DNA-烷基转移酶(AGT)抑制剂及其在抗肿瘤耐药作用方面的研究进展
赵瑞凡a，任婷a，甄岩*b
(北京工业大学 a. 生命科学与生物工程学院 环境与病毒肿瘤学北京市重点实验室,
b．环境与能源工程学院，北京 100124)
摘要：烷化剂类抗癌药物可攻击细胞DNA分子众多部位，产生一系列DNA加合物，影响DNA复制和转录等过程，从而诱导细胞变异或凋亡。O6-烷基鸟嘌呤-DNA-烷基转移酶(O6-alkylguanine-DNA-alkyltransfer-ase, AGT)是哺乳动物体内普遍存在的一种DNA修复蛋白酶，可使受损DNA得以修复，导致肿瘤细胞对化疗药物产生耐药性，降低肿瘤化疗的效果。就近年来有关DNA烷化损伤、AGT介导的肿瘤细胞的耐药性以及AGT抑制剂的应用研究进展进行综述。
关键词：O6-烷基鸟嘌呤-DNA-烷基转移酶；耐药性；AGT抑制剂
中图分类号：O621.2 文献标识码：A 文章编号：0258-3283(2018)
DNA AlkylTransferase Inhibitors and Inhibitory Effect on Resistance to Treatments with Anticancer Drugs ZHAO Rui-fana, REN Tinga, ZHEN Yan*b (a. Beijing Key Laboratory of Environment and Viral Oncology, College of Life Science and Bioengineering, b. College of Environmental and Energy Engineering , Beijing University of Technology, Beijing 100124, China), Huaxue Shiji, 2018, 40(4)
Abstract: Anticancer alkylating agents are able to attack some points of DNA in the cells and produce different types of DNA adducts, which affect the DNA replication and transcription and lead to cell mutation or apoptosis. O6-alkylguanine-DNA-alkyltransferase (AGT) is a kind of DNA repair protease that generally exists in the body of mammals. By repairing DNA alkylation damage, AGT causestumor cells to be resistant to chemotherapy drugs and the effect of tumor chemotherapy to be reduced. In this work, the recent progress of the research on the DNA alkylation damage, AGT mediated the resistance of tumor cells, and the application of AGT inhibitors research is summarized.
Key words：O6-alkylguanine-DNA-alkyltransferase; resistance; AGT inhibitor
不同(001)晶面暴露比例锐钛矿二氧化钛的可控合成
陈星晖，高慧芳，崔子祥*
（太原理工大学 化学化工学院，山西 太原 030024）
摘要：使用P25(Degussa)二氧化钛作为钛源，二乙醇胺作为形貌控制剂，通过两步水热法制备了含有不同比例的高能（001）晶面的锐钛矿二氧化钛。实验探究了水热温度、二乙醇胺的用量对产物（001）晶面暴露比例的影响。用X射线衍射仪(XRD)、扫描电镜(SEM)对所制备含有不同比例（001）晶面产物的物相和形貌进行表征分析，计算了不同产物含有的（001）晶面的比例。实验结果表明：二乙醇胺的用量对（001）晶面的暴露比例有很大影响，增加二乙醇胺的用量，产物的（001）面增多。通过控制反应中二乙醇胺的用量，制备出（001）晶面暴露比例为15% ～ 80%的产物。
关键字：纳米二氧化钛；001晶面；水热合成
中图分类号：TB34 文献标识码：A 文章编号：0258-3283(2018)
Controllable Synthesis of Anatase Titanium Dioxide with Different (001) Facet Exposure Ratio CHEN Xing-hui, GAO Hui-fang, CUI Zi-xiang* (College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Shanxi 030024, China), Huaxue Shiji, 2018, 40(4)
Abstract：Anatase titanium dioxide with different proportions of high energy (001) facet was prepared by two-step hydrothermal method using P25 as titanium source and diethanolamine as morphology control agent. The exposure rate of high energy (001) facet could be controlled. The effects of the hydrothermal temperature and the amount of diethanolamine were investigated. The phase and structure of the TiO2 products with different ratios of (001) facet were confirmedby X - ray diffraction (XRD) and scanning electron microscopy (SEM). The proportion of (001) crystal facet of different products was calculatedviathe SEM patterns. The experimental results shows that the amount of diethanolamine has a great influence on the exposure ratio of (001) crystal face, and increasing the amount of diethanolamine will lead the increase of the proportion of exposed (001) facet. By controlling the amount of diethanolamine used in the reaction, the (001) crystal face exposure ratio of products can be varied from 15% to 80%.
Key words: Nano titanium dioxide; (001) crystal facet; hydrothermal synthesis
缩酮席夫碱阴离子受体的合成、表征及阴离子识别研究
刘峥*1，韩佳星1，王浩1，魏席1，张淑芬1, 2
（1. 桂林理工大学 化学与生物工程学院 电磁化学功能物质广西区重点实验室，广西 桂林541004；2.大连理工大学 精细化工重点实验室，辽宁 大连 116024）
摘要：随着经济与科学技术的发展，阴离子对医药、生命科学、环境保护、农业生产和工业催化等领域的研究有着越来越重要的影响，因此，阴离子识别技术与阴离子受体的设计合成有着广阔的发展前景。合成了3种1,10-邻菲罗琳-5,6-二酮缩（硝基）苯肼席夫碱阴离子受体（R3-1、R3-2和R3-3），应用比色法和紫外-可见吸收光谱法研究了受体分子对阴离子的识别性能。结果表明，受体R3-1、R3-2和R3-3均对阴离子有一定的识别能力，其中R3-3的识别效果最好。分析R3-3的紫外-可见吸收光谱，计算得出R3-3对F−、AcO−和H2P
的结合常数Ka分别为6956（R2 = 0.9859）、4730（R2 = 0.9873）和3754（R2 = 0.9787）；检出限分别为2.88×10-6（R2 = 0.9912）、7.7×10-6（R2 = 0.9953）、1.47×10-5 mol/L（R2 = 0.9929）。
关键词: 席夫碱；阴离子；比色法；紫外-可见吸收光谱法
中图分类号：O622 文献标识码：A 文章编号：0258-3283（2018）
Synthesis, Characterization and Anion Recognition of Schiff Base Anion Receptors LIU Zheng*1, HAN Jia-xing1, WANG Hao1, WEI Xi1, ZHANG Shu-fen1,2 (1. College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, China; 2. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China), Huaxue Shiji, 2018, 40(4)
Abstract: With the development of economy and science and technology, anion has more and more important influence in the fields of medicine, life sciences, environmental protection, agricultural production and industrial catalysis. Anion recognition technology and the design and synthesis of anion receptors have broad prospects for development. In this work, three 1,10-phenanthroline-5,6-dione (nitro) phenylhydrazine Schiff base anion receptors were synthesized(R3-1、R3-2 and R3-3). The recognition properties of the anions were investigated by colorimetry and UV - Vis absorption spectroscopy. The results show that the receptors R3-1, R3-2 and R3-3 have a certain ability to recognize the anions, of which R3-3 is the best. The binding constants Ka of R3-3 to F-, AcO- and H2PO4 were 6956 (R2 = 0.9859), 4730 (R2 = 0.9873) and 3754 (R2 = 0.9787), respectively, by analyzing the UV-Vis absorption spectra of R3-3. The detection limits were 2.88 × 10-6mol / L (R2 = 0.9912), 7.7 × 10-6mol / L (R2 = 0.9953) and 1.47 × 10-5mol / L (R2 = 0.9929), respectively.
Key words: Schiff base; anion; colorimetry; UV-Vis absorption spectroscopy
一种新型双子阳离子表面活性剂的相转移催化性能研究
张振伟，孙硕，张庭兰，潘忠稳*
(安徽大学 化学化工学院，安徽 合肥 230601)
摘要：以环己烯二甲酸二甲酯、N, N-二甲基-1, 3-丙二胺、溴代十二烷为原料，合成了一种新型双子阳离子表面活性剂KB-12。以KB-12作为相转移催化剂，研究其对乙酸钠和氯乙酸乙酯反应的催化性能。结果表明，在30 ℃下，反应速率常数K与KB-12浓度c符合线性方程K=0.122+5.735c；当KB-12的浓度为0.012 mol/L时，反应表观活化能降低至11.136 kJ/mol。对比了不同阳离子表面活性剂的催化效果，催化活性顺序为KB-12＞十六烷基三甲基溴化铵＞四丁基溴化铵＞十二烷基三甲基溴化铵＞苄基三甲基氯化铵。
关键词：合成；阳离子Gemini表面活性剂；相转移催化
中图分类号： 文献标识码：A 文章编号：0258-3283（2018）
Phase Transfer Catalytic Properties of Novel Cationic Gemini Surfactant ZHANG Zhen-wei, SUN Shuo, ZHANG Ting-lan, PAN Zhong-wen*(School of Chemistry and Chemical Engineering, Anhui University, Hefei 230601, China), Huaxue Shiji, 2018, 40(3)
Abstract: A novel cation Gemini surfactant (KB-12) was synthesized with dimethyl cis-1, 2, 3, 6-tetrahydrophthalate, N, N-dimethyl-1, 3-propyldiamine, and 1-bromododecane. Using KB-12 as phase transfer catalyst, the reaction of the catalytic properties of sodium acetate anhydrous and ethyl chloroacetate was investigated. The result showed that at the 30℃, the reaction rate constant K was linearly related to the catalyst concentration of KB-12, the linear equation was K=0.122+5.735c, and when the KB-12 was 0.012 mol/L. The apparent activation energy can be reduced by 11.136 kJ/mol. The catalytic effect of different cationic surfactants was compared, the order of catalytic effects was KB-12 >N, N, N-trimethylhexadecan-1-aminium bromide >tetrabutyl ammonium bromide >dodecyltrimethylammonium bromide >benzyltrimethylammonium chloride.
Key words：synthesize; cationic Gemini surfactant; phase transfer catalysis
ZnCl2/凹土和酸化凹土固体酸催化傅克烷基化反应的活性比较
吴洁*1，杨珊珊2
(1. 江苏卫生健康职业学院，江苏 南京 211800；2. 江苏省凹土资源利用重点实验室，江苏 淮安 223005)
摘要: 以甲苯和苄氯的傅克烷基化反应为模型反应，以产物中单苄基甲苯的选择性（SMBT）为考察指标，比较了以凹土(ATP)为载体负载ZnCl2的固体酸催化剂（ZnCl2/ATP）和凹土本身经酸化后形成的酸化凹土（H+/ATP）的催化活性。通过BET、XRD、NH3-TPD等手段对催化剂的结构和性能进行表征，考察并比较了催化剂制备条件和傅克反应条件对催化活性的影响。结果表明，催化剂的催化活性受酸化凹土的盐酸浓度、催化剂干燥方式、傅克反应时间、尤其是催化剂用量的影响。当催化剂用量由0.5 g/mL增至1.5 g/mL时，H+/ATP的选择性由78.6%提高至97.9%，远高于ZnCl2/ATP的83.5%，催化剂不同的活性受各自酸强度和酸量的影响，其高活性归功于活性组分和载体的协同作用。
关键词: 凹土；ZnCl2；固体酸催化剂；催化活性；傅克反应
中图分类号：O643 文献标识码：A 文章编号：0258-3283(2018)
Catalytic Activities of Immobilized Catalysts with ZnCl2/Attapulgite and Acidified Attapulgite in Friedel-Crafts Alkylation Reaction WU Jie*1，YANG Shan-shan2(1. Jiangsu Health Vocational College，Nanjing 211800；2. Key Laboratory for Palygorskite Science and Applied Technology of Jiangsu Province, Huaian 223005, China), Huaxue Shiji, 2018, 40(3)
Abstract：The catalytic activities of the immobilized ZnCl2 catalysts (ZnCl2/ATP) with attapulgite（ATP）as support were compared with the acidified ATP (H+/ATP) by the friedel-crafts alkylation of toluene and benzyl chloride, and the selectivity of monobenzyltoluene (SBET%) was selected as the indicator. The structures and the properties of the catalysts were characterized by BET, XRD and NH3-TPD. The effects of the preparation and alkylation reaction condition on the catalytic activities were investigated. The results showed that the catalytic activities were affected by the concentration of HCl, drying method, reaction time and catalysts amount, especially. SBET% of H+/ATP increased from 78.6% to 97.9% when the amount increased from 0.5 to 1.5 g/mL, which was higher than that of ZnCl2/ATP with 83.5%. The different activity of the two catalysts was dependent on the acid strength and amount, and the enhanced activities of the prepared catalysts were attributed to the synergistic effect of the active constituent and carrier.
Key words：attapulgite; ZnCl2; immobilizedcatalyst; catalytic activity; Friedel-Crafts reaction
新型比色荧光指示剂的设计合成及对亚硫酸氢根的测定
闫语1，朱宝存*2
（1. 济南市历城第二中学，山东 济南 250105；2 济南大学 资源与环境学院，山东 济南 250022）
摘要：亚硫酸氢盐被广泛用于食品和饮料的防腐剂，但浓度过高时对人体和环境均会产生严重的危害，因此发展定量检测亚硫酸氢根的方法非常重要。为了高效、定量检测亚硫酸氢根，采用双键加成的反应原理，设计合成了一种基于TCF（2-二氰亚甲基-3-氰基-4,5,5-三甲基-2,5-二氢呋喃)的具有高选择性、高灵敏度的亚硫酸氢根比色荧光指示剂。利用荧光光谱仪的高灵敏度，该指示剂可以对亚硫酸氢根进行高灵敏定量检测，测定荧光波长为620 nm，浓度范围为1 ～ 9 µmol/L，相关系数0.9937，检出限为0.03 µmol/L，对其他阴离子的响应较弱，选择性较好。糖类食品中亚硫酸氢根的测定结果证明了该方法准确、可靠。此外，在指示剂溶液中加入亚硫酸氢根时，颜色出现从蓝色到无色的变化，可以作为亚硫酸氢根的裸眼指示剂，为环境中亚硫酸氢根的检测提供一种新的分析方法。
关键词：亚硫酸氢根；荧光指示剂；比色指示剂；裸眼检测
中图分类号：O657 文献标识码：Ａ 文章编号：0258-3283（2018）
A Novel Colorimetric and Fluorescent Probe for Bisulfite: Design, Synthesis and Application for Determination of Bisulfite YAN Yu1, ZHU Bao-cun2 (1. Jinan Licheng No.2 High School, Jinan 250105, China; 2. School of Resources and Environment, University of Jinan, Jinan 250022, China), Huaxue Shiji, 2018, 40(4)
Abstract：The bisulfite is widely used as preservatives in food and beverage, and has serious hazards to human body and environment at higher concentration. It is very important to develop the detection method of bisulfite. For the efficient and quantitative determination of bisulfite, a highly selective and sensitive fluorescent probe was synthesized based on the TCF (2-dicyanomethylene-3-cyano-4, 5, 5-trimethyl-2,5-dihydrofuran) via double bond addition reaction. The results show excellent selectivity and high sensitivity for the determination of bisulfite by fluorescence spectrometer. The fluorescence spectrum was 620 nm, the concentration range was 1 ~ 9 µmol/L, the correlation coefficient was 0.9937 and the detection limit was 0.03 µmol/L. The determination results of bisulfite in three kinds of sugar samples demonstrated the proposed method was accurate and reliable. In addition, the as-synthesized probe exhibited the color of solution turned from blue to colorless upon addition of bisulfite, which indicated that it can serve as a “naked-eye” indicator and would provide a promising method for the detection of bisulfite in environment.
Key words：bisulfite; fluorescent probe; colorimetric probe; “naked-eye” indicator
手性磷酸在氮杂Diels-Alder反应中的应用
黄帅，曹国锐*
（青岛科技大学 化工学院，山东 青岛 266042）
摘要：氮杂Diels-Alder反应是构建六元含氮杂环的有效方法之一。近年来，手性磷酸作为一类高效绿色的有机小分子催化剂，在不对称催化反应中的应用备受关注，例如Diels-Alder、傅克烷基化、曼尼希反应等。根据Diels-Alder反应的分类，分别从正常电子需求和反电子需求的氮杂Diels-Alder反应着手，综述了1,1'-联二萘酚(BINOL)骨架及1,1'-螺二氢茚-7,7'-二酚(SPINOL)骨架的手性磷酸催化作用下，活泼双烯体与亚胺的正常电子需求氮杂Diels-Alder反应和氮杂双烯体与富电子烯烃的反电子需求氮杂Diels-Alder反应，并展望了手性磷酸在氮杂Diels-Alder反应中的应用前景，以期引起读者对该领域的兴趣与关注。
关键词：氮杂Diels-Alder；手性磷酸；催化；Povarov反应
中图分类号：O626.3 文献标识码：A 文章编号：0258-3283（2018）
Application of Chiral Phosphoric Acid in Aza-Diels-Alder Reaction HUANG Shuai, CAO Guo-rui* (College of Chemical Engineering，Qingdao University of Science and Technology, Qingdao 266042，China), Huaxue Shiji, 2018, 40(4)
Abstract: Aza-Diels-Alder reaction is one of the most effective ways to construct a six-membered nitrogen-containing heterocyclic ring. In recent years, chiral phosphoric acid has attracted much attention as an efficient green organic small molecule catalyst for asymmetric reactions such as Diels-Alderreaction, Friedel-Crafts alkylation, Mannich reaction and so on. Based on the classification of Diels-Alder reaction, this work reviews the aza-Diels-Alder reaction of normal-electron demand and inverse-electron demand respectively, and reviews the enantio selective aza-Diels-Alder reaction catalyzed by chiral phosphoric acid of 1,1'-binaphthol (BINOL) backbone and 1,1'-spirobiindane-7,7'-diphenol (SPINOL) backbone, for example ,the normal-electron demand aza-Diels-Alder reaction of some active dienes with imine and inverse-electron demand aza-Diels-Alder reactions of aza-dienes with electron-rich olefins. The application prospects of chiral phosphoric acid in aza-Diels-Alder reaction are prospected in order to arouse readers' interest and attention in this field.
Key words: aza-Diels-Alder; chiral phosphoric acid; catalyzed; Povarov reaction
超高效液相色谱-高分辨质谱法测定磷脂酰胆碱的含量
黄思静*1，朱斌1，汪义杰2
(1. 华南理工大学 分析测试中心，广东 广州 510640；2. 珠江水利科学研究院，广东 广州 510611)
摘要：建立了用超高效液相色谱-高分辨质谱（UPLC-ESI-Q-TOF）测定磷脂酰胆碱含量的分析方法。样品直接用乙醇溶解，超声萃取20 min，然后取适量提取液于8000 r/min高速离心5 min，最后有机膜过滤后用UPLC-ESI-Q-TOF检测。该方法的标准曲线在相关浓度范围内呈良好线性关系，检测线性范围为2.31 ～ 231 mg/L，线性相关系数为R2 = 0.9998。磷脂酰胆碱的检出限为1.0 mg/kg，定量限为2.3 mg/kg。采用阴性饲料粉末进行加标回收实验，3个浓度水平的添加样品均重复测定8次，加标回收率为88.20% ～ 93.50%，其RSD均小于10%，能得到较好的精密度。用该方法可测定饲料粉末、大豆磷脂和大豆磷脂软胶囊中磷脂酰胆碱的含量，方法灵敏度高、重复性好、定量准确。
关键词：磷脂酰胆碱；超高效液相色谱-高分辨质谱；饲料粉末；大豆磷脂；大豆磷脂软胶囊
中图分类号： 文献标识码：A 文章编号：0258-3283（2017）
UPLC-ESI-Q-TOF for Determination of Phosphatidylcholine HUANG Si-jing*1, ZHU Bin1, WANG Yi-jie2 (1. Analytical and Testing Center，South China University of Technology，Guangzhou 510640, China; 2. Pearl River Hydraulic Research Institute, Guangzhou 510611, China), Huaxue Shiji, 2018, 40(3)
Abstract：A method was established for the determination of phosphatidylcholine using ultra performance liquid chromatography-high resolution mass spectrometry (UPLC-ESI-Q-TOF). The samples were dissolved by ethanol directly, ultrasonic extracted for 20 min. Then, some extracting solution was centrifuged under a high speed of 8000 r/min for 5 min. Finally, samples were filtered by organic membrane before detected by UPLC-ESI-Q-TOF. The standard curve had a good linear relationship in the concentration range. The linear concentration range was from 2.31 to 231 mg/L，the linear correlation coefficient was R2= 0.9998. The detection limit of the method was 1.0 mg/kg, and the quantification limit was 2.3 mg/kg. The negative feed powder samples were used to carry out the recovery experiment, and the samples of 3 concentration levels were repeated eight times, the recoveries were from 88.20% to 93.50%, the RSDs were less than 10%, which can get good precision. This method can be used to determine the phosphatidylcholine in feed powder, soybean phospholipid and soft capsule of soybean phospholipid. The method had high sensitivity, good repeatability and accurate quantification.
Key words：phosphatidylcholine; UPLC-ESI-Q-TOF; feed powder; soybean phospholipid; soft capsule of soybean phospholipid
meso-苯基-4-吡啶基取代卟啉混合物的正相高效液相色谱定量分析方法的建立
赵文伯，王娇娇，崔艳艳，秦会安*
（郑州师范学院 化学化工学院，河南 郑州 450044）
摘要：本文采用SunFire® Prep Silica正相色谱柱，选用V（二氯甲烷）∶V（正己烷）=60∶40为流动相，在检测波长为417 nm，流速为1 mL/min，柱温为25 ℃的条件下，建立了对meso-苯基-4-吡啶基取代卟啉混合物进行定量分析的正相高效液相色谱方法。在该定量分析方法中，6种卟啉的标准曲线线性相关系数均大于0.9993，相对标准偏差均小于1.28%，加标回收率在96.4% ～ 103.9%之间。实验结果表明，该定量分析方法可用于meso-苯基-4-吡啶基取代卟啉混合物的同时测定。
关键词：meso-苯基-4-吡啶基取代卟啉；正相高效液相色谱；定量分析
中图分类号：O657.7 文献标识码：A 文章编号：0258-3283（2018）
Normal Phase Liquid Chromatography Based Method to Quantity Determine Meso-phenyl-4-pyridyl Substituted Porphyrins ZHAO Wen-bo, WANG Jiao-jiao, CUI Yan-yan, QIN Hui-an* (College Chemistry and Chemical Engineering, Zhengzhou Normal University, Zhengzhou 450044, China), Huaxue Shiji, 2018, 40(4)
Abstract：A method for the quantitative analysis of meso-phenyl-4-pyridyl substituted porphyrins was established by normal phase high performance liquid chromatography（NP-HPLC）. NP-HPLC was carried out on a SunFire® Prep Silicanormal column，using V（dichloromethane）∶V（n-hexane）=60∶40 as the mobile phase and the detection was performed by PAD detector at 417 nm，of which flow rate was 1.0 mL/min and the column temperature was 25 ℃. In the quantitative analysis method, the linear correlation coefficients of all the six porphyrins were more than 0.9993, the relative standard deviations were less than 1.28%, and the recoveries were between 96.4% and 103.9%. This method can be used for the simultaneous determination of meso-phenyl-4-pyridyl substituted porphyrins.
Key words: Meso-phenyl-4-pyridyl substituted porphyrin; normal phase high performance liquid chromatography; quantitative analysis
石墨炉原子吸收光谱法直接测定铁镍基高温合金中银、砷、铋、铅、硒、碲
张亮亮*，雷亚宁
（中航金属材料理化检测科技有限公司，陕西 西安 713801）
摘要：采用PinAAcle 900T型石墨炉原子吸收光谱仪，实现了铁镍基高温合金中痕量银、砷、铋、铅、硒、碲元素的直接测定，分析过程简便快捷，测定结果准确可靠。为了有效消除基体干扰，基于仪器优越的纵向交流塞曼效应扣除背景这一优点，同时，实验选用铁镍基标准样品建立工作曲线，并在该方法条件下考察了溶样酸和石墨炉温度制度条件。试验结果表明：各元素在其试验条件下均获得了较好的工作曲线，其线性相关系数R2均高于0.998；试验测得样品GBW01631中银、砷、铋、铅、硒、碲元素的回收率在94% ～ 110%之间；样品GBW01632和GBW01634中各元素的相对标准偏差RSD（n=6）分别介于1.6% ～ 9.6%和0.85% ～ 6.4%之间，即试验获得了良好的准确度和精密度。分析方法中各元素的检出限分别为：Ag 0.040 μg/L、As 0.46 μg/L、Bi 0.16 μg/L、Pb 0.25 μg/L、Se 0.49 μg/L、Te 0.91 μg/L。
关键词：铁镍基高温合金；石墨炉原子吸收光谱法；石墨炉温度制度；银；砷；铋；铅；硒；碲
中图分类号：O657.31 文献标识码：A 文章编号：0258-3283（2018）
Direct Determination of Silver, Arsenic, Bismuth, Lead, Selenium and Tellurium in Iron-nickel-base Superalloy by Graphite Furnace Atomic Absorption Spectrometry Method ZHANG Liang-liang*，LEI Ya-ning (AVIC Metal Test Technology Company Limited, Xi'an 713801, China ), Huaxue Shiji, 2018, 40(3)
Abstract: Direct determination of trace silver (Ag), arsenic (As), bismuth (Bi), lead (Pb), selenium (Se) and tellurium (Te) elements in iron-nickel-base superalloy was achieved by PinAAcle 900T model graphite furnace atomic absorption spectrometry (GFAAS). The analytical process is simple and reliable. In order to effectively eliminate matrix interference, considering first the superior performance of instrument that longitudinal alternating Zeeman effect deduct background. Meanwhile, working curves were built with iron-nickel-base standard sample, then the dissolved sample acid and the conditions of graphite furnace temperature program were investigated under this method. The linear correlation coefficients R2 of working curves were greater than 0.998. The recovery for Ag, As, Bi, Pb, Se, Te was between 94% and 110% in iron-nickel-base superalloy sample GBW01631. The relative standard deviation RSD (n = 6) of each element in sample GBW01632 and GBW01634 was between 1.6% ~ 9.6% and 0.85% ~ 6.4% respectively, that is to say, experiment obtained high accuracy and precision. The detection limits for each element in the method were 0.040 μg/L Ag, 0.46 μg/L As, 0.16 μg/L Bi, 0.25 μg/L Pb, 0.49 μg/L Se, 0.91 μg/L Te.
Key words: iron-nickel-base superalloy; graphite furnace atomic absorption spectrometry method; graphite furnace temperature program; Ag；As；Bi；Pb；Se；Te
天然花青素分光光度法测定豆类中的痕量钼（VI）
严进
(南通职业大学 化学与生物工程学院，江苏 南通 226007)
摘要：以紫薯中提取物天然花青素作为测定钼（VI）的显色剂。在硫酸介质中，钼（VI）与天然花青素在抗坏血酸溶液存在下配位生成稳定的蓝色化合物，该化合物最大吸收波长在680 nm处，据此建立了天然花青素测定钼（VI）的新分光光度法。在最佳实验条件下，钼（VI）的质量浓度在0.01 ~ 0.24 µg/mL范围内符合比尔定律，回归方程为A = 4.1363c(µg/mL)+0.004，相关系数r=0.9991，表观摩尔吸光系数为3.97×105 L/(mol·cm)，方法检出限为2.10×10-3 μg/mL。考察了20 多种共存离子的影响，结果表明该方法具有良好的选择性。方法用于豆类中痕量钼（VI）的测定，相对标准偏差＜0.79%，试样加标回收率在98.6% ~ 101.3%之间，豆类中钼（VI）的测定结果与原子吸收光谱法的测得值相近。
关键词：花青素；显色剂；钼（VI）；分光光度法
中图分类号：O657. 32 文献标识码：A 文章编号： 0258-3283（2018）
Determination of Trace Molybdenum in Bean Samples with Natural Anthocyanins Spectrophotometry YAN Jin(School of Chemical and Biological Engineering, Nantong Vocational University, Nantong 226007, China), Huaxue Shiji, 2018, 40(3)
Abstract: The natural anthocyanins was extracted from purple sweet potato was used as a color-developing agent for the determination of molybdenum. In H2SO4 medium, a blue stable composition of MO(VI) with natural anthocyanins in presence of ascorbic acid was formed. Its absorption maximum is at the wavelength of 680 nm. Based on this reaction, a spectrophotometric method for the determination of MO(VI) was proposed. At the optimum conditions, Beer′s law was obeyed with the mass concentration of MO(VI) in the range of 0.01 ~ 0.24 µg/mL. The linear regression equation A = 4.1363c(µg/mL)+0.004, correlation coefficient r=0.9991 and the apparent molar absorptivity was 3.97×105 L/(mol·cm) at the wavelength of 680 nm. The limit of detection was 2.10×10-3 μg/mL. The interferences of foreign ions were also investigated. The procedure has been used to determine trace molybdenum in beans samples, with the relative standard deviation of below 0.79% and the average recovery of 98.6% ~ 101.3%. Results obtained by this method were consistent with the results found by atomic absorption spectrophotometry.
Key words: natural anthocyanins; color-developing agent; MO(VI); spectrophotometry
快速溶剂萃取高效液相色谱法测定蔬菜中烯禾啶和麦草畏残留
金党琴*，丁邦东，王元有，龚爱琴，徐洁，周慧
（扬州工业职业技术学院 ，江苏 扬州 225127）
摘要：用乙腈作为提取剂快速萃取蔬菜中的烯禾啶和麦草畏，采用高效液相色谱法进行烯禾啶和麦草畏残留量测定。使用Dionex C18色谱柱，以V(乙腈)∶V(3%甲酸) = 80∶20为流动相，流速为1.0 mL/min，紫外检测器，检测波长为252 nm，建立一种从蔬菜中快速溶剂萃取烯禾啶和麦草畏结合高效液相色谱法测定其残留量的方法。结果表明，烯禾啶和麦草畏保留时间为4.87、3.84 min，线性相关系数为0.9978和0.9982。在7个质量分数添加水平范围内，回收率分别在93.24% ～ 102.51%和91.00% ～ 104.14%之间，相对标准偏差（RSD）分别在1.93% ～ 5.92%和3.51%% ～ 6.11%之间，方法检出限分别为0.012、0.020 mg/kg。该方法简单、快速、灵敏度高、准确度好，能够满足蔬菜中烯禾啶和麦草畏残留量的检测要求。
关键词：快速溶剂萃取；高效液相色谱；烯禾啶；麦草畏；蔬菜
中图分类号：O657.7 文献标识码：A 文章编号：0258-3283（2018）
HPLC Determination of Sethoxydim and Dicamba in Vegetables with Accelerated Solvent Extraction JIN Dang-qin*, DING Bang-dong, WANG Yuan-you, GONG Ai-qin, XU Jie, ZHOU Hui( , Yangzhou Polytechnic Institute, Yangzhou 225127, China), Huaxue Shiji, 2018, 40(3)
Abstract: A method was described for determination of sethoxydim and dicamba residues in vegetables by high-performance liquid chromatography (HPLC) with accelerated solvent extraction. Sethoxydim and dicamba in vegetables were accelerated extraction of acetonitrile, and were determined by HPLC. Samples were separated on the Dionex C18 column with a mobile phase of acetonitrile-3% formic acid (80:20, by volum) at the speed of 1.0 mL/min. The UV detector wavelength was 252 nm. The retention times for sethoxydim and dicamba were 4.87 and 3.84 min, the linear correlation coefficients were 0.9978 and 0.9982, respectively. At the seven spiked levels, the recoveries for sethoxydim and dicamba were 93.24% ～ 102.51% and 91.00% ～ 104.14%, the relative standard deviations were 1.93% ～ 5.92% and 3.51% ～ 6.11%, the limits of detection were 0.012 and 0.020 mg/kg, respectively. The method is simple, rapid, sensitive and accurate, which can meet the detection requirements for sethoxydim and dicamba residues in vegetables.
Key words: accelerated solvent extraction; HPLC; sethoxydim; dicamba; vegetables
气相色谱-质谱法测定日化产品包装材料中非邻苯酯类增塑剂含量的研究
李树恒[1]，赵海娟2，李文伟2，何山1，张峻松*1
(1. 郑州轻工业学院 食品与生物工程学院，河南 郑州 450002；
2. 河南中烟工业有限责任公司安阳卷烟厂，河南 安阳 455000)
摘要：采用超声辅助二氯甲烷萃取，利用HP-5MS毛细管柱和质谱选择离子检测器建立了市售日化产品包装材料中12种非邻苯酯类增塑剂含量的检测方法。结果表明，各目标化合物分离良好，非邻苯酯类增塑剂含量在0.005 ～ 0.5 mg/mL范围内，线性相关系数均达到0.999以上。该方法具有较低的检出限和定量限，分别为0.222 ～ 0.507和0.740 ～ 1.691 μg/mL。在高、中、低3个加标浓度下，12种非邻苯酯类增塑剂的回收率在83.11% ～ 113.67%之间，RSD为1.387% ～ 6.065%（n = 5）。该方法操作较为简便，可满足快速准确分析的要求，适于日化产品包装材料中非邻苯酯类增塑剂含量的监控。
关键词：日化产品；包装材料；非邻苯酯类增塑剂；气相色谱-质谱联用
中图分类号：TQ414.99；O657.63 文献标识码：A 文章编号：0258-3283（2017）
Analysis of Non-phthalic Ester PlasticizersContent in Chemicals Packing Materials by Gas Chromatography-mass Spectrometry LI Shu-heng1, ZHAO Hai-juan2, LI Wei-wei2, DONG Zhen-shan1, ZHANG Jun-song*1(1. Colloge of Food and Bioengineering, Zhengzhou University of light Industry, Zhengzhou 450001, China; 2. Anyang Cigarette Factory，China Tobacco He'nan Industrial Co, Ltd, Anyang 455000，China)
Abstract: The 12 kinds of non-phthalic ester plasticizersthat may existed in everyday chemicals shopping strategy for consumers of everyday chemicals packing materials were extracted with ultrasound-assisted of dichloromethane and determined by gas chromatography equipped with HP-5MS capillary columnand mass spectrometry detector. Results showed that each component has good separation and peak shape. The calibration curve showed good linearity when 12 kinds of non-phthalic ester plasticizers concentration was in the range of 0.005 ～ 0.5 mg/mL with correlation coefficient of 0.999 or above.The LOD and LOQ of the method are 0.222 ~ 0.507 μg/mL and 0.740 ~ 1.691 μg/mL, respectively. The average recoveries ranged from 83.11% to113.67% (RSD = 1.387% ～ 6.065%, n = 5). The method was simple and accurate which can be used for the determination of non-phthalic ester plasticizers in cosmetic packing materials.
Key words: daily chemicals; packing materials; non-phthalic ester plasticizers; GC- MS
一种含纳米稀土材料手性整体柱的制备
李英杰，郑伟伟，高立娣*，秦世丽
（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：采用一步键合法制备以烯丙基-β-环糊精和改性纳米氧化钇为单体的有机-无机杂化整体柱，并考察了改性纳米氧化钇用量、反应温度和反应时间对整体柱制备的影响。通过IR、N2吸附-脱附、SEM和EDS对整体柱柱内固定相进行表征。整体柱内固定相与柱壁键合紧密，有较大的孔径，改性纳米氧化钇均匀地分布在固定相中；整体柱具有良好的通透性和机械强度。运用该整体柱拆分盐酸地匹福林对映体和盐酸卡替洛尔对映体，两种手性药物均达到基线分离，说明该整体柱具有良好的手性拆分能力。
关键词：改性纳米氧化钇；整体柱；制备；手性药物；拆分
中图分类号： 文献标识码：A 文章编号：0258-3283（2018）
Preparation of Chiral Monolithic Column Containing NanosizedRare Earth Materials LI Ying-jie, ZHENG Wei-wei, GAO Li-di*, QIN Shi-li（College of Chemistry and Chemical Engineering，Qiqihar University，Qiqihar 161006，China）, Huaxue Shiji, 2018, 40(4)
Abstract: Organic-inorganic hybrid monolithic columnwas prepared by one-step reaction method, using allyl-β-cyclodextrin and modified nanosized-yttrium oxide as the monomers. And the effects of the dosage of modified nanosized-yttrium oxide, reaction temperature and reaction time were investigated in prepared monolithic column process. The stationary phase of monolithic column was characterized by IR, N2 adsorption-desorption, SEM and EDS. The results showed that the internal stationary phase was close to the column wall, had a larger pore size and uniform distribution of the modified nanosized-yttrium oxide. The monolithic column had good permeability and mechanical strength. The enantiomers of hydrochloric dipivefrin and hydrochloric carteolol were separated using the self-prepared monolithic column. And two kinds of chiral drugsreached the baseline separation, which indicated that the monolithic column had good chiral resolution ability.
Key words: modified nanosized-yttrium oxide; monolithic column; preparation; chiral drugs; separation
基于罗丹明B的Cu2+选择性荧光探针的合成与表征
李东洋a，宋越超a，袁梦婷a，陈慧敏a，林泽材a，张军*a,b
(海南医学院 a. 热带医学与检验医学院环境监测实验室，b. 国际教育学院，海南 海口 571199)
摘要：设计合成了一种基于罗丹明B为发光团的高选择性荧光探针。相对于其他常见金属离子，该探针对Cu2+具有较好的选择性和灵敏度。优化实验条件，在乙醇-水溶液（V(乙醇) : V (水) = 4 : 1，pH 7.3，50 mmol/L HEPES）测试介质中，探针对浓度在2.0×10−6 ～ 7.0×10−6 mol/L范围内Cu2+呈现良好的线性响应，检出限为6.7×10-7 mol/L。Job’ plot实验表明，探针与Cu2+以1︰1结合。可逆实验表明，探针与Cu2+的配合是可逆性的，其识别原理为Cu2+的加入导致探针P罗丹明内酯结构开环而发射出强的荧光。
关键词：Cu2+；罗丹明B；荧光探针
中图分类号：O622. 7 文献标识码：A 文章编号：0258-3283（2018）
Synthesis and Characterization of Cu2+-Selective Fluorescent Probe Based on Rhodamine B
LI Dong-Yanga, SONG Yue-Chaoa, YUAN Meng-Tinga, CHEN Hui-Mina, LIN Ze-Caia, ZHANG Jun*a,b (a. Laboratory of Environment Monitoring, School of Tropical and Laboratory Medicine, b. School of International Education, Hainan Medical University, Haikou 571199, China), Huaxue Shiji, 2018, 40(4)
Abstract：A rhodamine derivative was synthesized and characterized as Cu2+-selective fluorescent probe. Study showed that this proposed probe has good selectivity and sensitivity to Cu2+ compared to other tested metal ions. With optimal conditions, probe worked in a wide linear range of 2.0×10−6 ～ 7.0×10−6 mol/L with a detection limit of 6.7×10-7 mol/L Cu2+ in ethanol-water solution (V(ethanol) : V (water) = 4 : 1, 50 mmol/L HEPES, pH 7.3). The 1:1 binding mode of with Cu2+ was proved by Job’ plot experiment. The coordination of with Cu2+ is reversible, and the reaction mechanism is due to the metal ion-induced ring opening of rhodamine spirolactam.
Key words：Cu2+; rhodamine B; fluorescent probe
苯并咪唑类化合物的合成及荧光性能
宋立美*，李江涛，张宇，宋瑞娟，王留昌
（西安文理学院 化学工程学院，陕西 西安 710065）
摘要：将3, 4-二氨基苯甲酸与甲酸、羟基乙酸在加热回流的条件下分别反应合成5-羧基苯并咪唑与2-羟甲基-5-羧基苯并咪唑。以硝酸铈铵与过氧化氢为催化剂和氧化剂，使3, 4-二氨基苯甲酸与对苯二甲醛在极性非质子性溶剂DMF中反应合成1, 4-(双5-羧基苯并咪唑)苯。通过熔点测试、IR、1HNMR对所合成的化合物进行了结构表征，并通过激发光谱、发射光谱研究了其荧光性能。
关键词：苯并咪唑类化合物；3, 4-二氨基苯甲酸；合成；荧光
中图分类号： O626 文献标识码：A 文章编号：0258-3283（2018）
Synthesis and Fluorescent Properties of Benzimidazole Compounds SONG Li-mei*, LI Jiang-tao, ZHANG Yu, SONG Rui-juan, WANG Liu-chang(School of Chemical Engineering, Xi′an University, Xi′an 710065, China), Huaxue Shiji, 2018, 40(3)
Abstract: 5-Carboxy-benzimidazole and 2-hydroxymethyl-5-carboxy-benzimidazole were synthesized respectively using 3, 4-diaminobenzoic acid and formic acid (glycolic acid) as the reactants under reflux conditions. In polar aprotic solvent DMF, 1, 4-bis (5-carboxy-benzimidazole) benzene was synthesized with 3, 4-diaminobenzoic acid and terephthalic aldehyde as reactants, hydrogen peroxide asoxidant and ammonium cerium nitrate as catalyst. The structures of the compounds were confirmed by melting point test, IR and 1HNMR. And the fluorescent properties were investigated by excitation and emission spectra.
Key words: benzimidazole compounds; 3, 4-diaminobenzoic acid; synthesis; fluorescence
可视化检验射击残留物的荧光探针的合成及应用研究
李宏达*，王辉
（中国刑事警察学院 法化学系，辽宁 沈阳 110035）
摘要：为了探索利用荧光探针对射击残留物进行可视化分析，设计、合成一种新型香豆素衍生物的荧光探针1，并对射击者手面虎口处的残留物进行了分析，可以实现快速识别射击残留物。研究结果表明，探针1能够专一识别射击残留物不受其他类似分析物和底火成分的干扰；探针1能够在很宽的pH范围内识别射击残留物，响应速度不到1 min。我们将探针1成功地应用于实际样品分析中，并且实现了可视化识别（颜色由蓝色变为无色）射击残留物。最终，我们希望将此方法应用在涉枪案件中射击残留物的可视化分析，为案件侦查发挥一定的作用。
关键词：荧光探针；硫离子检测；射击残留物检测
中图分类号：D918.93 文献标识码：A 文章编号：0258-3283（2018）
Synthesis and Application of Visual Detection for Gunshot Residue Based on Fluorescence Probe
LI Hong-da*, WANG Hui (Department of Forensic Chemistry, Criminal Investigation Police University of China, Shenyang 110035, China), Huaxue Shiji, 2018, 40(4)
Abstract: To explore the visual analysis based on fluorescent probes for gunshot residue, a new type of coumarin derivatives of fluorescent probe 1 was synthesized, and analyzes for residue in the opisthenar of the shooter, and which could realize the purpose of the quick identification. The results showed that probe 1 could identify the gunshot residues without interference from other similar analysts and artillery primer. Probe 1 can detect to shooting residues at a wide range of pH level, and the response time is less than 1 min. It was successfully applied to visual identification of probe 1 for shooting residue (color from blue to colorless) in the actual sample analysis. In the end, this method can be used to the visual analysis of gunshot residues in gun cases.
Key words: fluorescent probe; Sulphide detection; gunshot residue
油酸酰胺聚氧乙烯醚（5）磷酸酯的合成及性能研究
张一波，朱国华*，喻红梅，华平
（南通大学 化学化工学院，江苏 南通 226019）
摘要：以油酸酰胺聚氧乙烯醚（5）为原料、五氧化二磷为磷酸化试剂合成了油酸酰胺聚氧乙烯醚（5）磷酸酯。通过正交实验优化的工艺条件为：n(油酸酰胺聚醚（5）) : n(五氧化二磷) = 2.5 ︰ 1，于60 ℃下酯化反应6 h，总酯含量可达98%。通过红外光谱、核磁共振确定了产物的结构。测定了产物的性能，并与原料性能进行比较分析。结果表明，产物具有更好的分散性能、乳化性能和耐碱性，是一种性能良好的多功能表面活性剂。
关键词：油酸酰胺聚氧乙烯醚（5）； 磷酸酯； 合成； 表面活性剂
中图分类号：TQ423.2 文献标识码：A 文章编号：0258-3283（2018）
Synthesis and Properties of OleatePolyoxyethyleneEther(5) Phosphate Ester ZHANG Yi-bo, ZHU Guo-hua*, YU Hong-mei, HUA Ping ( School of Chemistry and Chemical Engineering, Nantong University, Nantong 226019, China), Huaxue Shiji, 2018, 40(4)
Abstract: Oleate polyoxyethylene ether (5) phosphate ester (OAEFP) was synthesized by oleate polyoxyethylene ether (5) (OAEO5) using phosphorus pentoxide as phosphorylation reagent. The optimal reaction conditions were chosen through orthogonal test that the molar ratio of OAEO5 to phosphorus pentoxide was 2.5︰1, the esterification reaction temperature was 60, reaction time was 6 h. The total ester content was up to 98%. The structure was confirmed by IR. Performance of the product was compared with the raw material. Results showed that the product had better dispersion properties, emulsifying properties and alkali resistance. OAEFP was multifunctional surfactant with good properties.
Key words: oleatepolyoxyethylene ether (5); phosphate ester; synthesis; surfactant
6-氨基-7-甲氧基喹唑啉的合成
张帅波，金岩，李振建，刘潮，冯柏成*
（青岛科技大学 化工学院，山东 青岛 266042）
摘要：以3-硝基-4-氯苯甲酸为原料，经酯化、硝化、水合肼还原、环合、氯化、氢化等反应得到标题化合物。整个反应过程成本低、操作简便、节约时间、符合工业化的要求。探讨了还原2, 5-二硝基-4-氯苯甲酸甲酯时水合肼用量、反应温度、反应时间和催化剂的用量，氯化反应中氯化试剂、助溶剂以及温度等因素对目标产物的影响。结果表明，当n（2, 5-二硝基-4氯苯甲酸甲酯）: n（80%水合肼）= 1 : 2.5、反应温度为78 ℃、反应时间为3 h、FeCl3用量为0.6 g、活性炭用量为0.15 g时，还原效果最佳；以SOCl2为氯化试剂、DMF为催化剂，温度80 ℃时，收率及纯度最高。目标产物结构通过元素分析、13CNMR、IR、1HNMR以及MS确定，为新型酪氨酸激酶抑制剂的合成提供依据。
关键词：6-氨基-7-甲氧基喹唑啉；有机化合物；合成；酪氨酸激酶抑制剂；医药中间体
中图分类号：TQ460 文献标识码：A 文章编号：0258-3283（2018）
Synthesis of Tyrosine Kinase Inhibitor Intermediate ZHANG Shuai-bo, JIN Yan, LI Zhen-jian, LIU Chao, FENG Bai-cheng*（College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042，China），Huaxue Shiji, 2018, 40(3)
Abstract: A tyrosine kinase inhibitor intermediate 6-amine-7-methoxyquinazoline was synthesized from 3-nitro-4-chlorobenzene acid via esterification, nitration, hydrazine hydrate reduction, cyclization, chlorination, hydrogenation. The process is low cost, manipulation easily, and suitable for industrial production. The effects of hydrazine hydrate dosage, reaction temperature, reaction time and catalyst dosage were discussed, and the chlorination reagent, cosolvent, the reaction temperature on the target products were investigated. The optimal conditions were the molar ratio of n(2, 5-dinitro-4-methyl benzoate) : n(hydrazine hydrate)=1 : 2.5, reaction temperature 78 ℃, reaction time 3 h, 0.6 g FeCl3, 0.15 g activated carbon, the yield was best. When SOCl2 was used as the chlorination reagent and solvent, DMF was used as the catalyst, temperature was 80 ℃, the yield and purity were best. The structure of the target molecules was confirmed by elemental analysis, 13CNMR, IR, 1HNMR and MS, it could also provide evidence for the synthesis of tyrosine kinase inhibitors.
Key words：6-amine-7-methoxyquinazoline；organic compound；synthesis；tyrosine kinase inhibitor；medicine intermediate
3, 5-二碘苯磺酰氯的合成研究
郭理云a, b，赵庆平a, b，赵春深a, b，季春a, b，李焱*a, b, c
（贵州大学 a. 化学与化工学院，b. 药学院 贵州省合成药物工程实验室，c. 先进技术研究院，贵州 贵阳 550025）
摘要：标题化合物是一种重要的化工中间体，广泛应用于医药、农药、材料等领域。目前，此化合物的合成路线未见文献报道。以4-硝基苯胺作为起始原料，经取代、重氮化、还原和磺化4步反应得到了标题化合物，探索了碘化剂、硫酸质量分数、还原剂、反应温度和亚硝酸投料量对产品收率的影响，优化了工艺条件，总收率达56.28%。其化学结构经IR、MS、1HNMR和13CNMR确证。该方法原料廉价易得、操作简单、反应条件较为温和且收率较高，适合工业化生产。
关键词：4-硝基苯胺；3,5-二碘苯磺酰氯；合成
中图分类号：O626.1 文献标识码：A 文章编号： 0258-3283（2018）
Synthesis of 3, 5-Diiodobenzenesulfonyl Chloride GUO Li-yuna, b,ZHAOQing-ping a, b, ZHAO Chun-shen a, b, JI Chun a, b, LI Yan* a, b, c(a. School of Chemistry and Chemical Engineering, b. Guizhou Engineering Laboratory for Synthetic Drugs, School of Pharmacy, c. The Research Institute of Advanced Technology, Guizhou University, Guiyang 550003, China）, Huaxue Shiji, 2018, 40(3)
Abstract: 3, 5-Diiodobenzenesulfonyl chlorideis an important chemical intermediates, and is widely used in medicine, pesticides, materials and other fields. The synthetic route is not reported in the literature. In this paper, the target compound was synthesized by substitution, diazotization, reduction, and sulfonation with 4-nitroanilineas the starting material. The effects of the iodination agent, sulfuric acid concentration, reducing agent, reaction temperature and nitrite dosage on the yield of the product were investigated, the technological condition had been optimized. The total yield was 56.28%. The chemical structure was confirmed by IR, MS, 1HNMR and 13CNMR.The raw materials are cheap and easy to get in this method. It is easy to operate and controland the yield was higher in each step. It is suitable for industrial production.
Key words: 4-nitroaniline; 3, 5-diiodobenzenesulfonyl chloride; synthesis
环丙基甲酸的合成工艺研究
谢振东，高中良*，田帅
（河北工业大学 化工学院，天津 300130）
摘要：标题化合物是一种重要的化学中间体。在氯化锌的作用下，1, 4-丁内酯与异丙醇、SOCl2反应经一步开环-酯化生成4-氯丁酸异丙酯。在NaOH作用下，4-氯丁酸异丙酯合环缩合生成环丙烷甲酸异丙酯，优化环丙烷甲酸异丙酯水解酸化生成环丙基甲酸的工艺。在环丙基甲酸异丙酯水解之后，先蒸出异丙醇再酸化可以防止蒸馏过程中环丙基甲酸与异丙醇再次酯化生成环丙基甲酸异丙酯。并将文献中的萃取剂乙酸乙酯换为二氯甲烷，优点是除去了后处理过程中的副产物环丙烷甲酸乙酯和乙酸异丙酯。经优化后不仅减少了副反应而且提高了产率，总收率为75.1%。目标产物及中间体经1HNMR和IR表征并分析确认。
关键词：1, 4-丁内酯；相转移催化；环丙基甲酸；合成
中图分类号：TQ235 文献标识码：A 文章编号：0258-3283（2018）
Synthesis of Cyclopropyl Acid XIE Zhen-dong，GAO Zhong-liang*，TIAN Shuai（School of Chemical Engineering，Hebei University of Technology，Tianjin 300130，China）, Huaxue Shiji, 2018, 40(3)
Abstract：Cyclopropylcarboxylic acid is an important chemical intermediate. Under the action of thionyl chloride, 1, 4-butyrolactone and isopropanol, SOCl2 reaction by one-step ring-esterification to produce 4-chlorobutyric acid isopropyl ester. Under the action of NaOH, 4-chlorobutyric acid isopropyl ester ring condensation to produce cyclopropanecarboxylic acid isopropyl ester. Optimization of hydrolysis and acidification of isopropyl formate with cyclopropane to produce formic acid. The first distillation of isopropyl alcohol can be removed during the post-treatment cyclopropyl formic acid and isopropyl alcohol esterification again to produce propyl cyclopropylchloroformate. The isopropyl alcohol is distilled off and then the acid extract of the extractant in the original document is changed to methylene chloride. The advantage is that the by-product cyclopropanecarboxylic acid ethyl ester and isopropyl acetate are removed during the post-treatment. Optimized not only reduces side effects but also increases yield. The overall yield was 67.6%. The target product and intermediates were confirmed by 1HNMR and IR.
Key words: 1, 4-butyrolactone; phase transfer catalysis; cyclopropane carboxylic acid; synthesis
无溶剂乌尔曼反应高效合成吡啶胺
胡学成a, b，郑静a，郑春阳*a, b
（湖北师范大学 a. 化学化工学院，b. 文理学院，湖北 黄石 435002）
摘要：以2-溴吡啶和2-氨基吡啶为原料，通过采用改进后的乌尔曼反应，在无溶剂条件下，控制反应原料比例，高效地合成了两种多吡啶胺化合物，即2, 2'-二吡啶胺和2, 2', 2''-三吡啶胺。产物结构通过电喷雾质谱、核磁共振进行了确证和表征。另外，2, 2', 2''-三吡啶胺的高氯酸盐结构经X-射线衍射进行了确认。晶体结构显示，质子化的三吡啶胺盐中存在强烈的N…H‒N分子内氢键作用。
关键词：无溶剂；乌尔曼反应；合成；表征；晶体结构
中图分类号：O625.63 文献标识码：A 文章编号：0258-3283（2018）
Solvent-Free Synthesis of Pyridylamine Using Ullmann Reaction HU Xue-chenga, b, ZHENG Jinga, ZHENG Chun-yang*a, b(a. College of Chemistry and Chemical Engineering, b. School of Art and Science, Hubei Normal University, Huangshi 435002, China), Huaxue Shiji, 2018, 40(3)
Abstract: Two pyridylamine compounds (2, 2'-dipyridylamine and 2, 2', 2''-tripyridylamine) were effectively synthesized starting from 2-bromopyridine and 2-aminopyridine using Ullmann reaction under solvent-free condition and controlling the proportion of raw materials. The compositions and structures were characterized by ESI-MS, 1HNMR and 13CNMR, and the structure of 2·ClO4 was confirmed by single crystal X-ray diffraction.
Key words: solvent-free; Ullmann reaction; synthesis; characterization; single crystal
N-甲基-1-（甲硫基）-2-硝基乙烯胺的环保合成工艺
薛子桥1，田克情2，王娇1，杨田1，张萍*1
（1. 河北师范大学 化学与材料科学学院 化学国家级实验教学示范中心，河北 石家庄 050024；
2. 河北化工医药职业技术学院 化学与环境工程系，河北 石家庄 050026）
摘要：硝基甲烷和二硫化碳作用生成硫醇钾盐，再经胺化和甲基化反应是工业生产N-甲基-1-（甲硫基）-2-硝基乙烯胺主要采用的方法。该工艺产生的废气、废液无法处理，使整个生产受限。对该工艺进行了优化和改进，确定了甲基化反应的另一产物为硫酸单甲酯钾盐，研究了溶剂的回收使用、废气废液的处理，优化后的工艺成本降低、环保，适合工业化生产。3步反应的总收率为42%，外标含量为98.8%。
关键词：N-甲基-1-（甲硫基）-2-硝基乙烯胺 ；硫酸单甲酯钾盐； 废气废液处理
中图分类号：O622.3 文献标识码：A 文章编号：0258-3283（2018）
Environmental Synthesis Process of N-Methyl-1-(methylthio)-2-nitroethenamine XUE Zi-qiao1, TIAN Ke-qing2, WANG Jiao1, YANG Tian1, ZHANG Ping*1（1. National Demonstration Center for Experimental Chemistry Education, College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang 050024, China; 2. Environment and Chemical Engineering, Hebei Chemical and Pharmaceutical College, Shijiazhuang 050026, China）, Huaxue Shiji, 2018, 40(3)
Abstract：The main method of industrial production of N-methyl-1-(methylthio)-2-nitroethenamine is the formation of potassium thiolate through nitromethane and carbon disulfide followed the amination and methylation reactions. The waste gas and liquid produced by the process cannot be processed, so the whole production is limited. In this work, the process is optimized and improved, another product of the methylation reaction is determined to be potassium monomethyl sulfate, the recovery of solvent and the treatment of waste gas and liquid are also investigated. The optimized process is lower cost, environmental and suitable for industrial production. The total yield is 42% by 3 steps reaction, and the external standard content is 98.8%.
Key words：N-methyl-1-(methylthio)-2-nitroethenamine; potassium monomethyl sulfate; waste gas and liquid treatment
超声辅助铜催化合成α-卤代甲基酮
兰立新，肖洁，鄢东，易卫国*
(湖南化工职业技术学院 制药与生物工程学院，湖南 株洲 412000)
摘要：α-卤代甲基酮不仅是有机合成的重要中间体，也是许多药物分子中的重要结构片段。发展了超声辅助下铜催化卤代炔烃水合反应制备α-卤代甲基酮化合物的新方法。考察了反应催化剂的种类、酸的种类、反应温度以及溶剂对反应的影响。研究结果表明，在超声条件下，以5 mol% Cu(OTf)2为催化剂，40 ℃反应1 h，卤代炔烃能够以良好的反应产率反应得到水合产物α-卤代甲基酮。该反应具有广泛的反应底物适用性，为高效合成含有α-卤代甲基酮结构的复杂化合物提供了一种新的途径。
关键词：水合反应；铜催化；超声；α-卤代酮
中图分类号：O621.25 文献标识码：A 文章编号：0258-3283（2018）
Synthesis of a-Haloketones by Ultrasound-promoted Copper-catalysis LAN Li-xin, XIAO Jie, YAN Dong, YI Wei-guo*( , Hunan Chemical Vocational Technology College, Zhuzhou 412000, China), Huaxue Shiji, 2018, 40(3)
Abstract：α-Halomethylketones are very improtant synthetic intermediates as the building blocks for the synthesis of various drug molecules. A novel ultrasound-promoted highly efficient synthesis of a wide range of α-halomethylketones from haloalkynes is described. The influences of catalyst, acid, reaction temperature and solvent were investigated, the result indicated that the reaction proceeds smoothly to give the corresponding products in good yields using 5 mol% Cu(OTf)2 for 1 h at 40 ℃. The structure of α-halomethylketone derivatives was confirmed by 1HNMR, 13CNMR and MS. The reactions are conducted under convenient conditions and with excellent yields, with broad substrate scope, including a variety of aromatic chloroalkynes and bromoalkynes.
Keywords：hydration reaction; copper catalysis; ultrasound; α-halomethylketone
