100029；2. School of Science ,Beijing University of Chemical Technology, Beijing 100029, China)
Abstract: This work described a method of developing reference materials (RM) of 28 kinds VOCs mixture in methanol for supporting national standards and environmental monitoring. The preparation of reference material used weighing method after purity was verified. The samples were selected by a random stratified scheme covering the whole batch, and a good homogeneity was obtained by single factor variance analysis. At room temperature, 4 degrees below zero and 20 degrees below zero, stability was value with linear model. The results indicated that the homogeneity and stability was fine and value was accurate, which meant the material could be used in drawing standard curve and assurance of environmental monitoring and other relative works.
Key words: volatile organic compounds (VOCs); reference material (RM); preparation; uncertain
基于萘酰亚胺为发光团的Zn2+荧光探针的合成与研究
文少白，李娜，季玉祥，于春伟*
(海南医学院 热带医学与检验医学院，海南 海口 571199)
摘要：设计合成了一种基于萘酰亚胺为发光团的Zn2+荧光探针。相对于其他常见金属离子，该探针对Zn2+具有较好的选择性。探针对Zn2+的识别机理为Zn2+的加入导致C=N异构化受阻，荧光增强。探针对Zn2+的线性检出范围为0.3 ～ 2 μmol/L，检出限为0.15 μmol/L。
关键词：荧光探针；萘酰亚胺；Zn2+
中图分类号：O622.7 文献标识码：A 文章编号：0258-3283（2017）
Synthesis and Characterization of a Zn2+-Selective Fluorescent Probe Based on NaphthalimideWEN Shao-bai, LI Na, JI Yu-xiang, YU Chun-wei* (School of Tropical and Laboratory Medicine, Hainan Medical University, Haikou 571199, China), Huaxue Shiji, 2017, 39(3)
Abstract：In this study, an aphthalimide fluorescent probe for selectively detecting Zn2+ was designed. Compared to other metal ions, our proposed probe showed high selectivity to Zn2+. The “off-on” enhancement of fluorescent of probe was due to the rotation restriction of C=N bonds in naphthalimide caused complexed with Zn2+. The linear range of probe to Zn2+ was 0.3 ～ 2.0 μmol/L with a detection limit of 0.15 μmol/L.
Key words：fluorescent probe; naphthalimide; Zn2+
丙二醇甲醚气固相催化合成甲氧基丙酮
陈涛，宁斌科*，林双政，王列平，杨建明
（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：以丙二醇甲醚为原料，利用共沉淀法制备的Cu-ZnO为催化剂，在固定床反应器中催化脱氢合成甲氧基丙酮。考察了催化剂制备工艺和反应条件对催化活性的影响，并对催化剂的稳定性进行了研究。结果表明，催化剂最佳制备条件是：铜锌物质的量比为0.5，沉淀温度为55 ℃，55 ℃老化1 h，采用硝酸钠改性，400 ℃焙烧4 h。催化剂最佳反应工艺：240 ℃下还原4 h，反应温度为250 ℃，液空时速为40 mL/h，氮载气速度为150 mL/min。催化剂在120 h内稳定性良好。
关键词：丙二醇甲醚；甲氧基丙酮；铜-氧化锌-三氧化二铝；催化剂制备
中图分类号：O623.4 文献标识码：A 文章编号0258-3283(2017)
Synthesis of Methoxyacetone from Propylene Glycol Monomethyl Ether by Gas-solid Catalytic Reaction CHEN Tao, NING Bin-ke*, LIN Shuang-zhen, WANG Lie-ping, YANG Jian-ming (Xi′an Modern Chemistry Research Institute, Xi′an 710065, China), Huaxue Shiji, 2017, 39(3)
Abstract: Methoxyacetone was synthesized from proprylene glycol monomethyl ether using co-precipitated copper-zinc oxide as catalyst in fixed-bed reactor. Optimal preparation of catalysts was studied and the best conditions for targeted reaction were investigated. Results showed that the optimal parameters for Cu-ZnO catalysts are listed as followed: nCu︰nZn=0.5, precipitation temperature of 55 ℃, aging temperature of 55 ℃ for 1 h, being modified by sodium nitrate, and being annealed at 400 ℃ for 4 h. Meanwhile, the optimal condition for the reaction of converting proprylene glycol to methoxyacetone is obtained to be first reduced at 240 ℃ for 4 h, then going through reaction under 240 ℃.The liquid space velocity and flowing rate of nitrogen should be 40 mL/h and 150 mL/min, respectively. The as-made catalyst showed excellent stability in the time duration of 120 h.
Key words: proprylene glycol monomethyl ether; methoxyacetone; copper-zinc oxide-aluminum oxide; catalyst optimization
光引发和微波聚合快速制备分子印迹毛细管电色谱整体柱[1]
左国强*1，崔海燕1，郑伟1，张裕平2
(1. 济源职业技术学院 冶金化工系，河南 济源 459000；
2. 河南科技学院 应用化工研究所，河南 新乡 453003)
摘要：以光引发和微波聚合的方式快速制备了以对羟基苯甲酸为模板的分子印迹毛细管电色谱整体柱。实验结果表明，光聚合整体柱材料较微波聚合整体柱材料颗粒大、孔径大、通透性好，两种方法制备的整体柱都显示出了较好的印迹效果，可实现羟基苯甲酸异构体的分离，但由于后者孔径小、通透性差，需采用p-CEC模式。同时，两种方法制备的整体柱还能够实现中性化合物的分离。
关键词：分子印迹；毛细管电色谱；整体柱
中图分类号：O652.1 文献标识码：A 文章编号： 0258-3283（2017）
Capillary Electrochromatography of Molecularly Imprinted Monolithic Columnvia Photo-initiated and Microwave Polymerization ZUO Guo-qiang*1, CUI Hai-yan1, ZHENG Wei1, ZHANG Yu-ping2 (1. Department of Metallurgy and Chemical Engineering, Jiyuan Vocational and Technical College, Jiyuan 459000, China; 2. Institute of Applied Chemistry, Henan Institute of Science and Technology, Xinxiang 453003, China), Huaxue Shiji, 2017, 39(3)
Abstract: A 4-hydroxybenzoic acid imprinted column was prepared by in situ photo-initiated and microwave polymerization in a capillary column. The results show that the particle diameter and pore size of monolithic column materials by in situ photo-initiated is larger than microwave irradiation. Meanwhile, the former has good permeability. Good molecular recognition was achieved for p-hydroxybenzoic acid and good resolution of isomers can be realized. In addition, the mode of pressure-driven capillary electrochromatography is needed on the monolithic column by microwave irradiation, caused by small particle diameter and pore size. Furthermore, some neutral compounds could also be baseline-separated on the imprinted polymer columns by photo initiated and microwave irradiation.
Key words: molecularly imprinted polymer; capillary electrochromatography; monolith
合成冰片中差向异构体的拆分
崔杏，李述敏，王丽丽，张吉泉* ，汤磊*
（贵州医科大学 药学院，贵州 贵阳 550004）
摘要：研究了合成冰片中异构体拆分的新方法。以合成冰片为原料，根据不同构型异构体与酸酐进行酯化反应能力的差异形成其酯化物。利用手性拆分剂对该酯化物进行拆分，通过手性液相分析各组分比例。拆分结果显示，龙脑含量从60.0%提高至90.6%，对合成冰片中龙脑与异龙脑的分离有显著效果。
关键词：冰片；拆分；手性；合成
中图分类号：R914.5 文献标识码：A 文章编号：0258-3283（2017）
Resolution of Epimers from Synthetic Borneol CUI Xing, LI Shu-min, WANG Li-li, ZHANG Ji-quan*, TANG Lei*(School of Pharmacy, Guizhou Medical University, Guiyang 550004, China ), Huaxue Shiji, 2017, 39(3)
Abstract: We proposed a new method for the resolution of epimers from synthetic borneol. The method involves the different esterification of borneol epimers into the formation of estolides and the resolution with chiral agents in chiral HPLC. The results showed that this method could remarkably increase the purity of borneol from 60.0% to 90.6%, demonstrating its high suitability for resoluting epimer from synthetic borneol.
Key words: borneol; resolution; chiral; synthesis
2-氯-4-硝基苯基-β-D-吡喃岩藻糖苷的合成
沈生强，张建军*
（中国农业大学 理学院 化学试剂研发平台，北京 100193）
摘要：2-氯-4-硝基苯基糖苷是一类重要的糖基酶底物试剂，在相关酶抑制剂制备、酶生物活性研究中有着广泛的应用。以D-半乳糖为原料，通过4步反应得到中间体D-岩藻糖；再经乙酰化制备1, 2, 3, 4-三-O-乙酰基-α, β-D-吡喃岩藻糖，溴代反应获得1-溴-2, 3, 4-三-O-乙酰基-α-D-吡喃岩藻糖，通过溴代糖与2-氯-4-硝基苯酚偶联，立体选择性获得2-氯-4-硝基苯-2, 3, 4-三-O-乙酰基-β-D-吡喃岩藻糖基糖苷，最后脱除乙酰基保护得标题化合物。该化合物可以作为一种新型的β-D-岩藻糖苷酶底物试剂，用于酶活性测试，其合成方法未见文献报道。
关键词：β-D-岩藻糖苷；2-氯-4-硝基苯酚；合成；糖苷酶底物
中图分类号：O621. 3 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of 2-Chloro-4-nitrophenyl-β-D-fucoside SHEN Sheng-qiang, ZHANG Jian-jun* (Scientific Reagent Platform, Department of Applied Chemistry, China Agricultural University, Beijing 100193, China), Huaxue Shiji, 2017, 39(3)
Abstract: 2-Chloro-4-nitrophenyl as a very important fluorogenic group has been used for synthesis many glycoside enzyme substrates which are widely applied in the research of its related enzyme inhibitor sandenzyme activities. In this work, a novel compound 2-chloro-4-nitrophenyl-β-D-fucoside has been designed and synthesized as enzyme substrate for β-D-fucosidase. Firstly, D-fucose was synthesized from the commercially inexpensive D-galactose as the starting material in four steps. Secondly, 1-bromo-2, 3, 4-tri-O-acetyl-α-D-fucoside was prepared from D-fucose via acetylization and bromination. Thirdly, the 1-bromo-2, 3, 4-tri-O-acetyl-α-D-fucoside was coupled to fluorescein 2-chloro-4-nitrophenol to obtain 2-chloro-4-nitrophenyl-2, 3, 4-tri-O-acetyl β-D-fucoside in the way of stereoselectivity. At last, the target compound 2-chloro-4-nitrophenyl-β-D-fucoside was obtained from 2-chloro-4-nitrophenyl-2, 3, 4-tri-O-acetyl-β-D-fucoside via deacetylation.
Key words: β-D-fucoside; 2-chloro-4-nitrophenol; synthesis; glycoside enzyme substrate
精确合成多溴代二苯醚类化合物
沈宏1，崔凯*2
（1．江苏开放大学 ，江苏 南京 210089；
2．南京大学金陵学院 化学与生命科学学院，江苏 南京 210036）
摘要：用间氯过氧苯甲酸和三氟甲磺酸做酸性氧化体系，以多种溴代碘苯及溴代苯合成了溴代二苯基碘盐。再以其同溴代苯酚在碱性条件下反应，精确合成各种多溴代二苯醚。该合成方法简便、反应条件温和、后处理简单、产品纯度好、收率高。
关键词：精确合成；溴代二苯醚；溴代二苯基碘盐；间氯过氧苯甲酸；三氟甲磺酸
中图分类号：O625．322 文献标识码：A 文章编号：0258-3283（2017）
Accurate Synthesis of Polybrominated Diphenyl Ethers SHEN Hong1, CUI Kai*2 (1. ，Jiangsu Open University, Nanjing 210089, China; 2. School of Chemistry & Life Science, Nanjing University Jinling College, Nanjing 210036, China)，Huaxue Shiji, 2017, 39(1),
Abstract: A series of polybrominated diphenyliodonium trifluoromethanesulfonic salt were synthesized from brominated iodobenzene and brominated benzene catalyzed by m-chloroperoxybenzoic acid and trifluoromethanesulfonic acid. Then corresponding polybrominateddiphenyl ethers were accurately synthesized with them and brominated phenol in alkaline condition. The advantages of the procedure are: mild reaction condition, easy operation, simple after-treatment, high yield and purity of products.
Key words：accurate synthesis; polybrominated diphenyl ethers; polybrominated diphenyliodonium trifluoromethanesulfonic salt; m-chloroperoxybenzoic acid; trifluoromethanesulfonic acid
咪唑基多芳胺类化合物的合成
耿师科，郝占忠，马学林*
(包头师范学院 化学学院 材料化学与物理重点实验室，内蒙古 包头 014030)
摘要：无氧条件下，环己烷作溶剂，以咪唑为酸性组分与芳香醛和芳香胺反应，通过多组分Mannich 反应，“一锅法”成7种新型咪唑基多芳胺类化合物，产率81% ～ 88%。产物通过IR、1HNMR和元素分析确定。该方法具有操作简单、条件温和、产率高、选择性高等特点。
关键词：咪唑衍生物；Mannich反应；一锅法
中图分类号：O643.37 文献标识码：Ａ 文章编号：0258-3283（2017）
Synthesis Multi Aromatic Amine Compounds with Imidazole GENG Shi-ke, HAO Zhan-zhong, MA Xue-lin* (College of Chemistry, Key Laboratory of Materials and Physical Chemistry, Baotou Normal College, Baotou 014030，China)
Abstract：Under anaerobic conditions and cyclohexane as solvent, novel multi aromatic amine compounds were synthesized with imidazole, aromatic aldehydes and aromatic amines by three component "one pot" Mannich reaction. The yield reached 81%～ 88%. The products are confirmed by IR, 1HNMR and elemental analysis. This process has advantages of simple, mild conditions, high yield and high selectivity.
Key words：imidazole derivatives；Mannich reaction；one pot
2-甲萘醌的合成研究
方耀思，王建安，陆玉龙，洪丹丹，陈锡生，杨义文*
（嘉兴学院 生物与化学工程学院，浙江 嘉兴 314001）
摘要：工业上多采用硫酸/铬酐（或重铬酸钠）氧化2-甲基萘合成2-甲萘醌，但此法会产生大量的含铬废水，环境污染严重。研究了以硝酸钴为催化剂、Oxone为氧化剂催化氧化2-甲基萘合成2-甲萘醌的新方法。研究表明，当以5 mol%硝酸钴为催化剂、Oxone为氧化剂、乙腈/水为溶剂，在反应温度为25 ℃、反应时间为16 h时，2-甲基萘的转化率和2-甲萘醌的产率分别为82.6%和51.2%。该反应可在室温下进行，反应平稳、绿色、环保、节能、高效。
关键词：硝酸钴；2-甲基萘；2-甲萘醌；室温
中图分类号：O643.32；O625.46 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of 2-Methylnaphthalene-1, 4-dione FANG Yao-si, WANG Jian-an, LU Yu-long, HONG Dan-dan, CHEN Xi-sheng, YANG Yi-wen*(College of Biology and Chemical Engineering, Jiaxing University, Jiaxing 314001, China), Huaxue Shiji, 2017, 39(3)
Abstract: The industrial process for the preparation of 2-methylnaphthalene-1, 4-dione is from 2-methylnaphthalene oxidized by sulfuric acid /chromic anhydride (or sodium dichromate). But the method generates a large amount of chromium-containing waste water, which seriously pollutes the environment. In this work, a new method of synthesis of 2-methylnaphthalene-1, 4-dione from 2-methylnaphthalene using cobalt(Ⅱ) nitrate as catalyst and oxone as oxidant was investigated. The results showed, under the optimized reaction conditions, 5 mol% of cobalt(Ⅱ) nitrate catalyst, oxone oxidant, CH3CN/H2O solvent, 25 ℃ reaction temperature, and 16 h reaction time, the conversion of 2-methylnaphthalene and the yield of 2-methylnaphthalene-1, 4-dione could reached 82.6% and 51.2%, respectively. The reaction could proceed at room temperature with the advantages of green, environmental protection, energy-saving and high-efficiency.
Key words: cobalt(Ⅱ) nitrate; 2-methylnaphthalene; 2-methylnaphthalene-1, 4-dione; room temperature
基于选择性羟基保护合成3-烷基-5, 7-二羟基-6-氯-4-色满酮
李洪爽*，张瑞泽，郭爽
(泰山医学院 药理学研究所，山东 泰安 271016)
摘要：以2, 4, 6-三羟基苯甲酸为起始原料，经氯代、脱羧、酰化得1-(3-氯-2, 4, 6-三羟基苯基)烷基酮，接着采用MOMCl进行选择性羟基保护，随后经环合、脱保护得两个标题化合物，总收率分别为30.9%和32.2%。产物结构经1HNMR、ESI-MS进行确证。此合成方法具有原料廉价易得、操作简单、收率较高等特点，适合在多酚羟基存在条件下利用选择性酚羟基保护策略区域选择性地合成目标产物。
关键词：选择性保护；3-烷基-5, 7-二羟基-6-氯-4-色满酮；合成
中图分类号：O626 文献标识码：A 文章编号：0258-3283（2017）
Synthesis of 3-Alkyl-5, 7-dihydroxy-6-chloro-4-chromanones Based on Selective Protection of the Hydroxyl Groups LI Hong-shuang*, ZHANG Rui-ze, GUO Shuang (School of Pharmaceutical Sciences, Taishan Medical University, Tai′an 271016, China), Huaxue Shiji, 2017, 39(3)
Abstract：1-(3-Chloro-2, 4, 6-trihydroxyphenyl)alkylketones were successively prepared by chlorination, decarboxylation and acylation using 2, 4, 6-trihydroxybenzoic acid as the starting material. Selective protection of the hydroxyl groups of the intermediates 4 with MOMCl followed by cyclization and deprotection delivered two 3-alkyl-5, 7-dihydroxy-6-chloro-4-chromanones with the total yield of 30.9% and 32.2%, respectively. The structures of the target products were confirmed by 1HNMR and ESI-MS. This protocol features cheap and available materials, simple operation and high yields, which is suitable for the synthesis of the target products regioselectively in the presence of multi-hydroxyl groups using the strategy of selective protection of the hydroxyl groups.
Key words：selective protection; 3-alkyl-5, 7-dihydroxy-6-chloro-4-chromanone; synthesis
酪氨酸蛋白磷酸酶SHP-2抑制剂PHPS1及其类似物的合成
崔志文，蒋丝绒，闵真立*，杨凯文，朱月，胡霞敏*
(武汉科技大学 医学院，湖北 武汉 430065)
摘要：以冰醋酸为溶剂，苯肼及其衍生物与取代酰基乙酸乙酯反应得到吡唑啉酮类中间体。然后再与由苯胺衍生物制备的重氮盐反应，最后得到苯基腙吡唑酮衍生物PHPS1及其类似物，并通过1HNMR、IR和MS对其结构进行确证。为苯基腙吡唑酮类SHP-2抑制剂的合成提供了新思路。
关键词：SHP-2抑制剂；PHPS1；合成
中图分类号：O621.3；R914.5 文献标识码：A 文章编号： 0258-3283（2017）
Synthesis of Tyrosine Protein Phosphatases SHP-2 Inhibitor PHPS1 and Its Analogues CUI Zhi-wen, JIANG Si-rong, MIN Zhen-li*, YANG Kai-wen, ZHU Yue, HU Xia-min*（Department of Pharmacology, Wuhan University of Science and Technology, Wuhan 430065, China）, Huaxue Shiji, 2017, 39(3)
Abstract: Phenylhydrazine and its derivatives reacted with ethyl substituted acylacetates to obtaina serial of pyrazolone intermediates in acetic acid which followed by reactions with the diazonium salts prepared from aniline derivatives, and the phenylhydrazonopyrazolone derivative PHPS1 and its analogues were synthesized. The structures of the products were confirmed by 1HNMR, IR and MS. This work gives a new idea on the synthesis of phenylhydrazonopyrazolone SHP-2 inhibitor.
Key words: SHP-2 inhibitor; PHPS1; synthesis
合成联苯-4-甲酸的新方法
王海洋*1，刘佳2，金丹1，臧娜2，王守凯1,2
（1. 中钢集团鞍山热能研究院有限公司，辽宁 鞍山 114044；
2. 中唯炼焦技术国家工程研究中心有限责任公司，辽宁 鞍山 114044）
摘要：以联苯和草酰氯为原料，通过傅克酰基化反应合成联苯-4-酮酸乙酯，经碱性水解得联苯-4-酮酸，在双氧水作用下，酮酸发生氧化脱羰基反应，得目标产物。对酰化条件进行了优化并详细考察了氧化剂种类、双氧水浓度、物料配比、反应温度和时间对氧化脱羰基反应的影响，确定较佳的工艺条件：10%双氧水作氧化剂，n (联苯-4-酮酸) : n (双氧水) = 1︰2，反应时间3 h，反应温度0 ~ 5 ℃。在此条件下，联苯-4-甲酸收率81.9%（以原料联苯计），纯度99.5%（HPLC面积归一化法）。产物结构经过熔点、1HNMR和 13CNMR表征。
关键词：联苯；草酰氯；联苯-4-甲酸；联苯-4-酮酸；联苯-4-酮酸乙酯
中图文分类号：O625.53 文献标识码：A 文章编号：0258-3283（2016）
Novel Synthesis of Biphenyl-4-carboxylic Acid WANG Hai-yang*1, LIU Jia2, JIN Dan1, ZANG Na1, WANG Shou-kai1, 2（1. Sinosteel Anshan Research Institute of Thermo-energy Co., Ltd, Anshan 114044, China; 2. National Engineering Research Center for Coking Technology, Anshan 114044, China）, Huaxue Shiji, 2016, 38(12)
Abstract：Biphenyl-4-carboxylic acid was synthesized from biphenyl and oxalylchloride by Friedel-Crafts acyl reaction, alkaline hydrolysis and oxidative decarboxylation. The effects of reactions on the yield of biphenyl-4-carboxylic acid have been investigated and the optimized conditions are as follows: 10% H2O2 as the oxidative reagent, the molar ratio of biphenyl-4-keto acid vs H2O2 is 1 : 2, the reaction temperature is 0 ～ 5 ℃ and the reaction time is 3 h. Under the optimized conditions, the yield of biphenyl-4-carboxylic acid can reach 81.9% and the purity is higher than 99.5%(HPLC area normalization method). The obtained biphenyl-4-carboxylic acid has been identified by MP, 1HNMR, 13CNMR and MS.
Key words: biphenyl; oxalylchloride; biphenyl-4-keto acid; biphenyl-4-carboxylic acid; biphenyl-4-keto acid ethyl ester
