SSZ-13分子筛合成、性能优化及成本调控研究进展
胡晨晖1,2，陈锡炯3，刘春红*1,2，杜凯敏1,2，卓佐西1,2，陈亮4，林贻超4
（1. 浙江省火力发电高效节能与污染物控制技术研究重点实验室 浙江 杭州 311121；2. 浙江浙能技术研究院有限公司，浙江 杭州 311121；3. 浙江浙能长兴发电有限责任公司，浙江 湖州 313000；4. 中国科学院宁波材料技术与工程研究所，浙江 宁波 315201）
摘要：SSZ-13分子筛因其有序孔道结构、大比表面积、高催化活性、良好水热稳定性等，近年来被广泛应用于催化合成、环境保护、新能源等多个领域。首先，介绍了水热合成法、固相研磨法、干胶转换法等SSZ-13分子筛合成方法，并指出了各自优缺点；其次，针对目前SSZ-13分子筛普遍存在积炭能力弱、催化活性不高的问题，介绍了孔道结构和晶粒尺寸等优化调控方法；再者，从模板剂的使用、合成条件、晶种等方面，阐述了降低SSZ-13分子筛合成成本和提高合成效率的调控方法。在此基础上，提出了开发绿色、环保、低成本、高效率的新型SSZ-13分子筛合成方法，而面向不同领域的多功能新型SSZ-13分子筛是当前迫切需要解决的问题。
关键词：SSZ-13分子筛；合成；性能；成本；效率
中图分类号：O643.3 文献标识码：A 文章编号：0258-3283（2020）
Progress in Synthesis, Optimizing Performance and Regulating Cost of SSZ-13 Zeolite HU Chen-hui1,2, CHEN Xi-jiong3, LIU Chun-hong*1,2, DU Kai-min1,2, ZHUO Zuo-xi1,2, CHEN Liang4, LIN Yi-chao4 (1. Zhejiang Provincial Key Laboratory of Energy Conservation & Pollutant Control Technology for Thermal Power, Hangzhou 311121, China; 2. Zhejiang Energy Group R&D Institute Co., Ltd., Hangzhou 311121, China; 3. Zhejiang Zheneng Changxing Power Generation Co., Ltd., Huzhou 313000, China; 4. Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China), Huaxue Shiji, 2020, 42(11), ～
Abstract：SSZ-13 zeolite has been widely used in many fields in recently years such as catalytic synthesis, environmental protection and new energy fields because of its ordered pore structure, large specific surface area, high catalytic activity and good hydrothermal stability. First, some conventional synthesis methods of SSZ-13 zeolite were summarized, including hydrothermal synthesis, solid grinding and dry-gel conversion, and the advantages and disadvantages of these synthesis methods were discussed. Then, owing to the low carbon deposition resistance and low catalytic activity of SSZ-13 zeolite, the optimization methods of pore structure and grain size were reviewed. In addition, the controlling methods for decreasing the synthesis cost and improving the synthesis efficiency of SSZ-13 zeolite were described from the aspects of templates, synthesis conditions and seeds etc. The green SSZ-13 zeolite synthesis method with low cost and high efficiency was proposed, and the new multi-functional SSZ-13 zeolites for different fields are urgently needed.
Key words：SSZ-13 zeolite; synthesis; performance; cost; efficiency
引用本文：胡晨晖，陈锡炯，刘春红，等. SSZ-13分子筛合成、性能优化及成本调控研究进展[J]. 化学试剂, 2020, 42(11): 1273-1279。
缺位磷钨酸盐/CdS纳米粒子电致变色膜的制备及性能研究
薛俊礼，谭佳宁，祁岳，冯素洋，张洁，马慧雪，杨艳艳*
（吉林化工学院 化学与制药工程学院，吉林 吉林 132022）
摘要：通过层接层自组装技术，以缺位Dawson结构磷钨酸盐α-K10P2W17O61·20H2O、CdS纳米粒子和聚乙烯亚胺为原料，构筑PEI/[P2W17/PEI]20和PEI/[P2W17/PEI-CdS]20复合膜，探究CdS纳米粒子的添加对复合膜电致变色性能的影响。采用紫外-可见吸收光谱、红外光谱、扫描电镜和X射线光电子能谱对复合膜进行表征，并利用紫外-可见吸收光谱和电化学工作站联机对两种复合膜的电致变色性能进行对比研究。研究表明：CdS纳米粒子复合膜PEI/[P2W17/PEI-CdS]20的光反差提高8.59%，着色效率从48.61 cm2/C提高到了77.03 cm2/C，循环200圈后透过率仍能保持原来状态的96.91%，具有良好的稳定性。CdS纳米粒子复合为缺位磷钨酸盐电致变色性能提高提供了新的方法。
关键词：电致变色；缺位磷钨酸盐；CdS纳米粒子；层接层自组装技术；电化学测试
中图分类号：O657.1 文献标识码：A 文章编号：0258-3283(2020)--
Fabrication and Electrochromic Performance of Lacunary Phosphotungstate/CdS Nanocomposites XUE Jun-li, TAN Jia-ning, QI Yue, FENG Su-yang, ZHANG Jie, MA Hui-xue, YANG Yan-yan* (College of Chemistry and Pharmaceutical Engineering, Jilin Institute of Chemical Technology, Jilin City 132022, China), Huaxue Shiji, 2020, 42(11), ～
Abstract: The PEI/[P2W17/PEI]20 and PEI/[P2W17/PEI-CdS]20 composite films constructed by lacunary phosphotungstate α-K10P2W17O61·20H2O (P2W17), CdS nanoparticles and poly (ethylene imine) were prepared by layer-by-layer self-assembly method. The composite films were investigated via UV-Vis spectrophotometer, IR spectroscopy, scanning electron microscope and X-ray photoelectron spectroscopy. The electrochromic properties of the composite films were detected by UV-Vis spectrophotometer and electrochemical workstation. By the addition of CdS nanoparticles, the optical contrast of the PEI/[P2W17/PEI-CdS]20 composite film was increased by 8.59%, the coloring efficiency was improved to 77.03 cm2/C from 48.61 cm2/C, and the transmittance retained 96.9 1% of its original value after 200 cycles, which showed excellent stable. The CdS nanoparticles composite provides a new method to improve electrochromic properties of lacunary phosphotungstate.
Keywords: electrochromic; phosphotungstate; CdS nanoparticles; layer-by-layer assembly method; electrochemical measurement
引用本文：薛俊礼, 谭佳宁, 祁岳, 等. 缺位磷钨酸盐/CdS纳米粒子电致变色膜的制备及性能研究[J]. 化学试剂, 2020, 42(11): 1280-1286.
Fe3O4@CG磁性吸附材料对水中染料的吸附特性研究
邵俊*1，郭丰艳1，桑蓉栎2，严春亮2
（1. 唐山学院 环境与化学工程系，河北 唐山 063000；2. 华北理工大学 分析测试研究中心，河北 唐山 063000）
摘要：以咖啡渣（CG）为原料，利用化学共沉淀法制备Fe3O4@CG磁性吸附材料。通过元素分析仪、比表面积及孔径分析仪、振动样品磁强计、X-射线光电子能谱仪、X-射线衍射仪、场发射扫描电子显微镜等分析表明，Fe3O4均匀地分布在CG表面，磁性吸附材料复合成功。所得Fe3O4@CG孔隙结构发达，表面有丰富的Fe-O、C=O和C-O含氧活性官能团，测得平均孔径为7.70 nm，主要为介孔，BET比表面积为27.70 m2/g。吸附材料的磁化强度可达39.85 emu/g，具有顺磁性。吸附性能结果发现，投加量分别为30 g/L和12 g/L，pH分别为9和5时，Fe3O4@CG对200 mg/L的亚甲基蓝（MB）和刚果红（CR）具有高效吸附能力，对应的脱色率为95.72%和89.83%。常温下，Fe3O4@CG对两种染料的吸附过程均符合准二级动力学模型和Langmuir吸附等温线，吸附量分别达到12.06 mg/g（MB）和34.43 mg/g（CR），属于均相、优惠型的单分子层化学吸附。
关键词：吸附；咖啡渣；Fe3O4@CG；磁性；染料；脱色率
中图分类号：X703.1 文献标识码：A 文章编号：0258-3283（2020）
Adsorption Characteristics of Dyes onto Fe3O4@Coffee Grounds Magnetic Adsorbent in Aqueous Solution SHAO Jun1*, GUO Feng-yan1, SANG Rong-li2, YAN Chun-liang2（1. Department of Environmental and Chemical Engineering, Tangshan University, Tangshan 063000, China;2. Analytical and Testing Research Center, North China University of Science and Technology, Tangshan 063000, China）
Abstract: With coffee grounds used as raw material, Fe3O4 @ coffee grounds (Fe3O4@CG) magnetic adsorbent was prepared through chemical co-precipitation method. The samples were characterized by elemental analysis, specific surface area analyzer, vibrating sample magnetometer, X-ray photoelectron spectroscopy, X-ray diffraction and field emission scanning electron microscopy. The results indicated that coffee grounds were modified by magnetic Fe3O4 particles uniformly and the magnetic adsorbent was successfully prepared. Fe3O4@CG had well internal porosity and hydrophilic function groups of Fe-O, C=O and C-O. The adsorbent shared a lot of mesopores, while the average pore size of the magnetic adsorbent was 7.70 nm and the surface area reached to 27.70 m2/g. The saturation magnetization was 39.85 emu/g, indicating good paramagnetism. The removal rate of MB and CR on Fe3O4@CG reached 95.72% and 89.83%, respectively, under the following conditions: the initial mass concentration was 200 mg/L, the pH value was 9 and 5, and the dosage was 30 g/L and 12 g/L, respectively. At 298 K, the maximum adsorption capacity of MB and CR reached the values of 12.06 mg/g and 34.43 mg/g, respectively. The pseudo-second-order kinetic model and Langmuir isotherm model were more suitable for describing the adsorption of MB and CR on Fe3O4@CG, suggesting that the progress was a homogeneous and preferential monolayer chemical adsorption.
Key words: adsorption;coffee grounds; Fe3O4@ coffee grounds; magnetic; dyes; decolorization
引用本文：邵俊，郭丰艳，桑蓉栎，等. Fe3O4@CG磁性吸附材料对水中染料的吸附特性研究[J]. 化学试剂，2020, 42（11）：1287-1293.
α-Fe2O3纳米微球的制备及对ppb水平的H2S气敏性能研究
付双*，李红梅，孙革，潘虹，孙明睿
(齐齐哈尔医学院 药学院，黑龙江 齐齐哈尔161006)
摘要：采用溶剂热法制备了多级结构的氧化铁前驱体，再经300 ℃热处理后得到α-Fe2O3多级结构的纳米微球。通过XRD、BET、SEM和TEM等手段对产物结构和形貌进行表征。结果表明，合成的α-Fe2O3纳米微球直径约为500 nm。此外，将α-Fe2O3纳米微球制备成厚膜型气敏元件并进行了气敏性能测试，在工作温度为150 ℃时，α-Fe2O3纳米微球对硫化氢气体有良好的选择性和较高的灵敏度，最低检出限可以达到0.05 ppm，对10 ppm硫化氢的响应值为10.5，α-Fe2O3纳米微球可被用于制备硫化氢气体传感器。
关键词：溶剂热法；α-Fe2O3；纳米微球；硫化氢；气体传感器
中图分类号：TP212.2 文献标识码：A 文章编号：0258-3283（2020）--
Synthesis of α-Fe2O3 Nanospheres and Gas-sensing Property to H2S at ppb Level FU Shuang, LI Hong-mei, SUN Ge, PAN Hong, SUN Ming-rui (College of Pharmacy, Qiqihar Medical University, Qiqihar 161006, China), Huaxue Shiji, 2020, 42(11), ～
Abstract: Hierarchical Fe2O3 precursors were prepared by a simple solvothermal method. Subsequently, hierarchical α-Fe2O3 nanospheres were obtained via calcining the precursors at 300 °C. The composition and morphology of the products were analyzed by XRD, BET, SEM and TEM. The results indicated that the α-Fe2O3 nanospheres have a diameter of ca. 500 nm. Furthermore, the sensor based on α-Fe2O3 nanospheres exhibited good selectivity and high response to H2S gas at an operating temperature of 150 °C. The detection limit towards H2S gas was 0.05 ppm, and the response of this sensor to 10 ppm H2S attains 10.5. The obtained results demonstrate that the α-Fe2O3 nanospheres are a promising material for the preparation of H2S gas sensors.
Key words: solvothermal method; α-Fe2O3; nanospheres; gas sensor
引用本文：付双，李红梅，孙革，等. α-Fe2O3纳米微球的制备及对ppb水平的H2S气敏性能研究[J]. 化学试剂, 2020, 42(11): 1294-1298.
鹿油-鹿茸多肽乳剂凝胶的制备及其体外透皮吸收的研究
刘哲，张宏梅，冯宪敏，梁娟，张子怡，崔佰吉*
（吉林医药学院药学院，吉林吉林 132013）
摘要：筛选最佳鹿油-鹿茸多肽乳剂凝胶处方并研究其体外透皮吸收情况。考察鹿茸多肽与鹿油及油水两相的比例，优选最佳鹿油-鹿茸多肽乳剂凝胶处方并考察其稳定性；以卡波姆974为凝胶基质，制备鹿油-鹿茸多肽乳剂凝胶并考察其稳定性；采用立式改良Franz扩散池，研究萜烯类化合物对鹿油-鹿茸多肽乳剂凝胶体外透皮吸收的影响。实验结果表明，最佳处方为m(鹿茸多肽)∶m(鹿油)= 1∶1，V(油相)∶V(水相) =1∶2，凝胶基质为1.5%卡波姆，促进剂为2.5%的香叶醇；此处方制得鹿油-鹿茸多肽乳剂凝胶的累积渗透量最大，Q12达到（350.26±27.98）μg/cm2，JS 为（22.71±1.73）μg/(cm2·h1)。所得鹿油-鹿茸多肽乳剂凝胶外观良好、性质稳定，且2.5%香叶醇处方组具有较高的累积渗透量，为今后鹿油-鹿茸多肽透皮制剂的开发提供理论依据。
关键词：鹿油；鹿茸多肽；乳剂凝胶；透皮吸收；萜烯类化合物
中图分类号：R944.9 文献标识码：A 文章编号：0258-3283（2020）
Preparation of Deer Oil - Pilose Antler Polypeptide Emulgelsand Transdermal Administration Study in Vitro Percutaneous Permeability LIU Zhe, ZHANG Hong-mei, FENG Xian-min, LIANG Juan, ZHANG Zi-yi, CUI Bai-ji*（College of PharmacyJilin Medicine University,Jilin132013,China), Huaxue Shiji, 2020, 42(11), ～
Abstract:A suitable emulgel formulation of deer oil - pilose antler polypeptide was prepared and the effects of different absorption enhancers on its percutaneous absorption in vitro were investigated using rat skin and diffusion cell technique. The effects of the ratio of antler polypeptide to deer oil and the ratio of oil-water were investigated and the stability of formulation was studied. Emulgels of deer oil - pilose antler polypeptide were loaded withCarbomer974 as a matrixand investigated their stability. The transdermal absorption properties of deer oil - pilose antler polypeptideemulgels were investigated by Franz diffusion cell methodin vitro. The result showed that the mass ratios of m(pilose antler polypeptide)∶m(deer oil) =1:1（0.5g:0.5g）and V(oil)∶V(water) =1:2（4mL:8mL）, respectively. Formulation prepared using1.5% Carbomer showed desirable characteristics and appearance. Deer oil - pilose antler polypeptideemulgel using 2.5% geraniol showed highest cumulative permeation amount (Q12) of (350.26±27.98) μg/cm2 and fluxrate of (22.71±1.73) μg/(cm2·h1).The highest cumulative permeation amount was obtained with geraniol 2.5% in indomethacinliposome gels. The health cosmetics of pilose antler polypeptide have good potential for transdermal delivery.
Key words: deer oil; piloseantler polypeptide; emulgel; percutaneous absorption; terpenes
引用本文：刘哲，张宏梅，冯宪敏，等. 鹿油-鹿茸多肽乳剂凝胶的制备及其体外透皮吸收的研究[J].化学试剂，2020，42(11)：1299-1304。
3-乙酰基香豆素衍生物的合成及抗血小板聚集活性
何冰,刘红,肖维玉,张强,张群英*1
（安徽中医药大学药学院，安徽合肥 230038）
摘要：以水杨醛、乙酰乙酸乙酯为原料合成3-乙酰基香豆素，其酮羰基与盐酸羟胺反应得到肟，利用肟羟基与不同碳数的二溴烷烃反应得到相应的溴代肟醚，再与吗啉反应得到5个标题化合物。其结构经过红外光谱、核磁共振氢谱和质谱确证。采用Born比浊法，对中间体和5个标题化合物进行了以ADP为诱导剂的体外抗血小板聚集的活性试验，结果表明，标题化合物的活性均强于对照药阿司匹林，其中化合物4d的活性最强。
关键词：3-乙酰基香豆素；肟醚；抗血小板凝聚
中图分类号：R916文献标识码：A文章编号：0258-3283（2020）
Synthesis and Antiplatelet Aggregation Activity of 3-Acety-coumarins Derivatives HE Bing, LIU Hong, XIAO Wei-yu, ZHANG Qiang, ZHANG Qun-ying*(College of Pharmacy, Anhui University of Chinese Medicine, Hefei 230038, China), Huaxue Shiji, 2020, 42(11), ～
Abstract: 3-Acetyl-coumarin was obtained by the reactions between salicylaldehyde and ethyl acetoacetate followed by treating with dibromoalkanes ( 2～6 carbons) in the presence of K2CO3 to provide the compounds 3-acethlcoumarin bromoether (3a～3e), these compounds were then reacted with morpholine to give the target compounds 3-acetyl-coumarins cerivatives. Structures were confirmed by 1HNMR, IR, and MS. The intermediate and five target compounds were tested for the anti-platelet aggregation activity of ADP as an inducer by Born turbidimetry. In vitro-platelet aggregation activity results show that compounds 4d has the best activity, compounds 4a～4e showed significant anti-platelet aggregation activities comparable to stronger than that of control aspirin. Particularly, the compound 4d showed excellent anti-platelet aggregation activity.
Key words: 3-acetyl-coumarin; anti-platelet; oxime ethers
引用本文：何冰，刘红，肖维玉，等. 3-乙酰基香豆素衍生物的合成及抗血小板聚集活性[J].化学试剂，2020，42(11)：1305-1308。
二茂铁染料在敏化太阳能电池的研究进展
王磊1，李耀龙2，陈瑜*1
（1. 天津理工大学，化学化工学院，天津 300384；2.天津大格科技有限公司，天津 301700）
摘要:染料敏化太阳能电池（DSSC）已成为低成本光伏最有前途的技术之一，也是作为基于传统太阳能电池的有前途的替代品，吸引了相当大的研究兴趣。目前为止，制作高效率的染料敏化太阳能电池，许多研究学者制作出了各种各样的敏化剂。染料敏化剂对光收集和电子注入效率都起着至关重要的作用。染料敏化剂可分为两种：金属有机染料敏化剂和非金属染料敏化剂。二茂铁或二茂铁衍生物可作为供电子基的有机染料敏化剂，可以提高太阳能电池的光电转化效率，受到越来越的关注。
关键字：有机光伏；太阳能电池；染料敏化剂；二茂铁；光电转换效率
中图分类号：O621.3 文献标识码：A 文章编号：0258-3283（2020）--
Progress of Ferrocene Dyes in Sensitized Solar Cells WANG Lei1, LI Yao-Long 2, CHEN Yu*1 (1. School of chemistry and chemical engineering, Tianjin University of Technology, Tianjin 300384, China; 2. Tianjin dag technology co., LTD., Tianjin 301700, China), Huaxue Shiji, 2020, 42(11), ～
Abstract: Dye-sensitized solar cells (DSSC) have become one of the most promising technologies for low-cost photovoltaics, and as promising alternatives to traditional solar cells, have attracted considerable research interest. So far, many researchers have produced a variety of sensitizers to produce highly efficient dye-sensitized solar cells. Dye sensitizers play a vital role in both light collection and electron injection efficiency. There are two types of dye sensitizers: metal-organic dye sensitizers and non-metallic organic dye sensitizers. Ferrocene and ferrocene derivatives can be used as electron-donor-based organic dye sensitizers, which can improve the photoelectric conversion efficiency of solar cells, which is receiving increasing attention.
Key words: organic photochemistry; solar cells; dye sensitizers; ferrocene; photoelectric conversion efficiency
引用本文：王磊, 李耀龙, 陈瑜. 二茂铁染料在敏化太阳能电池的研究进展[J]. 化学试剂, 2020, 42(11): 1309-1317.
氧化偶氮苯类化合物合成研究进展
黄子安1，李陵岚2，刘辉*1
（1. 武汉工程大学 材料科学与工程学院，湖北 武汉 430205；2. 湖北大学 化学化工学院，湖北 武汉 430062）
摘要：氧化偶氮苯化合物作为一类有机化工原料和中间体在染料、指示剂及液晶材料等方面具有重要的应用。工业上常采用葡萄糖等还原剂在碱性条件下还原芳香硝基化合物来制备氧化偶氮苯化合物，但该方法存在环境不友好的问题。简述了氧化偶氮苯化合物的发展现状，介绍了硝基化合物还原和氨基化合物氧化两条反应路线制备氧化偶氮苯化合物的相关研究，分析了两条合成路线的反应机理，讨论了催化体系和反应条件对选择性制备氧化偶氮苯的影响因素，总结了各种催化体系的优缺点，指出氧化偶氮苯合成方法应进一步发展高效、廉价的催化体系，发展无溶剂或以离子液体为溶剂的合成方法和以光、电等新能源驱动反应的合成方法，以实现氧化偶氮苯合成反应体系更加高效、绿色、经济和简便。
关键词：氧化偶氮苯化合物；芳香硝基化合物；氨基化合物；还原；氧化
中图分类号：TQ61 文献标识码：A 文章编号：0258-3283（2020）
Progress in the synthesis of azoxybenzene compound Huang Zian 1, Li Ling-lan 2, Liu Hui *1 (1. School of Materials Science and Engineering, Wuhan Institute of Technology, Wuhan 430205; 2. College of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062, China), Huaxue Shiji, 2020, 42(11), ～
Abstract: As a kind of organic chemical raw material and intermediate, azoxybenzene compound has important applications in dye, indicator and liquid crystal materials. In industry, the reduction of aromatic nitro compound with glucose or other reducing agents under alkaline conditions is often used to prepare azoxybenzene compound. However, the method is not environmentally friendly. We reviewed the development of azoxybenzene compound, introduced two reaction routes of reduction of aromatic nitro compound and oxidation of aromatic amino compound to prepare azoxybenzene compound, and analyzed the reaction mechanism of two synthetic routes. Also, we discussed the influence factors of catalytic system and reaction conditions on the selective preparation of azoxybenzene compound, and summarized the advantages and disadvantages of various catalytic systems. It is pointed out combined with the above that the synthesis method of azoxybenzene compound should be further developed with high efficiency and low cost catalytic system, solvent-free or ionic liquid as solvent and new energy driven reaction, so as to realize the synthesis reaction system more efficient, green, economic and simple.
Keywords: azoxybenzene compound; aromatic nitro compound; aromatic amino compound; reduction; oxidation
引用本文：黄子安，李陵岚，刘辉. 氧化偶氮苯类化合物合成研究进展[J]. 化学试剂, 2020, 42(11):1318-1326.
高效液相色谱法测定款冬花中款冬酮含量的不确定度评估
万浩芳，应佳妮*
(浙江中医药大学 中医药科学院，浙江 杭州 310053)
摘要：采用高效液相色谱（HPLC）法对款冬花中款冬酮含量测定的结果进行不确定度评估，明确影响不确定度的因素。参照《中华人民共和国药典》（2015版）一部款冬花含量测定方法，建立数学模型，对影响结果准确性的各个因素的不确定度进行计算和评估。该研究中，HPLC法测定款冬花中款冬酮含量的扩展不确定度为0.0028%。对照品引入过程对HPLC法测定款冬花中款冬酮含量的不确定度影响最大，严格控制此过程有利于提高检测结果的准确性，为款冬酮的质量控制提供参考依据。
关键词：款冬花；款冬酮；不确定度；液相；含量测定
中图分类号：R917.101 文献标识码：A 文章编号：0258-3283（2020）
Uncertainty Evaluation for Determination of Tussilagone in Farfarae Flos by High Performance Liquid Chromatography WAN Hao-fang, YING Jia-ni*(Academy of ChineseMedical Sciences, Zhejiang Chinese Medical University, Hangzhou 310053, China), Huaxue Shiji, 2020, 42(11), ～
ABSTRACT: To find out the impacting factors in uncertainty by analyzing the measurement uncertainty in the determination of tussilagone in Farfarae Flos by HPLC and provide the evidence for the measurement evaluation. The determination method of Farfarae Flos was according to Chinese Pharmaco-poeia (CP) 2015. A mathematical model is established to calculate and evaluate the uncertainty of each factor that affects the accuracy of the results. The expanded uncertainty for the HPLC determination of tussilagone is 0.0028%. The uncertainty is mainly caused by the weight of standard, focusing on this link can improve the accuracy of the results, can provide theory evidence for accurate control of the measurement method.
KEY WORDS: Farfarae Flos; tussilagone; Uncertainty of measurement; HPLC; content determination
引用本文：万浩芳，应佳妮. 高效液相色谱法测定款冬花中款冬酮含量的不确定度评估[J]. 化学试剂，2020，42（11）：1327-1330.
缬沙坦结构确证的建立
陈文霞1，高浩凌*1,2，白妍1，朱兰芳1，沈大冬1
(1. 浙江医药股份有限公司 研究院，浙江 绍兴 312500；2. 浙江昌海制药有限公司，浙江 绍兴 312300)
摘要：缬沙坦是一种血管紧张素-Ⅱ（Angiotensin-Ⅱ）受体拮抗剂，具有疗效确切、降血压效果持久稳定、副作用小、耐受性良好的特点，是继钙离子拮抗剂和血管紧张素转化酶抑制剂(ACEI)之后另一类具有竞争力的降压药。通过紫外吸收光谱（UV）、红外吸收光谱（IR）、高分辨质谱（HRMS）、核磁共振波谱（1H NMR、13C NMR、DEPT135、1H-1H COSY、HMQC、HMBC）数据和TGA/DSC对缬沙坦进行结构表征，并对其红外光谱和核磁共振波谱进行了详细的解析和归属。综合运用多种谱学方法确证了缬沙坦的结构，为其质量研究提供参考。
关键词：缬沙坦；抗高血压药；核磁共振；归属；结构确证；
中图分类号：O482.53 文献标识码；A 文章编号：0258-3283（2020）
Establishment of Valsartan Structural Elucidation CHEN Wen-xia1，GAO Hao-ling*1,2，BAI Yan1，ZHU Lan-fang1，SHEN Da-dong1 (Research & Development Center, Zhejiang Medicine Co., Ltd., Shaoxing 312500, China；2. Zhejiang Changhai Pharmaceutical Co., Ltd., Shaoxing 312300, China)
Abstract: Valsartan is an angiotensin-Ⅱ (Angiotensin-Ⅱ) receptor antagonist with definite curative effect, lasting and stable blood pressure lowering effect, low side effects, and good tolerance. It is a calcium ion antagonist and angiotensin invertase inhibitor (ACEI) is another competitive antihypertensive drug. Ultraviolet absorption spectrum (UV), infrared absorption spectrum (IR), high resolution mass spectrometry (HRMS), nuclear magnetic resonance (NMR) spectroscopy (1H NMR, 13C NMR, DEPT135, 1H-1H COSY, HMQC, HMBC) data and TGA/DSC confirmed the structure of valsartan, and analyzes and assigns its infrared spectrum and nuclear magnetic resonance spectrum in detail. A variety of spectroscopy methods are used to confirm the structure of valsartan and provide a reference for its quality research.
Key words: Valsartan; antihypertensive; nuclear magnetic resonance; assignment; structure elucidation
引用本文：陈文霞, 高浩凌, 白妍, 等. 缬沙坦结构确证的建立[J]. 化学试剂, 2020, 42(11):1331-1335。
气相色谱法测定PTMEG产品中微量丁醇含量
陈德义
（新疆蓝山屯河能源有限公司， 新疆 奇台 831800）
摘要：为准确测定高粘度聚合物中微量杂质的含量，本文选用气相色谱法，通过色谱参数和稀释溶剂的优化选择，用标准物质定性和外标工作曲线定量，建立了一种检测PTMEG中所添加微量正丁醇含量的方法，方法检出限1.6mg/kg，外标曲线相关系数R2=0.9994，加标回收率99.3%～100.4%，标准偏差和相对标准偏差分别为4.73mg/kg和0.39%，方法具有灵敏度高、重现性好、普适通用、准确可靠等特点，满足产品出厂控制需要。
关键字：气相色谱法；PTMEG；微量丁醇；高粘度聚合物；外标法。
中图分类号：O656.31 文献标识码：A 文章编号：0258-3283（2020）--
Determining the Trace Butanol Content in PTMEG Product by GC Method Chen De-Yi (Xinjiang Blue Ridge Tunhe Energy co., ltd., Qitai 831800，China), Huaxue Shiji, 2020, 42(11),～
Abstract：To determine the content of trace impurity accurately in high viscosity polymer, the GC method is chosen, By optimizing chromatographic parameters and selecting dilution solvents, identified by standard substances and quantified by the external standard method. A new method is established, which determine the trace additive content of n-butanol in PTMEG exactly. The detection limit is 1.6mg/kg, the correlation coefficient of the working curve is 0.9994, the recovery rate of adding the standard substance is 99.3%-100.4%, the standard deviation and the relative standard deviation of this method is 4.73mg/kg and 0.39%. The method is high sensitivity, good reproducible, accurate and reliable, it can satisfy the need for product delivery.
Key words： GC method, PTMEG, Trace n-butanol，high viscosity polymer，external standard method.
引用本文：陈德义. 气相色谱法测定PTMEG产品中微量丁醇含量[J]. 化学试剂, 2020, 42(11):1336-1340.
催化分光光度法测定水中微量碘的方法优化
贾亮亮*，尹红云
（河北省水文工程地质勘查院，河北 石家庄 050021）
摘要：旨在优化以催化分光光度法定量分析水体中微量碘的分析体系。在醋酸盐缓冲溶液体系中，碘催化4,4’-四甲基二氨基-二苯基甲烷与氯胺T发生氧化反应，生成蓝色配合物，通过测试该配合物的吸光度可定量分析水体中的碘。优化了分析体系中的测定波长、缓冲溶液的用量、显色剂的用量、氯胺T的浓度等实验条件。在优化的实验条件下，分光光度法的微量碘测定结果的相对标准偏差为2.1%，检出限为0.1 μg/L。该方法选择性好、操作简便、成本低、灵敏度高，满足水文地质工作对水中微量碘含量普查的要求。
关键词：催化分光光度法；水；方法优化；微量碘；4,4’-四甲基二氨基-二苯基甲烷；氯胺T
中图分类号：O657.32 文献标识码：A 文章编号：0258-3283（2020）--
Optimization of catalytic spectrophotometry for the determination of trace Iodine in water JIA Liang-liang*, YIN Hong-yun (The Institute of Hydrology and Engineering Geological Prospecting Hebei Province, Shijiazhuang 050021, China), Huaxue Shiji, 2020, 42(11), ～
Abstract: To optimize the analytical system for the quantitative analysis of trace iodine in water by catalytic spectrophotometry, in the acetate buffer solution system, 4,4’-tetramethyldiamino diphenylmethane and chloramine T reacted to form blue complex in the acetate buffer system, such as the measured wavelength, the amount of buffer solution, the amount of developer and the concentration of chloramines T. The experimental conditions were optimized. Under the best experimental conditions, the trace iodine in water was determined by spectrophotometry. The relative standard deviation was 2.1%, and the detection limit was 0.1 μg/L. The results show that the method had the advantages of good selectivity, simple operation, low cost and high sensitivity.It met the requirements of hydrogeological work for general survey of trace iodine content in water.
Key words: catalytic spectrophotometry; water; method optimization; trace iodine; 4,4’-tetramethyldiamino diphenylmethane; chloramine T
引用本文：贾亮亮，尹红云. 催化分光光度法测定水中微量碘的方法优化[J]. 化学试剂，2020, 42（11）：1341-1344.
DPP-4抑制剂LGT-6在不同种属肝微粒体中的代谢特征
张宇1.2，陈瑞2，张丽1,2，班玉娟1,2，汤磊2，朱高峰2，廖伟科*2
（1. 贵州医科大学 药学院，贵州 贵阳 550004；2.贵州省化学合成药物研发利用工程技术研究中心，贵州 贵阳550004）
摘要：研究降糖化合物LGT-6在人、比格犬、大鼠肝微粒体中的代谢稳定性，探讨其在不同种属肝微粒体中的代谢特征，为后期LGT-6的体内代谢提供参考依据。分别将LGT-6溶于由NADPH启动Ⅰ相代谢、UDPGA启动的Ⅱ相代谢以及二者共同启动的两相代谢孵育体系中，孵育至相应时间点终止反应，测定LGT-6的质量浓度，以计算LGT-6的剩余百分率与酶动力学参数。LGT-6在Ⅰ相代谢、Ⅱ相代谢及两相代谢中稳定性良好，不易受Ⅰ相代谢酶与Ⅱ相代谢酶的影响，预测LGT-6可能在人体内的驻留时间长、作用持久、生物利用度高，体内药动学与药效学性质俱佳，对Ⅱ型糖尿病的治疗作用更加显著。所创建的UPLC-MS/MS法适用于LGT-6的体外代谢研究，为后续体内代谢、毒理研究及动物模型的选择提供参考依据。但在Ⅰ相孵育体系中人肝微粒体的T1/2明显大于比格犬与鼠，这可能与物种之间的种属差异相关。
关键词：DPP-4抑制剂LGT-6；降糖；肝微粒体；代谢特征；酶动力学
中国分类号：R96 文献标识码：A 文章编号：0258-3283（2020）11--
Metabolic Stability of DPP-4 Inhibitor LGT-6 in Liver Microsomes of Different Species ZHANG Yu1,2 , CHEN Rui2, ZHANG Li1,2, BAN Yu-juan1,2, TANG Lei2, ZHU Gao-feng2, LIAO Wei-ke*2 (1. School of Pharmacy, Guizhou Medical University, Guiyang 550004, China; 2. Guizhou Provincial Engineering Technology Research Center for Chemical Drug R&D, Guiyang 550004, China), Huaxue Shiji, 2020, 42(11), ～
Abstract：To study the metabolic stability of hypoglycemic compound LGT-6 in human, beagle dog and rat liver microsomes, and to explore its metabolic characteristics in different species of liver microsomes, so as to provide reference basis for the metabolism of LGT-6 in vivo. LGT-6 was dissolved in phase I metabolism initiated by NADPH, phase II metabolism initiated by UDPGA and two-phase metabolism incubation system initiated by both of them, respectively, and incubated to the corresponding time point to stop the reaction. The mass concentration of LGT-6 was determined, and the residual percentage of LGT-6 and enzyme kinetic parameters were calculated. LGT-6 is stable in phase Ⅰ, phase Ⅱ and biphasic metabolism, and is not easily affected by phase Ⅰ and phase Ⅱ metabolic enzymes. It is predicted that LGT-6 may have long residence time, long-lasting effect, high bioavailability, good pharmacokinetics and pharmacodynamics in vivo, and has a more significant therapeutic effect on typeⅡ diabetes. The UPLC-MS/MS method established in this study is suitable for the study of metabolism of LGT-6 in vitro, and provides a reference basis for subsequent metabolic and toxicological studies in vivo and the selection of animal models. However, in phase I incubation system, the T1/2 of human liver microsomes was significantly larger than that of beagle dogs and mice, which may be related to the species differences among species.
Keywords：DPP-4 inhibitor LGT-6; Hypoglycemic; Livermicrosome; Metabolic characteristics; Enzyme kinetics
引用本文：张宇，陈瑞，张丽，等. DPP-4抑制剂LGT-6在不同种属肝微粒体中的代谢特征[J]. 化学试剂，2020，42（11）：1345-1350.
1,8-萘二酸构筑的六核锌配合物的合成、结构和荧光性质
许明媛*1，朱莉娜2，李涛1
(1. 潍坊护理职业学院 药学系，山东 潍坊 262500；2. 天津大学 化学系，天津 300072）
摘要：以ZnSO4·7H2O、1,10-邻菲罗啉（phen）和荧光发色团1,8-萘二甲酸酐（1,8-ndc）为原料，用水热法合成了一个新的六核配合物[Zn(1,8-ndc)(phen)(H2O)2]6·CH3OH·H2O，并对其进行了X-射线单晶衍射结构分析、红外光谱表征和荧光性质研究。单晶结构分析表明该配合物属于三方晶系，R-3空间群，单胞参数为a = 19.5181(6) Å，b = 19.5181(6) Å，c = 30.1722(2) Å，α = 90˚，β = 90˚，γ = 120˚。配合物中6个1,8-ndc配体桥联6个ZnⅡ离子，形成了一个封闭的环状六核配合物。荧光光谱分析表明，该六核锌配合物的荧光发射峰峰值显著增强，有望作为荧光探针用于生物及医学检测中。
关键词：锌配合物；1,8-萘二甲酸；1,10-phen；荧光性质
中图分类号：O641.4 文献标识码：A 文章编号：0258-3283（2020）
Synthesis, Crystal Structure and Fluorescent Properties of Hexanuclear Zinc Complex Constructed by 1,8-Naphthalene Acid XU Ming-yuan*1，ZHU Li-na2，LI Tao1 (1. Department of Pharmacy, Weifang Nursing Vocational College, Weifang 262500, China; 2. Department of Chemistry, Tianjin University, Tianjin 300072, China), Huaxue Shiji, 2020, 42(11)
Abstract: A new hexanuclear complex was synthesized with ZnSO4·7H2O, 1,10-phenanthroline (phen), and fluorescent chromophore 1,8-naphthalic anhydride (1,8-ndc) by the hydrothermal method and characterized by X- ray crystallography, IR spectroscopy and luminescent properties. X-ray single crystal structural analysis indicates that the complex crystallize in rhombohedral system and R-3 space group with crystal parameters of a = 19.5181(6) Å, b = 19.5181(6) Å, c = 30.1722(2) Å, α = 90˚, β = 90˚, γ = 120˚. In the complex six ZnⅡ ions are connectedby six 1,8-ndc bridges that alternately form a closed ring. The fluorescence spectra analysis shows that the fluorescence emission peak of the hexanuclear zinc complex increased effectively and may be used as a fluorescence probe in biological and medical detection.
Key words: zinc complex; 1,8-naphthalene acid; 1,10-phen; fluorescence properties
引用本文：许明媛，朱莉娜，李涛. 1,8-萘二酸构筑的六核锌配合物的合成、结构和荧光性质[J]. 化学试剂，2020，42(11)：1351-1354。
官能化3-吲哚吡喃衍生物的简便合成及其晶体结构
於露a,b，龚潘伟b，马莹b，朱松磊*b
（徐州医科大学 a.基础医学院，b.药学院，江苏 徐州 221004）
摘要：利用多组分一锅法反应，在微波照射条件下简便快速合成2-氨基-6-(3-吲哚基)-4-芳基-4H-吡喃-3,5-二腈化合物，并对目标产物进行了熔点、红外、核磁共振谱以及X-射线单晶衍射表征。产物单晶衍射结果表明：该晶体属于三斜晶系，空间群P-1，晶体参数为a = 0.9492(2) nm、b = 1.1417(3) nm、c = 1.2040(3) nm、α = 105.06(2)°、β = 103.20(3)°、γ = 111.19(3)°。在分子晶体结构中，合成新构建的吡喃环为平面构型，其与相连的吲哚环接近平行，其二面角为7.33(4)°；其与相连的芳环接近垂直构型，其二面角为87.89 (4)°。
关键词：吲哚-3-基吡喃；多组分反应；微波；晶体结构; 合成
中图分类号：O 626 文献标识码：A 文章编号：0258-3283（2020）
A Facile Synthesis of Functionalized Indol-3-yl Pyran Derivative and Crystal Structure YU Lua,b, GONG Pan-weib, MA Yingb, ZHU Song-lei*,b (a. School of Basic Medical Sciences, b. School of Pharmacy, Xuzhou Medical University, Xuzhou, Jiangsu 221004)
Abstract: A serial of indole-pyran heterocycles derivatives, 2-amino-4-aryl-6-(1H-indol-3-yl)-4H-pyran -3,5-dicarbonitrile, were synthesized by microwave-assistant one-pot three-component reaction and fully characterized by IR, 1HNMR and single X-ray diffraction. The crystal of the product 4d belongs to triclinic, space group P-1 with a = 0.9492(2) nm, b = 1.1417(3) nm, c = 1.2040(3) nm, α = 105.06(2)°, β = 103.20(3)°, γ = 111.19(3)°. In the crystal structure, the pyran ring adopts plane configuration, which linked with the indole ring for almost coplanar conformation. The pyran ring and attached benzene ring have nearly vertical conformation with the dihedral angle is 87.89 (4)°.
Key words: indol-3-yl-pyran, multi-component reaction, microwave reaction, crystal structure, synthesis
引用本文：於露，龚潘伟，马莹，等.官能化3-吲哚吡喃衍生物的简便合成及其晶体结构[J]. 化学试剂, 2020, 42(11)：1355-1360.
鹅去氧胆酸重结晶纯化及溶剂对其结晶形态影响研究
胡祥正*，王玲
(天津科技大学 化工与材料学院，天津 300457)
摘要：通过对鹅去氧胆酸重结晶液固比及温度的优化，建立了一种鹅去氧胆酸的重结晶纯化方法，并应用溶液重结晶法探究溶剂对鹅去氧胆酸性质和晶体形貌的影响，对重结晶后鹅去氧胆酸样品进行IR、HPLC、XRD、DSC以及SEM等表征。结果显示：样品最高收率达85.2%，纯度达99.9%。溶剂对鹅去氧胆酸重结晶的形态有较大影响。在不同种溶剂中重结晶后，鹅去氧胆酸晶体形貌呈现多样性，表现出表面和截面有孔的规则六棱柱、不规则颗粒状、片层状、表面光滑的实心六棱柱、表面光滑的中空六棱柱。
关键词：鹅去氧胆酸；重结晶；纯化；溶剂效应；晶体形态；晶体物性
中图分类号： O629.2 文献标识码：A 文章编号：0258-3283（2020）11
Crystallization Purification of Chenodeoxycholic Acid and Effect of Solvent on Crystal Morphology HU Xiang-Zheng*,WANG Ling (College of Chemical Engineering and Materials Science, Tianjin University of Science & Technology, Tianjin, 300457, China)
Abstract：A recrystallization method of chenodeoxycholic acid is established by optimization of recrystallization conditions，including liquid-solid ratio and recrystallization temperature．The influence of solvent on the properties and crystal morphology of chenodeoxycholic acid was investigated by solution recrystallization. The crystal properties were tested by IR, HPLC, XRD, DSC and SEM, respectively. The results show that the maximum yield of the sample is 85.2% and the purity is 99.9%, and the morphology of CDCA crystal is different in different solvents. In ethyl acetate, regular hexagonal prism with pores on its surface and cross section was formed; in acetonitrile, irregular granular crystal was formed; in ethyl acetate acetonitrile mixed solvent, layered crystal was formed; in ethyl acetate hexane mixed solvent, solid hexagonal prism crystal with smooth surface was formed; in ethyl acetate chloroform mixed solvent, hollow hex-prism crystal with smooth surface was formed.
Key words：chenodeoxycholic acid; recrystallization; solvent; crystal morphology
引用本文：胡祥正，王玲. 鹅去氧胆酸重结晶纯化及溶剂对其结晶形态影响研究[J]. 化学试剂，2020，42（11）：1361-1365.
新型多取代5-吡唑啉酮的合成与表征
任传清*，张强
（陕西理工大学 化学与环境科学学院 催化基础与应用重点实验室, 陕西 汉中 723000）
摘要：5-吡唑啉酮类化合物作为抗菌药物的母核结构，在天然产物和药物化合物方面应用广泛。以氢氧化钠为碱，2-二乙硫基亚甲基乙酰乙酰苯胺肟和对甲苯磺酰氯反应合成了一系列新型标题化合物，通过核磁共振、质谱分析对所得化合物的组成和结构进行表征，测定了产物的熔点，并对该反应机理进行了探讨。该合成方法处理简单、操作安全，该方法为合成的5-吡唑啉酮类衍生物提供了一种有效的途径。
关键词：乙酰乙酰苯胺肟；5-吡唑啉酮；氢氧化钠；杂环化合物
中图分类号：O626.2 文献标识码：A 文章编号：0258-3283（2020）
Synthesis and Characterization of Novel Polysubstituted 5-Pyrrazolone Compounds REN Chuan-qing, ZHANG Qiang (Shaanxi Key Laboratory of Catalysis, School of Chemical & Environmental Science, Shaanxi University of Technology, Hanzhong 723000, China), Huaxue Shiji, 2020, 42(11)
Abstract: 5-Pyrazolone compounds are widely used as key nucleus for antibacterial drugs in many natural products and pharmaceutical substances. The synthesis of novel polysubstituted 5-pyrazolone compounds were developed from 2-(bis(ethylthio)methylene) acetylanilidoxime and 4-toluene sulfonyl chloride in the presence of sodium hydroxide. The composition and structure has been confirmed by 1HNMR, 13CNMR and HR-MS. The melting point has been determined. Moreover, a mechanism for the reaction was proposed. The method is characterized by simple after-treatment and safe operation, the protocol provides an effective approach to synthesize 5-pyrazolone compounds.
Key words: acetylanilidoxime; 5-pyrazolone; sodium hydroxide; heterocyclic compounds
引用本文：任传清，张强. 新型多取代5-吡唑啉酮的合成与表征[J]. 化学试剂, 2020, 42(11): 1366-1369。
氢氧化铯催化端炔与二替加氟二硒醚反应制备(Z)-1,2-二替加氟硒基烯烃
喻爱和1，许新华*2
(1. 湖南机电职业技术学院 化工学院，湖南 长沙 410151； 2. 湖南大学 化学化工学院， 湖南 长沙 410082)
摘要：以CsOH.H2O作催化剂，以端炔与二替加氟二硒醚作为反应原料，N,N-二甲基甲酰胺（DMF）作为溶剂，氮气氛围下，反应在室温下能够有效进行，较高产率和高立体选择性的得到新型目标化合物，产率为56%～83%。通过1HNMR、13CNMR、IR和HRMS对目标产物进行确证，并提出了可能的反应机理，为目标化合物的制备提供了一个高效、温和的路径，对进一步研究含硒替加氟药物活性具有重要作用。
关键词：氢氧化铯；二替加氟二硒醚；端炔；催化；(Z)-1,2-二替加氟硒基烯烃
中图分类号：O627.6 文献标志码：A 文章编号：0258-3283（3283）--
Cesium Hydroxide-Catalyzed Synthesis of (Z)-1,2-Bistegafurselenoalkenes through the Selenation of Terminal Acetylenes with Ditegafur Diselenides YU Ai-he1, XU Xin-hua*2 (1. Hunan Mechanical and Electrical Polytechnic College，Changsha 410151, China; 2. College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China), Huaxue Shiji, 42(11), ～
Abstract: A highly stereoselective approach for the synthesis of (Z)-1,2-bistegafurselenoalkenes was demonstrated through the reaction of terminal acetylenes with ditegafur diselenides catalyzed by cesium hydroxide in DMF, under mild conditions and nitrogen atmosphere with 56%～83% yields. And all the desired products were confirmed by 1HNMR, 13CNMR, IR and HRMS. Then the possible reaction mechanism was also proposed. The method provides an efficient and mild route to (Z)-1,2-bistegafurselenoalkenes, which plays an important role in the further study of the pharmaceutical activity of tegafur containing selenium.
Key words: cesium hydroxide; ditegafur diselenides; terminal acetylenes; catalysis; (Z)-1,2-Bistegafurselenoalkenes
引用本文：喻爱和，许新华. 氢氧化铯催化端炔与二替加氟二硒醚反应制备(Z)-1,2-二替加氟硒基烯烃[J]. 化学试剂, 42(11): 1370-1376.
KI促进乙酰丙酮、CS2与苄氯及其衍生物缩合制备烯酮二硫缩酮类化合物
李小港*1，李雪琴1，申秀丽1，孙岩峰2
(1.宜春学院 化学与生物工程学院，江西 宜春 336000；2.浙江吉华集团股份有限公司 技术中心，浙江 杭州 311234)
摘要：以廉价的苄氯及其衍生物为原料代替苄溴与乙酰丙酮、CS2缩合，高收率的合成烯酮二硫缩酮类化合物。在室温下，以K2CO3作为碱，在N,N-二甲基甲酰胺溶剂中，KI能够有效的促进亲核反应进行，从而提高产物的收率。以4-溴苄氯参与的缩合反应为模式反应，考察了KI对反应的促进作用，20 mol%KI存在时反应12 h，即可得到90%的收率，而无KI时收率仅为69%。KI对于其他苄氯参与的反应同样有效，共合成8个化合物，收率68%～95%，目标产物结构通过核磁和元素分析进行了确证。
关键词：苄氯；烯酮二硫缩酮；KI；晶体结构；缩合反应
中图分类号：O621 文献标识码：A 文章编号：0258-3283（2020）11--
KI Promotes Condensation Between Acetylacetone, CS2, Benzyl Chloride and its Derivatives to Obtain Ketene Dithioacetals. LI Xiao-Gang*1, LI Xue-Qin1, SHEN Xiu-Li1, SUN Yan-Feng2 (1. College of Chemistry and Bioengineering, Yichun University, Jiangxi Yichun, 336000; 2. Technology Center, Zhejiang Jihua Group), Huaxue Shiji, 2020, 42(11), ～
Abstract: Using cheap benzyl chloride and its derivatives as raw material, ketene dithioacetals was obtained via the condensation between acetylacetone, CS2 with high yield. At room temperature, KI promotes the reaction, which used dimethylformamid as solvent and K2CO3 as base. The condensation between acetylacetone, CS2 and 4-bromobenzyl chloride was used as model reaction, and the promotion of KI for the condensation was investigated. In the presence of 20 mol% KI, the yield was 90%. On the contrary, the product was separated with only 69% yield in the absence of KI. The protocol was also efficient for the condensation of the substituted benzyl chloride, through which 8 ketene dithioacetals were obtained in 68%～95% yield.
Key words: benzyl chloride; 3-[bis-(4-bromo-benzylsulfanyl)-methylene]-pentane-2,4-dione; IK; crystal structure; condensation reaction
引用本文：李小港，李雪琴，申秀丽，等. KI促进乙酰丙酮、CS2与苄氯及其衍生物缩合制备烯酮二硫缩酮类化合物[J]. 化学试剂，2020，42（11）：1377-1380.
3-吡啶甲酰基吲哚类化合物的合成研究
徐孟华a，沈梦婷b，王盈盈b，黄乐浩*a,b
（温州医科大学 a.药学院，b.仁济学院，浙江 温州 325035）
摘要：为了发展一种高效简便合成3-吡啶甲酰基吲哚衍生物的合成方法，使用N-烷基芳香胺和吡啶甲酰基烯胺作为反应底物，通过考察催化剂、氧化剂、反应温度及溶剂对反应的影响来获得最优的反应条件。在最优反应条件下，吡啶甲酰基烯胺的sp2 C-H键与N-烷基芳香胺的邻位sp2 C-H键通过交叉氧化脱氢环化反应，一步及高区域选择性地合成了7个3-吡啶甲酰基吲哚衍生物。产物均通过1HNMR、13CNMR和HR-MS等分析方法进行结构表征。
关键词：钯催化；氧化偶联反应；3-吡啶甲酰基吲哚衍生物
中图分类号:O626.13 文献标识码:A 文章编号:0258-3283（2020）11--
Synthesis of 3-pyridinecarbonyl indoles XU Meng-huaa, SHEN Meng-tingb, WANG Ying-yingb, HUANG Le-hao*a,b (a. School of Pharmaceutical Sciences; b. Renji College, Wenzhou Medical University, Wenzhou 325035, China), Huaxue Shiji, 2020, 42(11), ～
Abstract: Palladium-catalyzed oxidative cross-coupling of the sp2 C-H bonds of picolinoylenamines with sp2 C-H bonds of N-alkylanilines to directly give high-value 3-picolinoylindole derivatives was reported. The substituted enamines were prepared by condensation of 2-acetylpyridine with N,N-dimethylformamide dimethyl acetyl. A range of N-alkylanilines can be used in this transformation. The optimal reaction was obtained with Cu(OAc)2 as the oxidant in benzotrifluoride at 90 ℃ for 24 h in the air. Under these conditions, the seven 3-picolinoylindole compounds were synthesized. The structure of all compounds were confirmed by 1HNMR, 13CNMR and HR-MS.
Key Words: palladium-catalyzed; cross-dehydrogenative coupling reaction; 3-picolinoylindole
引用本文：徐孟华, 沈梦婷, 王盈盈, 等. 钯催化N-烷基芳香胺和吡啶甲酰基烯胺反应合成3-吡啶甲酰基吲哚衍生物[J]. 化学试剂, 2020，42(11)：1381-1384.
高纯度2-溴苯并[9,10]菲的合成研究
段陆萌*1，陈婷1，李仲庆1，李继响1，马则群2，梁现丽1，杭德余*1
（1. 北京燕化集联光电技术有限公司，北京 102502；2. 北京理工大学 化学与化工学院，北京 100081）
摘要：标题化合物为有机发光、盘状液晶和生物医药等领域的重要中间体。高纯度的标题化合物的合成方法在文献中少有报道。以2-溴联苯为起始原料，先经过超低温锂化反应制成硼酸，再与2,5-二溴硝基苯进行Suzuki偶联反应制得(2-硝基-4-溴苯基)-1-1’-联苯，再经过铁粉还原得到(2-氨基-4-溴苯基)-1-1’-联苯，最后使用亚硝酸异戊酯关环制得标题化合物。该合成路线原料易得、操作简便、产品纯度高，适合工业化生产和市场高标准品质需求。化合物均经过氢谱和碳谱结构表征、高效液相色谱仪纯度测定，目标化合物还经过差示扫描量热仪和热重分析仪测试性能。
关键词：2-溴苯并[9,10]菲；高纯度；有机电致发光材料；三亚苯；稠环化合物
中图分类号：O626.13 文献标识码：A 文章编号：0258-3283（2020）
Synthesis of High Purified 2-Bromobenzo[9,10]phenanthrene DUAN Lu-meng*1, CHEN Ting1, LI Zhong-qing1, LI Ji-xiang1, MA Ze-qun2, LIANG Xian-li1, HANG De-yu*1 (1. Beijing Yanhua Jilian Optoelectronic Technology Co., Ltd., Beijing 102502, China; 2. School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China), Huaxue Shiji, 2020, 42(11)
Abstract: 2-Bromobenzo[9,10]phenanthrene is an important intermediate in some fields such as organic luminescence, disk liquid crystal and biomedicine. The synthesis method of high purity 2-bromobenzo [9,10] phenanthrene is rarely reported in literatures. An intermediate was prepared by Suzuki coupling reaction with 2,5-dibromonitrobenzene and 2-amino-4-bromophenyl-1,1’-biphenyl was obtained through 2-nitro-4- bromophenyl-1,1'-biphenyl being reduced by iron powder. The target compound was prepared by using isoamyl nitrite. Synthetic route of the compound was easy to operate, and the raw materials were easy to obtain. The target compound was suitable for industrialization and market high standard quality demand because of high purity. The structures of the each step compound were confirmed by 1HNMR and 13CNMR, the purity was determined by HPLC, and the performance of target compound was tested by DSC and TGA.
Key words: 2-bromobenzo[9,10]phenanthrene; high purity; organic electroluminescent materials; triphenylene; fused ring compound
引用本文：段陆萌，陈婷，李仲庆，等. 高纯度2-溴苯并[9,10]菲的合成研究[J]. 化学试剂, 42(11):1385-1389。
