石墨烯/氧化亚铜界面交互作用对储锂性能的影响

张小廷^{* 1, 2}，刘程程^{1, 3}，周继升¹，曹炬²，陈晓红¹，宋怀河¹

（1. 北京化工大学 化工资源有效利用国家重点实验室，北京  100029；2. 北京万源工业有限公司 石墨烯与储能技术研究中心，北京  100176；3. 清华大学 化学系，北京  100084）

摘要：通过一种简单的液相法以及随后的热处理合成了石墨烯/氧化亚铜复合材料（Cu₂O/GNSs）。通过扫描电子显微镜、透射电子显微镜、X射线衍射以及X射线光电子能谱对复合材料的形貌和结构进行了表征。当复合材料作为锂离子电池负极材料时，在50 mA/g电流密度下，首次可逆容量为447.5 mAh/g，经过90次循环以后，容量增加到613.5 mAh/g。在500和1000 mA g^-1下，可逆容量依然可达443.7和346.5 mAh/g，分别为50 mA/g电流密度下容量的99.1%和77.4%。Cu₂O/GNSs较高的容量以及优异的倍率性能应当归结于石墨烯与氧化亚铜之间的协同作用。

关键词：界面交互作用；石墨烯；氧化亚铜；锂离子电池

中图分类号：TB333       文献标识码：A      文章编号：0258-3283（2017）

Interfacial Interaction of Graphene/Cuprous Oxide and Its Impact on Li-ion Storage Performance ZHANG Xiao-Ting^{*1, 2}, LIU Cheng-Cheng^{1, 3}, ZHOU Ji-Sheng¹, CAO Ju², CHEN Xiao-Hong¹, SONG Huai-He¹

(1. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China; 2. Graphene and Energy Storage R&D Centre, Beijing Wanyuan Industry Co., Ltd., Beijing 100176, China; 3. Department of Chemistry, Tsinghua University, Beijing 100084, China), Huaxue Shiji, 2017, 39(7)

Abstract：Graphene/cuprous oxide hybrid material (Cu₂O/GNSs) was prepared by a simple solution method and subsequent annealing. The morphology and structure of as-prepared Cu₂O/GNSs composite was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectra (XPS). The Cu₂O/GNSs, used as an anode material, exhibited a reversible capacities of 447.5 mAh/g for the first charge process and 613.5 mAh/g after 90 cycles at 50 mA/g, respectively. At 500 and 1000 mA/g, the reversible capacities can reach 443.7 and 346.5 mAh/g, which are 99.1 % and 77.4 % of that at 50 mA/g. The high capacity and excellent rate performance could be attributed to the synergistic effect between Cu₂O and GNSs.

Key words: interfacial interaction; graphene; Cu₂O; lithium-ion battery

基于Mn-MOF的多孔碳/MnO复合材料的制备及催化性能研究

田小兵^1,3，丁艳花²，张小磊²，房永征²，张娜^*2

(1.武汉理工大学 资源与环境工程学院，湖北 武汉  430070； 2.上海应用技术大学 材料科学与工程学院，上海  201418；3.上海风享环保科技有限公司，上海  200436)

摘要：首先通过溶剂法制备甲酸锰（Mn-MOF）晶体，接着以Mn-MOF为前驱体，在惰性条件下制备了结构、形貌可控的多孔碳/MnO复合物。采用XRD、BET和SEM手段表征Mn-MOF前驱体和多孔碳/MnO复合物的结构、形貌等。结果表明，600 ℃下获得的多孔碳/MnO复合物含有立方相MnO和无定型多孔碳。将多孔碳/MnO复合物催化臭氧分解，催化率可达92.3%，重复利用性好。

关键词：甲酸锰晶体；多孔碳/MnO；臭氧；催化效率；

中图分类号: O643          文献标识码: A      文章编号：0258-3283（2017）

Preparation and Catalytic Property of Porous Carbon/MnO Composite Derived from Mn-MOF TIAN Xiao-bing¹，DING Yan-hua²，ZHANG Xiao-lei²，FANG Yong-zheng²，ZHANG Na^*2 (1. School of Resources and Environment, Wuhan University of Technology, Wuhan 430070, China; 2. School of Materials Science and Engineering, Shanghai Institute of Technology, Shanghai 201418, China; 3. Shanghai fanshare Co. Ltd., Shanghai 200436, China), Huaxue Shiji, 2017, 39(7)

Abstract: In this work, firstly, the formic acid manganese crystals (Mn-MOF) is successfully prepared by hydrothermal solvent method. Secondly, Mn-MOF precursor is calcinated at various temperature under nitrogen environment to obtain various porous carbon (PC)/MnO composite. At last, a series measurements including XRD, BET and SEM are employed to investigate the nanostructure and morphology of the Mn-MOF and PC/MnO composite. The results indicate that PC/MnO composite acquired at 600℃ composes of the cubic MnO and amorphous carbon. At the same time, the PC/MnO composite at 600 ℃ possesses the superior thermal catalytic property and the conversion of O₃ can be up to 92.3%, with the good recyclable performance.

Key words: Mn-MOF；C / MnO；ozone；MB；catalytic efficiency

原位聚合法制备聚酰胺6/ZnO纳米复合材料及性能研究

徐启杰，胡鹏^*，张爽，吉同超，张宁，潘庆才

（黄淮学院 化学化工系，河南 驻马店  463000）

摘要：以Zn₂(OH)₂CO₃为填料，采用原位生成法制备聚酰胺6/ZnO纳米复合材料。利用透射电子显微镜(TEM)、X射线衍射仪(XRD)、热重分析仪(TGA)、差热扫描量热仪(DSC)测试了纳米ZnO的粒径和分散性能，复合材料的结晶性能、热稳定性能。结果显示，Zn₂(OH)₂CO₃在聚酰胺6聚合体系中能够原位生成纳米ZnO，并均匀分散于聚酰胺6基体材料中。纳米ZnO在聚酰胺6基体材料中具有异相成核作用，提高了聚酰胺6的结晶度，然而对基体材料分子链运动的阻碍作用降低了结晶速率和晶体尺寸。通过万能拉力试验机、冲击试验机和高速环块摩擦试验机研究了纳米ZnO对聚酰胺6基体材料的力学性能和摩擦学行为的影响。当纳米ZnO的含量为0.2%时，拉伸强度和冲击韧性较纯聚酰胺6提高了75%，对摩擦学行为也有较好的改善作用。

关键词：复合材料；性能；测试；纳米ZnO

中图分类号：O635     文章标识码：A     文章编号：0258-3283（2017）

Preparation and Properties of Polyamide 6/ZnO Nanocomposite via In-situ Method XU Qi-jie，HU Peng^*, ZHANG Shuang, JI Tong-chao, ZHANG Ning, PAN Qing-cai (Department of Chemistry and Chemical Engineering, Huanghuai University, Zhumadian 463000, China), Huaxue Shiji, 2017, 39(7)

Abstract: The polyamide 6/ZnO nanocomposite was prepared readily by in-situ polymerization, with which Zn₂(OH)₂CO₃ was used as filler. This method was beneficial to reduce the calcining process of Zn₂(OH)₂CO₃ to obtain ZnO and the production cost of the preparation of polymer-nanoparticle composites. As-prepared composite was characterized by using X-ray diffractometer (XRD), thermogravimetric analyzer (TGA), differential thermal scanning calorimeter (DSC), and polarizing microscope (POM) to test the crystallization properties and thermal stability. The mechanical properties and friction performance of composite were evaluated via using high-speed ring friction testing machine, universal tensile testing machine, impact testing machine. As-obtained results showed that nano-ZnO was derived from Zn₂(OH)₂CO₃ in the process of in-situ polymerization of PA6/ZnO nanocomposite. Moreover, nano-ZnO with heterogeneous nucleation effect in the composite led to the improvement of the crystallinity of polyamide 6. Additionally, due to the hindering effect of nano-ZnO on the  movement of PA6 molecular chains, that reduced crystallization rate and crystal size of PA6 matrix. The results indicated that the mechanical properties and tribological properties of PA6/ZnO nanocomposites had the improvement than that of pure polyamide 6.

Key words: composite materials; performance; test; nano-ZnO

光谱法研究喹啉黄与牛血清白蛋白的相互作用及金属离子的影响

赵刚¹，殷志全¹，伊鲁东¹，董殿波²，赵芳³，顾佳丽^*1

（1. 渤海大学 化学化工学院，辽宁 锦州  121013；2. 辽宁省环境科学研究院，辽宁 沈阳  101613；3. 葫芦岛市连山区环境保护局，辽宁 葫芦岛  110160）

摘要：偶氮类人工合成色素喹啉黄影响儿童智力发育，被美国、欧盟等国家在食品中禁用。采用荧光和紫外光谱法研究了模拟生理条件下喹啉黄与牛血清白蛋白(BSA)的相互作用机制及常见金属离子(Cu²⁺、Zn²⁺、Mg²⁺)对BSA-喹啉黄体系的影响。实验结果表明，在金属离子存在下，喹啉黄对BSA的猝灭过程仍为静态猝灭，但作用力强弱有所变化，Zn²⁺、Mg²⁺的参与未改变喹啉黄与BSA之间的主要作用力，Cu²⁺的参与使两者之间的作用力由范德华力转变为疏水作用力。

关键词：喹啉黄；牛血清白蛋白；荧光猝灭

中图分类号：O657.3      文献标识码：A      文章编号：0258-3283（2017）

Effect of Metal Ionson the Interaction of Quinoline Yellow with Bovine Serum Albumin ZHAO Gang¹, YIN Zhi-quan¹, YI Lu-dong¹, DONG Dian-bo², ZHAO Fang³,GU Jia-li^*1 (1.College of Chemistry and Chemical Engineering, Bohai University, Jinzhou 121013, China; 2.Liaoning Academy of Environmental Sciences, Shenyan 110160, China; 3.Huludao Municipal Environmental Protection Bureau, Huludao 125001, China), Huaxue Shiji, 2017, 39(7)

Abstract: Quinoline yellow(Qy) has been banned in food by the European Union and othercountries and regions, because it can negatively affect on children'sintellectual development. The interaction between Qyand bovine serum albumin(BSA)under simulative physiological conditions was investigated by fluorescence spectrum and UV-vis spectrum. The effect of metal ions (Cu²⁺, Zn²⁺ and Mg²⁺) on the BSA-Qy system was also researched. The results indicated that the quenching mechanism of BSA by Qy was a static procedurewith the presence of metal ions. The quenching constant K_sv and K_pof Qy and BSA were increased, but the binding constant K was decreased in the presence of Cu²⁺ and Zn²⁺. The presence of Cu²⁺ changed the interaction pattern between Qy and BSA from Waals forces to hydrogen bonds.

Key words: quinoline yellow；bovine serum albumin；fluorescence quenching

一种湿固化聚氨酯的合成、表征及在文物中的应用

赵星¹，王丽琴*¹，卞尚¹，赵西晨²，董欣欣¹，乔成全¹

（1.西北大学 文化遗产学院 文化遗产研究与保护技术教育部重点实验室，陕西 西安 710069；

2. 陕西省考古研究院，陕西 西安 710054）

摘要：研制了一种文物保护用湿固化聚氨酯加固剂，利用分光光度计、万能材料试验机等对其透光性、机械性能和吸水性进行了表征，并应用于出土竹笥和炭化宣纸的加固保护。实验结果表明，聚氨酯薄膜无色透明，可见光区透光率为90%；断裂延伸率高达351.09%；水浸泡24 h后吸水率达53.65%，干燥后未出现明显形变，韧性和质量基本恢复到浸泡前状态。加固后竹笥和炭化宣纸的机械性能显著提高，加固效果良好；炭化宣纸表面肉眼无法识别的字迹信息经多光谱摄影后清晰可见。该研究为高湿环境下脆弱有机质文物加固、炭化纸质文物字迹恢复提供了一条新的途径。

关键词：湿固化聚氨酯；加固剂；高湿环境；有机质文物

中图分类号：TQ323.8；K854.3    文献标识码：A    文章编号：0258-3283（2017）

Synthesis and Application of Moisture Curable Polyurethane as theConsolidant for Cultural Relics ZHAO Xing¹, WANG Li-qin^*1, BIAN Shang¹, ZHAO Xi-chen², DONG Xin-xin¹, QIAO Cheng-quan¹ (1. Key Laboratory of Cultural Heritage Research and Conservation, College of Cultural Heritage, Northwest University, Xi′an 710069, China；2. Shanxi Archaeological Institute, Xi′an 710054, China), Huaxue Shiji, 2017, 39(7)

Abstract: The commonly used conservation materials for cultural relics nowadays could easily become whitish and showed poor ability of hardening when they were implemented in the archaeological excavation sites of high humidity. Accordingly, it could not meet the demand of being utilized on the fragile organic remains’ conservation. In this work, a kind of moisture curable polyurethane (MCPU) for the conservation of cultural relics was synthesized to solve the problems. Instruments such as a spectrophotometer and a universal material testing machine were utilized to test the transmittance, mechanical property and water absorption ability of MCPU. In addition, MCPU was performed to consolidate the carbonizedxuan paper and the zhusi residues (a kind of vessels which was made of plant fiber) excavated in the archaeological sites. The results illustrated that the cured MCPU film was transparent with 90% light transmittance within 400nm to 700nm range and the fracture elongation rate could reach 351.09%. The water absorption rate climbed to 53.65% after being immersed in water for 24 hours, the toughness and quality recovered to the original conditions before immersion and there were no discolorations, blisters, spots or obvious deformations after dehydration. The consolidation experiment showed that the mechanical properties of the zhusi and the carbonized xuan paper improved significantly after reinforcement with MCPU, and the manuscript information which could not be observed on the carbonized xuan paper could be clearly identified by a multispectral photography. Consequently, this work provides a new way for the consolidation of fragile organic relics in the humid environment and as well as the recovery of the manuscript on carbonized paper.

Key words: moisture curable polyurethane(MCPU)；consolidant；humid environment；organic relics

含Shiff碱结构的2-芳胺基嘧啶衍生物的合成

及体外抗肿瘤活性研究

李亚巍¹，孙勇兵²，王丹¹，殷世亮^*3，昌盛^*1

(1. 吉林医药学院 药学院，吉林 吉林  132013；2. 江西中医药大学 中药固体制剂制造技术国家工程研究中心，江西 南昌  330004；3. 沈阳医学院 基础医学院，辽宁 沈阳  1100342)

摘要：以2-甲基苯胺、3-乙酰基吡啶、N, N二甲基甲酰胺二甲基缩醛为起始原料，经硝化、加成、环合、还原、缩合等5步反应合成目标化合物。以伊马替尼为阳性对照药，采用台盼兰排染法，以慢性粒细胞白血病K562细胞为测试细胞株，对目标化合物进行体外抗白血病活性评价。所合成的18个化合物经¹HNMR和MS确证结构。初步药理实验结果表明，目标化合物对K562细胞有一定的抗肿瘤活性，但低于阳性对照药。酰胺键结构对保持活性有重要的影响，是药物与受体的重要结合位点。

关键词：2-芳胺基嘧啶衍生物；化学合成；抗肿瘤活性；Shiff碱；伊马替尼

中图分类号：R914.5       文献标识码：A          文章编号：0258-3283（2017）

Synthesis and Biological Evaluation of 2-Phenylaminopyrimidine Schiff BaseDerivatives LI Ya-wei¹，SUN Yong-bing²，WANG Dan¹，YIN Shi-liang^*3，Sheng Chang^*1 (1. College of Pharmacy, Jilin Medical University, Jilin 132013, China；2. National Engineering Research Center of Chinese Medicine Solid Preparation Manufacturing Technology，Jiangxi University of Traditional Chinese Medicine, Nanchang 330004, China；3.          , Shenyang Medical College，Shenyang 110034, China), Huaxue Shiji, 2017, 39(7)

Abstract: In order to elucidatethe structure-activity relationship of PAP derivative, a series of Imatinib analogues with Schiff base bearing PAP moiety were synthesized. The target compounds were synthesized by 6 steps with 2-methyl-5-nitroaniline, 3-acetylpyridine, DMF-DMA as the startmaterials. These compounds were tested to inhibit human leukemia cell lines K562 using trypan blue exclusion staining with Imatinib as positive control. The structures of the novel compounds were confirmedby ¹HNMR and MS. Preliminary pharmacological results showed that all of the compounds possessed potent antitumor activities but lower than Imatinib and lead compound. We considered that amide linkage is must be required to maintain the activity.

Key words: 2-phenylaminopyrimidine derivatives；synthesis；antitumor activity；Schiff base；Imatinib

乙酸1-氰基-2,2,2-三氟-1-苯乙酯的合成及表征

李腾，黄桂兰^*，袁铃，周世坤，杨旸

（防化研究院，北京  102205）

摘要：以氰化钠、三氟苯乙酮、乙酸酐为原料，通过亲核及酯化反应合成了标题化合物。实验考察了无水四氢呋喃、无水硝基甲烷溶剂对反应的影响，结果表明该反应在四氢呋喃溶剂中常温下即可顺利进行，且副产物较少，产率为76.3%。提纯后的化合物经NMR、HPLC-TOF/MS和GC-EI/MS进行结构表征，并考察了该化合物在不同溶剂中的稳定性及低浓度氰化钠衍生为目标化合物的衍生效率。

‍关键词：乙酸1-氰基-2,2,2-三氟-1-苯乙酯；氰化钠；三氟苯乙酮；合成；表征‍

中图分类号：O621.3                文献标识码：A           文章编号：0258-3283（2017）

Synthesis and Characterization of 1-Cyano-2,2,2-trifluoro-1-phenylethyl Acetate LI Teng，HUANG Gui-lan^*，YUAN Ling，ZHOU Shi-kun，YANG Yang（Research Institute of Chemical Defence，Beijing  102205，China）, Huaxue Shiji, 2017, 39(7)

Abstract：The compound of 1-cyano-2,2,2-trifluoro-1-phenylethyl acetate was synthesized from the sodium cyanide, 2, 2, 2-trifluoro acetophenone, acetic anhydride via the nucleophilic and esterification reactions. The influence for the synthesis reaction when using the anhydrous nitromethane and anhydrous tetrahydrofuran as reaction solvent was investigated. The results indicated that the reaction could be carried out smoothly and stably in tetrahydrofuran at room temperature and contained fewer by products with the yield of 76.3%. After purification, the structure was confirmed by NMR, HPLC-TOF/MS and GC-EI/MS. The stability of the compound in different solvents and the derivatization efficiency of the low concentration sodium cyanide derivative as the target compound were elucidated.

Key Words：1-cyano-2,2,2-trifluoro-1-phenylethylacetate；sodium cyanide；2, 2, 2-trifluoro acetophenone；synthesis；characterization

磁性二氧化钛-磷钨酸复合催化剂的制备及光催化性能研究

陈树娇，韩敏阳，刘忠成，牛萍^*

（德州学院 化学化工学院 山东省功能材料与配位化学高校重点实验室，山东 德州  253023）

摘要：采用层层自组装法成功制备了兼具磁性和光催化活性的双功能Fe₃O₄@SiO₂/(TiO₂/PW₁₂)₁₀复合微球，采用扫描电镜、红外光谱和X-射线能谱仪对所得微球进行了结构和形貌的表征。以甲基橙为模型污染物，研究了紫外光下Fe₃O₄@SiO₂/(TiO₂/PW₁₂)₁₀的光催化性质，系统考察了甲基橙溶液的初始浓度、溶液pH和无机氧化剂碘酸钾对复合膜催化效率的影响。动力学研究表明，在不同浓度甲基橙溶液中，染料的光催化降解遵循表观一级反应动力学。磁性Fe₃O₄纳米粒子的使用实现了反应后方便、快速和高效地分离回收催化剂。

关键词：TiO₂；磷钨酸；层层自组装；磁性微球；光催化性质

中图分类号：O611.3        文献标识码：A        文章编号：0258-3283（2017）

Fabrication of Titanium Dioxide-Tungstophosphate Acid Magnetic Microspheres and Photocatalytic Performance CHEN Shu-jiao, HAN Min-yang, LIU Zhong-cheng, NIU Ping^*(Key Laboratory of Coordination Chemistry and Functional Materials in Universities of Shandong, College of Chemistry and Chemical Engineering, Dezhou University, Dezhou 253023, China), Huaxue Shiji, 2017, 39(6)

Abstract：Photocatalytic microspheres (TiO₂/PW₁₂)₁₀ on magnetic Fe₃O₄@SiO₂ core-shell microspheres were fabricated by electrostatic layer-by-layer (LbL) self-assembly method. The microspheres were characterized by scan electron microscopy (SEM) and infrared spectroscopy (IR). Photocatalytic activities of obtained hybrid magnetic microspheres were tested via the degradation of aqueous methyl orange solution under UV irradiation. The effect of initial dye concentration, pH of solution and inorganic oxidant such as KIO₃ on MO degradation were checked in detail. Kinetics of MO photodegradation has been found to follow the first-order reaction at different initial concentration. The easy, fast and efficient separation of catalyst after catalytic reaction was achieved by the use of magnetic Fe₃O₄ substrate.

Key words: titanium dioxide; tungstophosphate acid; LbL self-assembly; magnetic microspheres; photocatalytic performance

1-（2-吡啶基）-3-甲基-4-三氟甲酰基-5-吡唑酮的合成

及其与Fe³⁺显色反应研究

刘华¹，赵春香²，郑大军³，刘念²，丁永杰^*2

（1. 河南省周口水文水资源勘测局，河南 周口  466003；2. 周口师范学院 化学化工学院，河南 周口 466001；3. 河南省周口市粮油产品质量监督检测中心，河南 周口  466001)

摘要：合成了新型的酰基吡唑啉酮标题化合物，通过红外、核磁、质谱和元素分析对其进行表征，并研究了其与Fe³⁺的显色反应。实验结果表明，该化合物对Fe³⁺具有高选择的显色反应特性，当Fe³⁺在0.18 ～ 1.8 μg/mL范围内与相对的吸光度呈良好的线性关系A = 0.423ρ－0.020（μg/mL），相关性系数为r = 0.9993，最低检出限为0.064 µg/mL（n = 11）。

关键词：酰基吡唑啉酮；光度法；Fe³⁺

中图分类号：O657.3          文献标识码：A          文章编号： 0258-3283（2017）     

Synthesis of 1-(2-Pyridyl)-3-methyl-4-trifluoroacetylpyrazol-5-one and Its Chromogenic Reaction with Fe³⁺ LIU Hua¹, ZHAO Chun-xiang², ZHENG Da-jun³, LIU Nian², DING Yong-jie^2*(1.Zhoukou Hydrology and Water Resources Survey Bureau, Zhoukou 466003, China; 2. College of Chemistry and Chemical Engineering, Zhoukou Normal University, Zhoukou 466001, China; 3.Zhoukou Grain and Oil Products Quality Supervision Detection Center, Zhoukou 466001, China), Huaxue Shiji, 2017, 39(7)

Abstract：A novel 4-acylpyrazolones compound of 1-(2-pyridyl)-3-methyl-4-trifluoroacetyl- pyrazol-5-one (PMTP) was synthesized. The structure was confirmed by IR, ¹HNMR, ESI-MS and elemental analysis. The color reaction PMTP and Fe³⁺ has been investigated in detail. The results showed that the PMTP has highly selectivity for Fe³⁺ in the chromogenic reaction. The absorbance (A) of the complex had good linear relationship with the contents of Fe³⁺ from 0.18 ～ 1.8 μg/mL. The liner regression equation was A ＝ 0.423ρ－0.020（μg/mL）with a detection limit of 0.064 µg/mL（n ＝ 11）and the linear correlation coefficient was 0.9993.

Key words：acylpyrazolone；spectrophotometry；iron(III)

六氟锑酸盐离子液体的研究进展

韩升，曾纪珺，唐晓博，张伟^*，杨志强，郝志军，吕剑^*

（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：六氟锑酸盐离子液体，具有常规离子液体的特性，如低蒸汽压、不挥发、物质溶解性好等，不仅可以作为溶剂，还可以通过调配阴阳离子比例或离子交换得到路易斯酸催化剂，在多种类型反应中得到应用。本文主要对近年来六氟锑酸盐离子液体的合成、结构、性质及其在反应中的应用进行综述。

关键词：六氟锑酸盐离子液体；合成；结构；应用

中图分类号：O645.13    文献标识码：A      文章编号：0258-3283（2017）

Progress in Hexafluoroantimonate Ionic Liquids HAN Sheng，ZENG Ji-jun，TANG Xiao-bo，ZHANG Wei^*，YANG Zhi-qiang，HAO Zhi-jun，LV Jian^* (State Key Laboratory of Fluorine & Nitrogen Chemical, Xi’an Modern Chemistry Research Institute, Xi’an 710065, China), Huaxue Shiji, 2017, 39(7)

Abstract:Hexafluoroantimonate ionic liquids have the characteristics of conventional ionic liquids, such as low vapor pressure, non-volatile, good solubility and so on. They can not only be used as solvent, but also can be used as Lewis acid catalysts via altering the ratio of anion and cation or ion exchange. Thus, they have been applied in various types of reactions. In this work, summary about the synthesis, structure, property and application in the reaction of hexafluoroantimonate ionic liquids in recent years has been done.

Key words: hexafluoroantimonate ionic liquids; synthesis; structure; application

双金属氰化络合物（DMC）催化有机反应的研究进展

周钰^{1, 2}，唐喆²，许琦^*2

（1.常州大学 石油化工学院，江苏 常州  213164；

2. 盐城工学院 化学化工学院，江苏 盐城  224051）

摘要：双金属氰化络合物（DMC）是一类少见的可催化多种反应体系的高效催化剂。该类催化剂被用来催化共聚反应合成聚酯、聚碳酸酯、聚（醚-碳酸酯）、聚硫代碳酸脂和聚（碳酸酯-酯）等多种生物降解性的聚合物。由于该类催化剂属于非均相催化剂，对其催化机理的认识仍处于经验层面，极大地限制了其发展和应用。本文总结了DMC在催化各类有机反应方面的研究进展，尤其对催化机理的认识和进展，旨在为人们认识其催化机制提供参考价值，并据此展望其在未来的发展趋势。

关键词：双金属氰化络合物；共聚反应；高效催化

Progress of Organic Reactions Catalyzed by Double Metal Cyanide Complex ZHOU Yu^1,2, TANG Zhe², XU Qi^*2 (1. College of Chemistry and Chemical Engineering, Changzhou University, Changzhou 213164, China; 2. School of Chemistry and Chemical Engineering, Yancheng Institute of Technology, Yancheng 224051, China), Huaxue Shiji, 2017, 39(7)

Abstract: The double metal cyanide complex (DMC) is a rare and highly efficient catalyst for a variety of reaction systems. This kind of catalyst was utilized to catalyze the alternating copolymerization for producing of polyester, polycarbonate, poly (ether carbonate), poly carbonate ester and poly (carbonate ester) with biodegradable polymer. Because this kind of catalyst belongs to heterogeneous catalyst, the catalytic mechanism is still in the level of experience and isn’t clear, which greatly limits its industrial application. This work summarizes the progress of DMC in various organic reactions, especially the catalytic mechanism in order to provide some information of DMC catalytic mechanism, and looks forward to the future development trend.

Key words: double metal cyanide complex；copolymerization；high efficiency catalyst

溴乙酰溴中二溴乙酰溴杂质分析方法研究

李乘欣，王雪萍，崔锋^*

（中国医药工业研究总院 上海医药工业研究院，上海  201203）

摘要：建立了间接测定溴乙酰溴中二溴乙酰溴含量的HPLC方法。将溴乙酰溴水解生成溴乙酸，辅以LC-MS技术，对其主要杂质进行定性研究。采用十八烷基硅烷键合硅胶柱，流动相为V (10 mmol/L三乙胺溶液)︰V (乙腈) = 5 : 95，检测波长为205 nm。溴乙酸与二溴乙酸在0.001 ～ 1.0 mg/mL 浓度范围内线性关系良好，平均回收率为99.3%，RSD 为0.87%，二溴乙酸相对校正因子为0.37。高效液相色谱法与离子色谱法测定结果一致，方法准确可靠，适于对溴乙酰溴原料中二溴乙酰溴杂质的控制。

关键词：溴乙酰溴；二溴乙酰溴；HPLC；LC-MS；离子色谱法

中图分类号：O657.7          文献标识码：A             文章编号：0258-3283（2017）

Determination of Dibromoacetyl Bromide Impurity in Bromoacetyl Bromide LI Cheng-xin, WANG Xue-ping, CUI Feng^*(Shanghai Institute of Pharmaceutical Industry, China State Institute of Pharmaceutical Industry, Shanghai 201203, China), Huaxue Shiji, 2017, 39(6)

Abstract: HPLC method was established for indirectly determining dibromoacetyl bromide impurity in bromoacetyl bromide. Bromoacetyl bromide was hydrolyzed into bromoacetic acid and a LC-MS method was used to do qualitative analysis of the main impurities in bromoacetyl bromide. A Thermo Acclaim 120 C18 column was used with the mobile phase of 10 mmol/L triethylamine solution (adjusted to pH 5.0 with phosphoric acid) : acetonitrile (5 : 95) at the detection wavelength of 205 nm. It was linear in the concentration range of 0.001 ～ 1.0 mg/mL for bromoacetic acid and dibromoacetic acid. The average recoveries of dibromoacetic acid were 99.3%, with RSDs of 0.87%. The relative correcting factors of dibromoacetic acid was 0.37. The quantitative result was no significant difference between using HPLC and ion chromatography. This method is accurate and reliable, and is suitable for detection of dibromoacetyl bromide in bromoacetyl bromide.

Key words: bromoacetyl bromide; dibromoacetyl bromide; HPLC; LC-MS; ion chromatography

气相色谱内标法测定食品接触制品水基模拟物中

环氧氯丙烷迁移量

王海波^*1，朱晓艳¹，吴倩¹，金米聪²，卢波¹

（1.宁波出入境检验检疫局，浙江 宁波  315012；2. 宁波市疾病预防控制中心 浙江省微量有毒化学物健康风险评估技术研究重点实验室 宁波市毒物研究与控制重点实验室，浙江 宁波  315010）

摘要：对于食品接触制品水基模拟物中环氧氯丙烷迁移量的测定，采用液液萃取法，简单高效。选择与待测物性状相近的环氧已烷作为内标物，采用内标法可以消除一些操作过程、仪器等因素的影响，使检测结果更加准确。比较外标法和内标法的回收率、精密度，结果显示采用外标法回收率为80.4% ～ 92.3%，内标法回收率为89.5% ～ 101.1%，同时内标法精密度更高。采用气相色谱FID检测器，内标法检出限为0.002 mg/kg，达到欧盟对食品接触制品模拟物中环氧氯丙烷迁移量的要求。

关键词：食品接触制品；环氧氯丙烷；内标法；迁移量

中图分类号：O657.7            文献标识码：A       文章编号：0258-3283（2017）

Determination of Epichlorohydrin Migration in Aqueous Food Contact Articles Simulants by Internal Standard Gas Chromatography WANG Hai-Bo^*1, ZHU Xiao-Yan¹, JIN Mi-Cong²，LU Bo¹(1.Ningbo Entry-Exit Inspection and Quarantine Bureau, Ni ngbo 315012, China; 2. Ningbo Municipal Center for Disease Control and Prevention, Key Laboratory of Health Risk Appraisal for Trace Toxic Chemicals of Zhejiang Province, Ningbo Key Laboratory of Poison Research and Control, Ningbo 315010, China), Huaxue Shiji, 2017, 39(7)

Abstract: For determination of epichlorohydrin migration in aqueous simulants of food contact articles, the liquid-liquid extraction method is simple and effective. Selecting epoxyhexane as the internal standard substance for its similar traits with epichlorohydrin, internal standard method can eliminate some operating procedural and instrumental impacts and make the results more accurate. The recovery rate of internal standard method is 90.8% ～ 101.1%, while that of external standard method recovery rate is 80.4% ～ 92.3%. Meanwhile, the precision of internal standard method is also superior to that of external standard method. The internal standard method detection limit using GC-FID is 0.002 mg/kg which meets EU requirements of epichlorohydrin migration in food contact articles simulants.

Key words: food contact articles；epichlorohydrin；internal standard method；migration

气相色谱法测定含糖食品中2-（4-甲氧基苯氧基）-丙酸钠

张翠芬¹，孙雪丽¹，董伟峰^*2，颜美³，李妍²，曹际娟²

（1. 大连职业技术学院 旅游与酒店管理学院，辽宁 大连  116035； 2. 辽宁出入境检验检疫局，辽宁 大连  116001；3. 大连工业大学 轻工与化学工程学院，辽宁 大连  116034）

摘要：利用气相色谱（FID）技术，对各种含糖食品中的抑甜剂2-（4-甲氧基苯氧基）-丙酸钠进行检测。样品酸化后，经乙醚提取，用带有FID检测器的气相色谱仪进行分离测定。方法的检出限为0.4 g/kg，平均回收率为91.2% ～ 107.7%，平均相对标准偏差（RSD）为3.6% ～ 4.6%。该方法能够满足一般含糖食品中2-（4-甲氧基苯氧基）-丙酸钠检测的需要。

关键词：含糖食品；2-（4-甲氧基苯氧基）-丙酸钠；气相色谱

中图分类号：TS202.3        文献标识码：A       文章编号：0258-3283（2017）

Determination of Sodium 2-(4-Methoxyphenoxy)propionate in Food Containing Sugar by Gas Chromatography ZHANG Cui-fen¹, SUN Xue-li ², DONG Wei-feng ², YAN Mei³, LI Yan² , CAO Ji-juan² ( 1. Dalian Vocational＆Technical College, Dalian 116035, China; 2. Liaoning Entry-Exit Inspection and Quarantine Bureau, Dalian 116001, China; 3. Dalian Polytechnic University, Dalian 116034, China), Huaxue Shiji, 2017, 39(6)

Abstract: In this work, the sodium 2-(4-methoxyphenoxy) propionate was detected by gas chromatography(FID). Samples were extracted with ether after acidification, the samples were separated and determined by the meteorological chromatograph with hydrogen flame ionization detector. The detection limit of the method is 0.4g/kg, the average recovery rate is 91.2% ～ 107.7%, the average relative standard deviation(RSD) is in 3.6% ～ 4.6%. The method can meet the detection needs of all kinds of food containing sugar in the sodium 2-(4-methoxyphenoxy) propionate.

Key words: food containing sugar; sodium 2-(4-methoxyphenoxy) propionate; gas chromatography

液相萃取法快速测定原油中硫化氢含量

林海，李春雄，王浪

（湛江出入境检验检疫局，广东 湛江  524022）

摘要：建立了液相萃取法快速测定原油中硫化氢含量的方法，通过优化实验条件，确定加热温度为60 ℃，载气流速为375 mL/ min。实验结果表明，该方法对原油中的硫化氢含量测定的加标回收率为97% ～ 110%之间，相对标准偏差为0.32% ～ 0.85%（n = 6）。方法操作简单、快速、重复性好，适用于原油中硫化氢含量的直接测定。

关键词：液相萃取法；原油；硫化氢。

中图分类号：O657.1      文献标识码：A      文章编号：0258-3283（2017）

Rapid Determination of Hydrogen Sulfide in Crude Oil by Liquid Phase Extraction LIN Hai, LI Chun-xiong, WANG Lang (Zhanjiang Entry-Exit Inspection & Quarantine Bureau, Zhanjiang 524022, China), Huaxue Shiji, 2017, 39(7)

Abstract: It is quite necessary to accurately determine hydrogen sulfide in crude oil, as it would corrode refinery equipment, pollute the environment and harm to human bodies. By optimizing experimental conditions, this work determined the heating temperature to be 60 ℃, and the flow rate of carrier gas to be 375 mL/min, which established a method for rapid determination of hydrogen sulfide in crude oil with liquid phase extraction. The recoveries and relative standard deviations of hydrogen sulfide in crude oil were in ranges of 97% ～ 110% and 0.32% ～ 0.85% (n = 6), respectively. Therefore, this simple, rapid and reproducible method is suggested for direct determination of hydrogen sulfide in crude oil.

Key words: liquid phase extraction method；crude oil；hydrogen sulfide

水中三硝基甲苯质量控制标准物质的研制

邢书才^*，田衎，樊强

（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）

摘要：研制了以三硝基甲苯为主要成分的水质计量用标准物质。用先密后疏的方式检验样品的稳定性，对样品的均匀性、稳定性分别运用单因素方差分析方法和线性模型进行考察，组织多个国内权威实验室对样品进行协作分析定值，并对定值结果进行合成标准不确定度和扩展不确定度评估。样品的定值结果为0.983 mg/L，扩展不确定度为0.046 mg/L。均匀性指标符合国家标准物质的技术要求，稳定性可达到24个月以上。可满足水质三硝基甲苯分析量值传递的需要，达到分析测试中质量保证的目的和要求。

关键词：水体环境；三硝基甲苯；标准物质；质量控制；量值传递

中图分类号：X832     文献标识码：A     文章编号：0258-3283（2017）

Development of Certified Reference Material of Trinitrotoluene in Water for Quality Control XING Shu-cai^*, TIAN Kan, FAN Qiang (State Environmental Protection Key Laboratory of Environmental Pollutant Metrology and Reference Materials Study, Institute for Environmental Reference Materials of Ministry of Environmental Protection, Beijing 100029, China), Huaxue Shiji, 2017, 39(6)

Abstract: The certified reference material of trinitrotoluene in water was developed. Its stability has been examined in regular order. The homogeneity of standard sample was evaluated by one-way ANOVA and the stability was evaluated by linear model. The certification was conducted by the cooperation of qualified in-network laboratories. The combined standard uncertainty and expanded uncertainty of standard sample were evaluated. The certified value was 0.983 mg/L and the extended uncertainty was 0.046 mg/L. The results indicated that the homogeneity in conformity with international standards for certified reference material. The stability was above 24 months. The reference material can be used as quality control sample for analysis of trinitrotoluene in water for transmission of measurement values.

Key words: water environment; trinitrotoluene; certified reference material; quality control; value transfer

稻壳灰负载氯磺酸催化苯并咪唑化合物的合成研究

雷英杰^*1，丁玫¹，吴新世¹，姚庆佳²

（1. 天津理工大学 化学化工学院，天津  300384； 2. 天津市斯芬克司药物研发有限公司，天津  300457）

摘要：以绿色廉价的稻壳灰为载体，接着吸附氯磺酸作为固体酸催化剂，微波辅助、无溶剂条件下，利用邻苯二胺和醛分子间的缩合反应一步法制备得到2-取代苯并咪唑类化合物，其结构经IR、¹HNMR和元素分析等加以确证。实验结果表明，600 ℃下煅烧的稻壳灰经氯磺酸处理后制备固体酸催化剂的用量为8 mol %，800 W功率下微波辐射反应5 ～ 10 min即可得目标化合物，且收率为87% ～ 97%，该催化剂易于回收并多次使用。

关键词：苯并咪唑；稻壳灰；氯磺酸；微波辐射

中图分类号：O626.2             文献标识码：A       文章编号：0258-3283（2017）

Synthesis of Benzimidazoles Catalysized by Chlorosulfonic Acid Supported on Rice Husk Ash LEI Ying-jie¹, DING Mei¹, WU Xin-shi¹, YAO Qing-jia² (1. School of Chemistry & Chemical Engineering, Tianjin University of Technology, Tianjin 300384, China；2. Sphinx Scientific Laboratory Corporation, Tianjin 300457, China), Huaxue Shiji, 2017, 39(7)

Abstract:Using rice husk ash as a green and cheap activated material to adsorb the chlorosulfonic acid as a powerful solid acid catalyst for the synthesis of 2-substituted benzimidazoles via the condensation reaction between o-aminothiophenol and aromatic or aliphatic aldehydes under microwave irradiation and solvent-free conditions was discussed. The structures of the corresponding products were confirmed by IR, ¹HNMR and elemental analysis. The results indicated that the rice husk ash burned at 600 °C and treated with sulfonation is efficient to catalyze the synthesis of a series of substituted benzimidazoles with good yields of 87% ～ 97% with the amount of 8 mol% under irradiation at 5 ～ 10 min respectively. Meanwhile, this catalyst could be recovered and reused without any appreciable loss of efficiency.

Key words: benzimidazoles; rice husk ash; chlorosulfonic acid; microwave irradiation

稳定性同位素氘标记对羟基苯甲酸正丁酯的合成与表征

王伟，王雪婷，杜晓宁^*

(上海化工研究院 上海稳定性同位素工程技术研究中心，上海  200062)

摘要：以对羟基苯甲酸-环-D₄为同位素原料，酸性条件下与正丁醇反应得到对羟基苯甲酸正丁酯-环-D₄。考察了酸性催化剂种类对产物同位素丰度的影响，筛选出最佳酸性催化剂对甲苯磺酸。通过单因素实验得到优化后的工艺参数，n（正丁醇）：n（对羟基苯甲酸-环-D₄）= 5 : 1，m（对甲苯磺酸）：m（对羟基苯甲酸-环-D₄）= 0.05 : 1，反应温度为95 ℃，反应时间为4.5 h。产物经GC-MS、¹HNMR和FT-IR进行分析，化学纯度 ＞99.0%，同位素丰度＞97 atom%D。

关键词：同位素内标试剂；对羟基苯甲酸正丁酯；尼泊金丁酯，稳定同位素标记；氘标记试剂

中图分类号：O628.2           文献标识码：A            文章编号：0258-3283（2017）

Synthesisand Characterization of Stable Isotope Deuterium Labelled Butyl 4-Hydroxybenzoate WANG Wei, WANG Xue-ting, DU Xiao-ning^* (Shanghai Engineering Research Center of Stable Isotope，Shanghai Research Institute of Chemical Industry，Shanghai 200062，China), Huaxue Shiji, 2017, 39(7)

Abstract: A new procedure for the synthesis of the deuterium labelled butyl 4-hydroxybenzoate has been developed. The effects of acid catalysts types on isotope abundance of butyl 4-hydroxybenzoate-ring-D₄ were investigated, and p-toluene sulfonic acid was chosen as the catalyst. The optimal reaction conditions were obtained as follows: The molar ratio of butyl alcohol to 4-hydroxybenzoic acid-ring-D₄ was 5 ∶ 1, the mass ratio of p-toluene sulfonic acid to 4-hydroxybenzoic acid-ring-D₄ was 0.05 ∶ 1, the temperature was 95 ℃, the reaction time was 3.5 h. The product butyl 4-hydroxybenzoate-ring-D₄ was confirmed via GC-MS. The chemical purity was above 99.0%, and the isotopic abundance was above 97 atom%D. The qualitative of product butyl 4-hydroxybenzoate-ring-D₄ was carried out by ¹HNMR and FT-IR.

Key words：isotope internal reagent；butyl 4-hydroxybenzoate；butyl paraben；stable isotope labeling；deuterium labeling reagent

SO₄^2-/TiO₂固体酸负载BINOL催化膦氢化反应

宋友德^{1, 2}，姚元勇^*1，舒华^*1

(1．铜仁学院 应用化学研究所 材料与化学工程学院，贵州 铜仁  554300；

2. 铜仁广播电视大学，贵州 铜仁  554300)

摘要：采用SO₄^2－型固体酸SO₄^2－/TiO₂的Lewis酸性位点与BINOL的Bronsted酸性位点进行负载，制备出具有较强双氢键供体的BINOL负载的SO₄^2－/TiO₂催化剂。以不同取代基团的芳香族伯胺和肉桂醛缩合制备的芳香族亚胺为催化底物，在10 mol% BINOL负载的SO₄^2-/TiO₂催化剂的催化作用下，与亚磷酸二烷基酯(亲核试剂)进行膦氢化反应。同时，通过对比固体酸SO₄^2－/TiO₂、BINOL与BINOL负载的SO₄^2－/TiO₂催化剂的催化活性，从而对BINOL负载的SO₄^2－/TiO₂催化剂进行客观地评价。另外，在较优的催化条件下，以BINOL负载的SO₄^2－/TiO₂为催化剂，成功地催化合成了α-氨基膦酸酯类衍生物，且产率可达82% ～ 89%。另外，基于氢键的作用模式，提出了适合于膦氢化反应较为合理的作用机理。

关键词：固体酸；BINOL负载的SO₄^2－/TiO₂；α-氨基膦酸酯；膦氢化反应

中图分类号：O621.3            文献标识码：A              文章编号：0258-3283（2017）

BINOL-Loaded SO₄^2-/TiO₂ Catalyst for α-Aminophosphonates Reaction SONG You-de^1,2，YAO Yuan-yong ^*1, SHU Hua^*1 (1. School of Material and Chemical Engineering, Institute of Applied Chemistry, Tongren University, Tongren 554300, China；2. Tongrenradio& TV University, Tongren 554300, China), Huaxue Shiji, 2017, 39(7)

Abstract: By loading of solid acid SO₄^2-/TiO₂with Lewis acidic sites onto BINOL with Bronsted acidic sites, the potent catalyst BINOL-Loaded SO₄^2-/TiO₂ with much potential double H-bonding donors have been prepared. The catalytic substrate of aromatic imines prepared by the condensation of diverse substitutes aromatic primary amine with cinnamylaldehyde was permitted to proceed hydrophosphonylation with dialkyl phosphate as nucleophile in the presence of solid acid BINOL-Loaded SO₄^2-/TiO₂ (10 mol%). Under the optimal conditions, the BINOL-Loaded SO₄^2-/TiO₂acted as valid catalyst was successfully utilized to afford α-aminophosphonate derivatives, in yields of 82% ～ 89%. Simultaneously, as comparing BINOL-Loaded SO₄^2-/TiO₂ with SO₄^2-/TiO₂ and BINOL in catalytic activity, BINOL-Loaded SO₄^2-/TiO₂ catalyst was objectively obtained assessment. In addition, relying on hydrogen-bonding interactions, the mechanism has been proposed for BINOL-Loaded SO₄^2-/TiO₂.

Key words: solid acid；BINOL-Loaded SO₄^2-/TiO₂；α-aminophosphonate；hydrophosphonylation

基于吖啶酮衍生物新型传感器的设计合成及性能研究

田林^{1, 2a, 2b}，盛风涛^2a，李同祥^2b，韩相恩^*1

( 1．中国矿业大学 化学化工学院，江苏 徐州  221116；2. 徐州工程学院 a. 化学化工学院，b. 食品（生物）工程学院，江苏 徐州  221018)

摘要：以吖啶酮为荧光团，引入离子识别基团设计合成了一种新型化学传感器ANSA。该化合物的结构通过氢谱、碳谱以及高分辨质谱进行确认。对传感器的性能研究试验表明，该传感器在水溶液中对Cu²⁺的识别具有专一性、强抗干扰性，pH 7左右时对Cu²⁺的识别作用最强，检出限为8.26×10^-8 mol/L。Job′s plot曲线表明，Cu²⁺与配体的比为2 : 1，该配体对多种形式的铜源都具有较好的识别作用。

关键字：设计；Cu²⁺；化学传感器；水溶液  

中图分类号：O657.3          文献标识码：A        文章编号：0258-3283（2017）

Synthesis and Performance of Novel Chemosensor Based on Acridone Derivatives TIAN Lin^{1, 2a, 2b}, SHENG Feng-tao^2a, LI Tong-xiang^2b, HAN Xiang-en^*1(1. School of Chemical Engineering and Technology, China University of Mining & Technology, Xuzhou 221116, China; 2. a. School of Chemical Engineering and Technology, b. School of food (Biological) Engineering, Xuzhou Institute of Technology, Xuzhou 221018, China), Huaxue Shiji, 2017, 39(7)

Abstract: A novel acridone chemosensor ANSA, which introduced a ion recognition group, was synthesized. The structures of compounds were confirmed by ¹HNMR, ¹³CNMR, HRMS. When the water buffer was chosen as a test solvent, ANSA had an excellent special identification capacity for Cu²⁺ and a strong anti-interference ability. The ability of recognition was strongest when pH of the buffer was about 7. The detection limit was 1.19 × 10^-11M. The complex of ANSA and Cu²⁺ was 1︰2. The chemosensor was the same recognition ability to Cu²⁺ when the copper salt was different.

Key words: design；Cu²⁺；chemosensor；water solution

α, β-不饱和三氟甲基酮与非环状酮的杂Diels-Alder反应研究

林敬^*，束云飞，马佳伟，王岑岭，戴兢陶

(盐城师范学院 化学与环境工程学院，江苏 盐城  224007)

摘要：探讨了α, β-不饱和三氟甲基酮与另一种非环状酮之间的杂Diels-Alder反应，通过对酸、酸的用量以及溶剂等因素的考察，确定了反应的最优条件。然后，实现了不同结构的α, β-不饱和三氟甲基酮与非环状酮的杂Diels-Alder反应，以最高86%的收率获得了含三氟甲基的四氢吡喃酮衍生物，其结构经¹HNMR、¹³CNMR表征。

关键词：α, β-不饱和三氟甲基酮；非环状酮；杂Diels-Alder反应；四氢吡喃酮衍生物

中图分类号：O626.3        文献标识码：A         文章编号：0258-3283（2017）

Hetero-Diels-Alder Reactions of α, β-Unsaturated Trifluoromethyl Ketones with Acyclic Ketones LIN Jing^*, SHU Yun-fei, MA Jia-wei, WANG Cen-ling, DAI Jing-tao (School of Chemistry & Environmental Engineering, Yancheng Teachers University, Yancheng 224007, China), Huaxue Shiji, 2017, 39(6)

Abstract: Hetero-Diels-Alder reactions of α, β-unsaturated trifluoromethyl ketones with another acyclic ketones were investigated. The effect of acids, the amounts of acid and solvents on the reaction were investigated and the optimal condition for the reaction was obtained. Then, hetero-Diels-Alder reactions of the different structure of α, β-unsaturated trifluoromethyl ketones with acyclic ketones, affording trifluoromethylated tetrahydropyranone derivatives in high yields (up to 86% yield). All compounds were fully confirmed by ¹HNMR and ¹³CNMR.

Key words: α, β-unsaturated trifluoromethyl ketones; acyclic ketones; hetero-Diels-Alder reactions; tetrahydropyranone derivatives

微通道反应器内合成高纯度碘化钾

凌芳^*，宋忠哲，薛循育，刘清龙

（国药集团化学试剂有限公司，上海  200002）

摘要：利用微通道反应器，研究了氢碘酸、甲酸溶液及氢氧化钾合成碘化钾的反应，考察了反应温度、原料配比、停留时间对碘化钾收率的影响。获得了较优的反应工艺条件：反应温度为85 ℃、停留时间为30 s、W(氢碘酸) ﹕ W(甲酸) ＝ 54%、W(氢氧化钾) ﹕ W(水) ＝ 31%。在该优化工艺条件下，碘化钾的产率为97%，产品纯度达到99%。实验结果表明，该方法具有反应时间短、产品收率高、绿色环保等优点。

关键词：碘化钾；微通道反应器；氢氧化钾

中图分类号：TQ124.6      文献标识码：A       文章编号：0258-3283（2017）

Synthesis of Potassium iodide in Micro-channel Reactor LINGFang^*, SongZhong-zhe, XUE Xun-yu, LIU Qing-long (Sinopharm Chemical Reagent Co.,Ltd, Shanghai 200002,China), Huaxue Shiji, 2017, 39(7)

Abstract：The use of micro channel reactor of hydroiodic acid, formic acid and potassium hydroxide potassium iodide synthesis reaction, reaction temperature, material ratio and residence time were investigated on the yield of potassium iodide. The optimum reaction conditions: the reaction temperature is 85 ℃, residence time of 30 s, W (hydriodide)︰W (formic acid) = 54%, W(KOH)︰W(Water) = 32%. In the optimum conditions, the yield of potassium iodide is 97%. This method has advantages of short reaction time，high product yield and green environment.

Key words：potassium Iodate；micro-channel reactor；potassium hydroxide

2-甲基-4-甲醛肟基苯甲酸甲酯的合成

黄道友¹，王勇²，李立威^*2，江国栋¹，袁颂东¹

(1. 湖北工业大学 化学化工学院，湖北 武汉  430068；2. 荆楚理工学院 湖北省荆门医药工业技术研究院，湖北 荆门  448000)

摘要：以2-甲基-4-溴苯甲酸为起始原料，经酰化和酯化反应制得2-甲基-4-溴苯甲酸甲酯，2-甲基-4-溴苯甲酸甲酯与氰化亚铜发生取代反应得到2-甲基-4-氰基苯甲酸甲酯，2-甲基-4-氰基苯甲酸甲酯与盐酸羟胺在碱性条件下反应得到目标产物2-甲基-4-甲醛肟基苯甲酸甲酯，总收率为61%，纯度为99.2%。反应过程中化合物的结构经IR、MS、¹HNMR和¹³CNMR等表征确证。该路线中目标产物肟经由氰基直接一步反应制得，工艺简单可靠、产品收率高。该方法为肟的合成提供了良好的实验基础。

关键词：2-甲基-4-溴苯甲酸；肟；合成；¹HNMR

中图分类号：O621.3        文献标识码：A        文章编号：0258-3283(2017)

Synthesis of 4-(Hydroxyimino-methyl)-2-methyl Benzoic Acid Methyl Ester HUANG Dao-you¹, WANG Yong², LI Li-wei^*2, JIANG Guo-Dong¹, YUAN Song-dong (1.School of Chemistry and Chemical Engineering, Hubei University of Technology, Wuhan 430068, China; 2.HubeiJingmen Institute of Pharmaceutical Industry Technology, Jingchu University of Technology, Jingmen 444800, China), Huaxue Shiji, 2017, 39(7)

Abstract：In this work, 4-bromo-2-methyl benzoic acid methyl ester was synthesized by acylated and esterified, with 2-methyl-4-bromo-benzoic acid as starting material. 4-Cyano-2-methyl-benzoic acid methyl ester was obtained by reaction of 4-bromo-2-methyl benzoic acid methyl ester with CuCN in DMF solution. Reaction of compound 3 with hydroxylamine hydrochloride in the presence of Na₂CO₃ affords product 4-(hydroxyimino-methyl)-2-methyl benzoic acid methyl ester. The total yield is 61% and its purity is 99.2%. All the compounds were fully characterized by IR, MS, ¹HNMR and ¹³CNMR, and all these datas indicate that compounds have been successfully prepared. This route from cyano to oxime is only one step, and this method is in simple operation and high yield. The method also provides a good experimental foundation for the synthesis of oxime.

Key words：4-bromo-2-methyl benzoic acid methyl ester；oxime；synthesis；¹HNMR

1, 3, 5-三(3, 3, 4, 4, 5, 5, 6, 6, 6-九氟己基)-1, 3, 5-三甲基环三硅氧烷的合成

向德轩^{*1a, 1b} ，向满^1a，刘婷^1a，陈欣²，李元祥^{1a, 1b}，胡扬剑^1a，王树华²

 (1. 怀化学院 a. 聚乙烯醇纤维材料湖南省工程实验室，b. 有机化学研究所，湖南 怀化  418000；2. 巨化集团 技术中心，浙江 衢州  324000)

摘要：标题化合物是一种合成共氟硅材料的重要单体。以全氟丁基乙烯和甲基二氯硅烷为原料，经硅氢加成反应合成了氟烃基甲基二氯硅烷，再经水解反应制得其水解产物，最后在CSOH催化下经裂解反应制备了目标化合物。产物经¹HNMR、¹³CNMR、¹⁹FNMR及IR确认结构。

关键词：全氟丁基乙烯；1, 3, 5-三(3, 3, 4, 4, 5, 5, 6, 6, 6-九氟己基)-1, 3, 5-三甲基环三硅氧烷；甲基二氯硅烷；硅氢加成反应；裂解反应

中图分类号：O627.41                文献标识码：A             文章编号： 0258-3283（2017）

Synthesis of 1, 3, 5-Tris(3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl)-1, 3, 5-trimethylcyclotrisiloxane XIANG De-xuan ^{*1a, 1b}, XIANG Man^1a, LIU Ting^1a, CHEN Xin², LI Yuan-xiang^{1a, 1b}, HU Yang-jian^1a, WANG Shu-hua² (1. Huaihua University, a. Hunan Engineering Laboratory for Preparation Technology of Polyvinyl Alcohol(PVA) Fiber Material, b.              Huaihua 418000, China; 2. Juhua Group Technology Center, Quzhou 324000, China), Huaxue Shiji, 2017, 39(6)

Abstract：1, 3, 5-Tris(3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl)-1, 3, 5-trimethylcyclotrisiloxane is a very important monomer for the synthesis of fluorine silicon material. In the work, (perfluorobutyl)ethylene and dichloromethylsilane were taken as the raw material. After hydrosilylation reaction, fluorinealkyl dimethyl dichlorosilane was synthesized. Then after hydrolysis, hydrolysate was obtained and finally 1, 3, 5-tris(3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl)-1, 3, 5-trimethylcyclotrisiloxane formed after crack reaction under the catalyst of CSOH. The product structure was confirmed via¹HNMR, ¹³CNMR, ¹⁹FNMR and IR. 

Key words: (perfluorobutyl)ethylene; 1, 3, 5-tris(3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl)-1, 3, 5-trimethylcyclo- trisiloxane; dichloromethylsilane; hydrosilylation reaction; crack reaction 

1, 6-二羟基-2-萘甲酸的合成研究

韩科展^a,c，张梦辉^a,c，周志旭^b,c，赵春深^*b,c

（贵州大学 a.化学与化工学院，b. 药学院，c. 贵州省发酵工程与生物制药重点实验室，贵州 贵阳  550003）

摘要：标题化合物是合成新型内分泌治疗剂的重要中间体，而其合成方法未见文献报道。本文以6-甲氧基-1-萘满酮为起始原料，经取代、氧化和水解3步反应得到目标产物，其结构经MS、¹HNMR、¹³CNMR和IR确证。该路线原料廉价易得、操作简单、后处理方便，总收率达69.5%，适合工业化生产。

关键词：1, 6-二羟基-2-萘甲酸；6-甲氧基-1-萘满酮；合成

中图分类号：O622.5    文献标识码：A    文章编号：0258-3283(2017)

Synthesis of 1,6-Dihydroxy-2-naphthoic Acid HAN Ke-zhan ^{a, c}, ZHANG Meng-hui ^{a, c}, ZHOU Zhi-xu ^{b, c}, ZHAO Chun-shen ^{* b, c} ( a. School of Chemistry and Chemical Engineering, b. School of Pharmaceutical Sciences, c. Key Laboratory of Guizhou for Fermentation Engineering and Biomedicine, Guizhou University, Guiyang 550003）, Huaxue Shiji, 2017, 39(7)

Abstract: 1, 6-Dihydroxy-2-naphthoic acid is an important intermediate for the synthesis of new endocrine the rapy medicine. In this work, 6-methoxy-1-tetralone was used as the starting material. The target product was obtained by three steps of substitution, oxidation and hydrolysis. The structures were confirmed by MS, ¹HNMR, ¹³CNMR and IR. The raw material of this route is cheap and easy to obtain, and the optimized process is simple in operation, short in reaction time and easy to purify. The total yield reaches 69.5%, which is suitable for industrial production.

Key words: 1,6-dihydroxy-2-naphthoic acid; 6-methoxy-1-tetralone; synthesis

4-羟基-7-甲氧基-8-硝基喹啉的合成

刘丹^*，李雪，刘智鑫，彭鹏辉，张毅

（沈阳化工大学 制药与生物工程学院，辽宁 沈阳  110142）

摘要：以间甲氧基苯胺和乙氧基亚甲基丙二酸二乙酯（EMME）为起始原料，经缩合、Gould-Jacobs高温环合、水解、脱羧、硝化反应，合成了4-羟基-7-甲氧基-8-硝基喹啉，总收率达48.74 %，其结构经ESI-MS、¹HNMR和IR确证。

关键词：间甲氧基苯胺；乙氧基亚甲基丙二酸二乙酯；4-羟基-7-甲氧基-8-硝基喹啉

中图分类号：R914.5        文献标识码：A           文章编号：0258-3283（2017）

Synthesis of 4-Hydroxy-7-methoxy-8-nitroquinoline LIU Dan^*, LI Xue, LIU Zhi-xin, PENG Peng-hui, ZHANG Yi（College of Pharmaceutical and Biological Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China）, Huaxue Shiji, 2017, 39(6)

Abstract: 4-Hydroxy-7-methoxy-8-nitroquinoline in overall yield of 48.74% was synthesized from 3-methoxy aniline by a five-step reaction of condensation, Gould-Jacobs cyclization, hydrolysis, decarboxylation and nitration. The structure was confirmed by ESI-MS, ¹HNMR and IR.

Key words: 3-methoxybenzenamine; EMME; 4-hydroxy-7-methoxy-8-nitroquinoline

3, 5-二甲氧基邻苯二甲酸酐的合成

夏晶，李毅，陈文章，汤磊^*

(贵州医科大学，贵州 贵阳  550004)

摘要：以 2, 4-二甲氧基-6-甲基苯甲酸乙酯为原料，经溴代、水解、氧化、环合、还原5步反应，合成了金丝桃素的中间体3, 5-二甲氧基邻苯二甲酸酐。其结构经¹HNMR和¹³CNMR表征。

关键词：3, 5-二甲氧基邻苯二甲酸酐；2, 4-二甲氧基-6-甲基苯甲酸乙酯；合成

中图分类号：R914.5       文献标识码：A        文章编号：0258-3283(2017)

Synthesis of 3,5-Dimethoxyphthalic Anhydride XIA Jing, LI Yi, CHEN Wen-zhang, TANG Lei^*( Guizhou Medical University, Guiyang 550004, China), Huaxue Shiji, 2017, 39(7)

Abstract: 3, 5-Dimethoxyphthalic anhydride which is the intermediates of hypericin was synthesized by using 2,4-dimethoxy-6-methyl benzoate as the raw material and via five-step reaction of bromo, hydrolysis, oxidation, cyclization, reduction. The structure were confirmed by ¹HNMR and ¹³CNMR.

Key words: 3, 5-dimethoxyphthalic anhydride；2,4-dimethoxy-6-methyl benzoate；synthesis

一种合成薏苡素的新方法

梁大伟^*，袁野，章斌，王悦秋

(雅安职业技术学院 药学检验系，四川 雅安  625000)

摘要：以邻氨基苯酚与二(三氯甲基)碳酸酯为原料，两者经成环反应、溴代、碘化亚铜催化甲氧基取代反应合成薏苡素，3步反应的总收率为57.0%，其结构经¹HNMR、¹³CNMR、IR、MS等表征。

关键词：薏苡素；碘化亚铜催化；甲氧基化；合成

中图分类号：      文献标识码：A           文章编号：0258-3283（2017）

New Synthetic Method of Coixol LIANG Da-wei^*, YUAN Ye, ZHANG Bin, WANG Yue-qiu (Department of Pharmacy & Medical Laboratory, Ya′an Polytechnic College, Ya′an 625000, China), Huaxue Shiji, 2017, 39(7)

Abstract: Coixol was synthesized from 2-aminophenol and triphosgene via cyclization, bromation and methoxylation, using copper iodide as a catalyst. The total yield was 57.0%, and the structure was confirmed by ¹HNMR, ¹³CNMR, IR and MS.

Key words: coixol；CuI-catalysis；methoxylation；synthesis