金属有机骨架材料载运抗肿瘤药物的研究进展
李婷，向灿辉*
（遵义医学院珠海校区 生物工程系，广东 珠海 519041）
摘要：抗肿瘤药物是当今的研究热点之一，增大抗肿瘤药物生物利用率的同时减小其不良反应是研究者亟待解决的问题之一。金属有机骨架材料因其比表面积和孔隙率大，是一类有潜力的药物载体材料。就金属有机骨架材料作为抗肿瘤药物的药物载体，增大抗肿瘤药物的生物利用率及减小其不良反应的研究进展进行综述，并对金属有机骨架材料在抗肿瘤药物载体方面的应用进行展望。
关键词：金属有机骨架材料；药物载体；抗肿瘤药物
中图分类号： R917 文献标识码：A 文章编号：0258-3283（2019）
Development of Metal-organic Frameworks for Anti-tumor Drug Delivery LI Ting, XIANG Can-hui* (Department of Bioengineering, Zhuhai Campus of Zunyi Medical University, Zhuhai 519041, China), Huaxue Shiji, 2019, 41(1),
Abstract: Increasing the bioavailability and reducing adverse reactions of anti-tumor drugs are issues urgently needed to be overcome. The excellent physicochemical properties like high porosity, high specific surface areas, and varied pore sizes of MOFs（metal-organic frameworks materials）make them promising materials in drug delivery. This work describes various species of MOFs. The achievements in the field of MOFs for anti-tumor drug carriers and delivery are also addressed. The application prospects of metal-organic frameworks for anti-tumor drug delivery are discussed.
Key words: metal-organic frameworks; drug carrier; anti-tumor drugs
邻羧基苯甲醛缩1,3-丙二胺席夫碱的合成工艺优化及结构表征
梁秋群1，刘峥*1，梁楚欣1，李海莹1，黄何香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：以邻羧基苯甲醛和1,3-丙二胺为原料，采用溶液法合成了一种新型席夫碱。通过L9（34）正交试验，得到该席夫碱的最佳合成工艺条件：反应温度为50 ℃，原料物质的量比为2.2︰1，反应时间为4 h，催化剂用量为0.15 mL。采用X-单晶衍射、红外光谱、紫外-可见光谱等测试方法对席夫碱进行结构表征，并通过荧光光谱、热重曲线等探讨其荧光性质和热稳定性质。结果表明，该席夫碱晶体属于单斜晶系，P21/n空间群，晶胞参数为：a=10.5759(10) Å，b=8.5175(6) Å，c=21.042(2) Å，α=90°，β=102.578(9)°，γ=90°，V=1850.0(3) Å3，Z=4，Dc=1.326 g/cm3，μ=0.09 mm–1，F(000)=780。该席夫碱具有良好的荧光性能与热稳定性能。
关键词：席夫碱；正交试验；荧光；热稳定；表征
中图分类号：O622.4 文献标识码：A 文章编号：0258-3283（2019）
Synthesis Optimization and Structural Characterization of 1,3-Propanediamine Schiff Base with O-carboxyl Benzaldehyde LIANG Qiu-qun1, LIU Zheng*1, LIANG Chu-xin1, LI Hai-ying1, HUANG He-xiang1, ZHANG Shu-fen1,2 (1. Guangxi Area Key Laboratory of Electromagnetic Chemical Functional Substance, 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, 2019, 41(1),
Abstract: A new Schiff base was synthesized by solution method from o-carboxyl benzaldehyde and 1,3-propanediamine. The optimum conditions for the synthesis of Schiff base were obtained through L9（34）orthogonal experiments. The optimum conditions of the Schiff base are as follows: the reaction temperature is 50 ℃, the molar ratio of raw materials is 2.2:1, the reaction time is 4 hours, and the amount of catalyst is 0.15 mL. The structure of Schiff base was comfirmed by X-ray diffraction, IR and UV-Vis spectra. The fluorescence properties and thermal stability of Schiff base were investigated by fluorescence spectra and thermogravimetric curves. The results show that the Schiff base crystal belongs to monoclinic system and the space group is P21/n. The unit cell parameters are as follows: a=10.5759(10) Å, b=8.5175(6) Å, c=21.042(2) Å, α=90°, β=102.578(9)°, γ=90°，V=1850.0(3) Å3, Z=4, Dc=1.326 g/cm3, μ=0.09 mm–1, F(000)= 780. The Schiff base has good fluorescence and thermal stability.
Key words: Schiff base; orthogonal test; fluorescence; thermostability; surface feature
石杉碱甲水凝胶微球的制备及体外释放评价
高璇，陈媛媛，刘媛媛，张红艳，余宇燕*
（福建中医药大学 药学院，福建 福州 350122）
摘要：以羟丙基甲基纤维素为（HPMC）为原料，二乙烯基砜（DVS）为交联剂，采用反相悬浮聚合法制备水凝胶微球。采用透射电子显微镜、纳米粒度仪对微球的粒径、形态进行表征。采用超滤离心法收集载药微球，透析袋法考察体外释放度。结果表明，制备的水凝胶微球粒径分布较均匀，分散性较好，载药量能达到3.8%以上。石杉碱甲水凝胶微球能够缓释石杉碱甲6 h。所制备的水凝胶微球对石杉碱甲具有一定的缓释作用。
关键词：石杉碱甲；纤维素；水凝胶微球；体外释放
中图分类号：R9 文献标识码：A 文章编号：0258-3283（2019）
Preparation and Vitro Release Evaluation of Huperzine-A Hydrogel Microspheres
GAO Xuan, CHEN Yuan-yuan, LIU Yuan-yuan, ZHANG Hong-yan, YU Yu-yan＊ (Pharmacy College of Fujian University of Traditional Chinese Medicine, Fuzhou 350122, China), Huaxue Shiji, 2019, 41(1)
Abstract: The hydrogel microspheres were prepared by reversed phase suspension polymerization using hydroxypropyl methylcellulose(HPMC) as raw material and vinyl sulfone(DVS) as cross-linking agent. The particle size and morphology of the microspheres were measured by TEM and nanoparticle size analyzer. The drug-loaded microspheres were collected by ultrafiltration and the dialysis method was used to evaluate the degree of in vitro release. The hydrogel microspheres were prepared with particle size distribution and good dispersibility, the drug loading is more than 3.8 %. Huperzine-A can be released by hydrogel microspheres for 6 h. Therefore, the prepared Huperzine-A hydrogel microspheres have certain release effect.
Key words：Huperzine-A; cellulose; hydrogel microspheres; in vitro release
吲哚-3-羧酸类化合物的设计、合成及体外降糖活性研究
张吉泉*1, 2，李述敏1，武婷婷1，彭金刚1，马晓1，汤磊*2
（贵州医科大学 1.药学院，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：以苯醌及3-氨基巴豆酸乙酯为原料，经环合、苄基化得到关键中间体5-苄氧基-2-甲基-1H-吲哚-3-甲酸乙酯。关键中间体经水解及酰胺化得到3个目标化合物，经磺酰化及水解可再次得到4个目标化合物，共合成7个目标化合物。其化学结构均经高分辨质谱、核磁共振氢谱及碳谱确证。人肝HepG2细胞上的促糖消耗活性显示，所合成化合物均具有一定的促糖消耗活性。其中，5-苄氧基-2-甲基-1-(4-氯苯甲酰基)-吲哚-3-甲酸的降糖活性与先导化合物相当。
关键词：糖尿病，吲哚，降糖活性，腺苷酸活化蛋白激酶，合成
中图分类号：R914 文献标识码：A 文章编号：0258-3283(2019)
Design, Synthesis and in vitro Hypoglycemic Activity of Indole-3-acid Derivatives ZHANG Ji-quan*1, 2, LI Shu-min1, WU Ting-ting1, PENG Jin-gang1, MA Xiao1, Tang Lei*2（1.College of Pharmacy, 2. Guizhou Provincial Engineering Technology Research Center for Chemical Drug R&D, Guizhou Medical University, Guiyang 550004, China）, Huaxue Shiji, 2019, 41(1), ～
Abstract: Starting from benzoquinone and (E)-ethyl 3-aminobut-2-enoate, the key intermediate ethyl 5-(benzyloxy)-2-methyl-1H-indole-3-carboxylate was synthesized via cyclization and benzylation, which was subjected to hydrolyzation and final amidation with various aryl acids to give three target compounds. The four desired compounds were also obtained from the key intermediate via sulfonylation and hydrolyzation. All the synthesized target compounds were confirmed by high resolution mass spectrometer (HRMS) and nuclear magnetic resonance (NMR) H and C spectrum. The glucose-consumption activity assay in HepG2 cell lines showed that all the synthetic compounds exhibited certain hypoglycemic activity, and 5- benzyloxy -2- methyl -1- (4- chlorobenzoyl) - indole -3- formic acid demonstrated comparable activity with the lead GY3.
Key words: diabetes; indole; hypoglycemic activity; AMP-activated protein kinase; synthesis
氮氧自由基TEMPO在合成化学中的应用进展
常盛，杨述祯，岳慧娟，杨丰科*
（青岛科技大学，山东 青岛 266000）
摘要:氧化反应及硝化反应是化学合成中的基础反应类型，但传统方法污染大且选择性差，绿色环保的实验方法更加受到青睐。2,2,6,6-四甲基哌啶-1-氧自由基是一种稳定的自由基，自发现以来被广泛地应用在化学合成中的各个领域中。因其具有高活性、高选择性和高稳定性，使它在醇的氧化反应和烯烃的硝化反应上得到广泛应用。以TEMPO在醇氧化反应及烯烃的硝化反应上的应用为方向，描述了2,2,6,6-四甲基哌啶-1-氧自由基在各种不同助氧化剂及硝化剂下参与的氧化反应及硝化反应，综述了最新的研究进展。
关键词：TEMPO；催化剂；氧化反应；硝化反应
中图分类号：O621.2 文献标识码：A 文章编号：0258-3283(2019)
Progress on Application of Nitroxide Radical TEMPO in Synthetic Chemistry CHANG Sheng, YANG Shu-zhen, YUE Hui-juan, YANG Feng-ke*(Qingdao University of Science and Technology, Qindao 266000, China), Huaxue Shiji, 2019, 41(1),
Abstract: Oxidation and nitration are the primary reactions types in chemical synthesis, but the traditional methods have the disadvantages of severe pollution and poor selectivity. The green environmental experiment method is more favored. 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) as green and stable free radical, has been widely used in various fields of chemical synthesis. It has been employed in the oxidation of alcohols and high stability. Based on the application of TEMPO in alcohol oxidation and olefin nitration, this work reviews the latest research progress with regards to the oxidation and nitration reactions of TEMPO under the presence of varying oxidants and nitrating agents.
Key words: TEMPO; catalysts; oxidation reaction; nitration reaction
脒参与的环加成反应的研究进展
马明，李兴，常宏宏，高文超，魏文珑*
（太原理工大学 化学化工学院，山西 太原 030024）
摘要：环加成是两个或多个分子通过结合生成环状化合物的反应，在有机合成中起着非常重要的作用。脒是一类重要的有机含氮化合物，作为有机合成中间体，他可与含有各种不饱和键的化合物发生不同类型的环加成反应来制备多种含氮杂环化合物；这些杂环化合物骨架广泛存在于医药、农药、材料和天然产物等分子结构中。对近几年脒与含有各种不饱和键化合物发生的各种环加成反应进行了综述，主要包括[3+3]、[3+2]、[3+5]、[4+2]和[2+3]等环加成反应，并对其发展方向进行了展望。
关键词：脒；环加成；不饱和键
中图分类号: 0626 文献标识码: A 文章编号: 0258-3283(2019)
Research Progress in the Cycloaddition Reactions of Amidines MA Ming, LI Xing, CHANG Hong-hong, GAO Wen-chao, WEI Wen-long* (College of Chemistry Engineering, Taiyuan University of Technology, Taiyuan 030024, China) Huaxue Shiji, 2019, 41(1), ～
Abstract: Cycloaddition is the formation of a cyclic compound via the reaction of two or more molecules, and it plays a very important role in organic synthesis. Amidines are very important nitrogen-containg compounds and they could react with various compounds having diverse unsaturated bonds to synthesize different nitrogen-containg heterocyclics. These heterocyclic skeletons are widely presented in the molecular structure of medicine, pesticides, materials and natural products. The recent progress in the cycloadditions of amidines with diverse compounds mainly bearing various unsaturated bonds is reviewed, including [3+3], [3+2], [3+5], [4+2] and [2+3] cycloaddition. Moreover, the prospects of future development are also discussed.
Key words: amidine; cycloaddition; unsaturated bonds
国内外氨基酸技术指标对比及分析方法研究进展
顾小焱1，郑琦1，陈浩云1，赵红莉*2，周丽芳2
(1.国药集团化学试剂有限公司，上海 200002；2.华东理工大学 化学与分子工程学院，上海 200237)
摘要：氨基酸是一切生命的物质基础，氨基酸的制备、分离纯化及分析检测等技术对生命科学和医药等的研究发展具有重要意义。随着上述研究及产业领域的快速发展，对高纯度氨基酸的需求也日益增加。发展高效的氨基酸分离纯化方法，建立不同纯度氨基酸的技术指标及标准分析方法，是规范行业发展、提升产品质量的关键。以L-谷氨酸为例，对比了国内外类似纯度产品的技术指标和分析方法；进一步综述了现阶段氨基酸的分离纯化及分析方法的发展概况。
关键词：氨基酸；技术指标；分离纯化；分析方法
中图分类号：O657.7 文献标识码：A 文章编号：0258-3283（2019）
Comparison of Technique Index at Home and Abroad and Determination Methods of Amino Acids GU Xiao-yan, ZHENG Qi, CHEN Hao-yun, Zhao Hong-li*2, Zhou Li-fang2(1. Sinopharm Chemical Reagent Co., Ltd, Shanghai 200002, China; 2. , East China University of Science and Technology, Shanghai 200237, China), Huaxue Shiji, 2019, 41(1)
Abstract：Amino acids are the physical basis of life. The preparation, separation and purification and determination of amino acids are of great significance for the development of life science and medicine. With the rapid development of related fields, the demand for high-purity amino acids is also increasing. The key to standardize industry development and enhance products quality is the development of efficient methods for the separation and purification, and the establishment of technique index and standard determination methods for amino acids with different purity. In this work, L-glutamic acid was taken as an example to compare the technique index and determination methods of the similar purity amino acids at home and abroad.Then, we reviewed the current methods for the separation and purification and determination of amino acids.
Key words：amino acids; technique index; separation and purification; determination methods
液态有机物储氢技术研究进展
赵琳，张建星，祝维燕，陈红香，张纪领，程金斌，张志梅，焦桂萍*
（中国船舶重工集团公司第七一八研究所，河北 邯郸 056000）
摘要：液态有机物储氢技术属于化学储氢的范畴，是近年来快速发展的一种氢能储运技术。国外对此项技术的研究和报道较多，而国内的研究才刚刚起步。对液态有机物储氢技术的原理进行介绍，并从储氢介质、脱氢模式和脱氢催化剂几个方面展开。通过对以上几个方面的介绍，旨在推动化学储氢技术特别是液态有机物储氢技术的进展。
关键词：有机物；脱氢；催化剂
中图分类号：TK91 文献标识码：A 文章编号：0258-3283(2019)1--
Research Progress of Hydrogen Storage Technology for Liquid Organic Matter ZHAO Lin, ZHANG Jian-Xing, ZHU Wei-Yan, CHEN Hong-Xiang, ZHANG Ji-Ling, CHENG Jin-Bin, ZHANG Zhi-Mei, JIAO Gui-Ping* (The 718th Research Institute of CSIC, Hebei 056000, China) Huaxue Shiji, 2019, 41(1), ～
Abstract: Hydrogen storage technology of liquid organic matter belongs to the category of chemical hydrogen storage and is a rapid development of hydrogen energy storage and transportation technology in recent years. There are many researches and reports on this technology abroad, and domestic research has just started. Through the introduction of the principle of hydrogen storage technology for liquid organics, several aspects of dehydrogenation, dehydrogenation, and dehydrogenation catalysts have been developed. Through the introduction of the above aspects, it aims to promote the progress of chemical hydrogen storage technology, especially hydrogen storage technology for liquid organics.
Key words: organic matter; dehydrogenation; catalyst
基于电沉积多孔碳修饰电极测定6-苄氨基嘌呤的研究
王洪杰a，王世彬a，陈慧平b，李鸿军a，聂秀芳a，张小远a，柳斌a，杜海军*a
(贵州民族大学 a.化学工程学院，b.预科教育学院，贵州 贵阳 550025)
摘要：利用恒电位法沉积多孔碳固定于玻碳电极表面，构建多孔碳修饰电极，利用线性扫描伏安法和脉冲伏安法研究了6-苄氨基嘌呤在多孔碳修饰电极上的电化学行为，建立了一种测定6-苄氨基嘌呤的电化学分析方法。结果表明，与玻碳电极相比，多孔碳修饰电极能显著提高6-苄氨基嘌呤的氧化峰电流。在优化的实验条件下，6-苄氨基嘌呤的氧化峰电流与6-苄氨基嘌呤浓度在1.0×10-7～4.0×10-5 mol/L范围内呈较好的线性关系，最低检测限为7.6×10-8 mol/L。本法用于黄豆芽中6-苄氨基嘌呤的测定，效果良好。
关键词：6-苄氨基嘌呤；多孔碳；电沉积；差分脉冲伏安法
中图分类号：O657.1 文献标识码：A 文章编号：0258-3283（2019）
Determination of 6-Benzylaminopurine by Linear Sweep Voltammetry with Ordered Mesoporous Carbon Modified Electrode via Electrodeposition WANG Hong-jiea, WANG Shi-bina, CHEN Hui-pingb LI Hong-juna, NIE Xiu-fanga, ZHANG Xiao-yuana, LIU Bina, DU Hai-jun*a (a.School of Chemical Engineering, b.College of Prep-education, Guizhou Minzu university, Guiyang 550025, China), Huaxue Shiji, 2019, 41(1),
Abstract: Ordered mesoporous carbon(OMC) were immobilized on the glassy carbon electrode(GCE) surface during the process of potentiostatic electrodeposition. The OMC modified electrode was used for the determination of 6-benzylaminopurine (6-BAP). The electrochemical behavior of the modified electrode was investigated by linear sweep voltammetry and differential pulse voltammetry. The experimental parameters were optimized, and an electroanalytical method for determining 6-benzylaminopurine was developed. The oxidation peak current of 6-BAP was enhanced significantly at the OMC/GCE, in contrast to that obtained at the bare GCE. Under the optimized experimental conditions, the oxidation peak current was proportional to the 6-BAP concentration in the ranges of 1×10-7～4.0×10-5 mol/L with a detection limit of 7.6×10-8 mol/L. OMC/GCE was easy to be prepared with good reproducibility. The proposed methodology was successfully applied to the detection of 6-BAP in the sprouted beans with satisfactory results.
Key words：6-benzylaminopurine; ordered mesoporous carbon; electrodeposition；differential pulse voltammetry
二维高效液相色谱测定绿豆芽中赤霉素、6-苄基腺嘌呤、4-氯苯氧乙酸和2,4-二氯苯氧乙酸
高宗林，曹旭妮*
（华东理工大学 食品科学与工程系，上海 200237）
摘要：在豆芽食品中对添加的植物生长调节剂的监控是十分重要的。在此基础上建立了绿豆芽抽提样品中赤霉素、6-苄基腺嘌呤、4-氯苯氧乙酸和2,4-二氯苯氧乙酸4种植物生长调节剂的二维高效液相色谱定量分析方法。实验中以ZB-10 C18 (ODS-AP，10 mm×10 mm)为第一维色谱柱，V（甲酸）：V（甲醇）：V（水） ＝ 1：10：89溶液为等度洗脱，实现绿豆芽样品的前处理净化；随后采用通过阀切换将被分析物转移至第二维色谱柱(Supersil ODS 2.5mm，4.6 mm×150 mm)，以甲醇-0.1%甲酸水溶液为流动相梯度洗脱，并以紫外254 nm为检测波长实现上述4种植物生长调节剂的分离分析。该方法中，赤霉素、6-苄基腺嘌呤、4-氯苯氧乙酸和2,4-二氯苯氧乙酸的线性范围分别为0.004 ～ 2、0.0001 ～ 0.2、0.005 ～ 2以及0.008 ～ 2 mg/mL，检测下限分别为 1.4、0.03、1.6、2.4 mg/mL；峰面积的RSD为2% ～ 3%，回收率为95% ～ 104%。实际样品的分析中，我们发现该绿豆芽样品中赤霉素和2, 4-二氯苯氧乙酸的添加量为18 mg/kg和6 mg/kg，4-氯苯氧乙酸为未检出。另外，我们还发现样品中由于存在干扰物而不能准确定量分析低浓度的6-苄基腺嘌呤。研究表明，该方法可以应用于绿豆芽的直接抽提样品，对其中的赤霉素、4-氯苯氧乙酸和2,4-二氯苯氧乙酸能准确进行定量分析，不需进一步的样品前处理。
关键词：赤霉素；6-苄基腺嘌呤；4-氯苯氧乙酸；2,4-二氯苯氧乙酸；二维高效液相色谱；绿豆芽
中图分类号：O657.7 文献标识码：A 文章编号：0258-3283(2019)--
Simultaneous Determination of Gibberellin Acid, 6-Benzyladenine, 4-Chlorophenoxyacetic Acid and 2,4-Dichlorophenoxyacetic Acid by Two-dimensional Liquid Chromatography GAO Zong-lin, CAO Xu-ni* (Department of Food Science & Technology, East China University of Science & Technology, Shanghai 200237, China), Huaxue Shiji, 2019, 41(1),
Abstract: A method for simultaneous determination of gibberellin acid, 6-benzyladenine, 4-chlorophenoxyacetic acid and 2,4-dichlorophenoxyacetic acid in mungbean sprouts was established by 2D-LC. The separation was first performed on the first-dimension column ZB-10 C18 (ODS-AP, 10 mm×10 mm). The analysts were trapped on this column for purification and the mobile phase used here was V (formic acid): V(methanol): V (water) =1:10:89 in isocratic elution mode．Then, the trapped analysts were transferred to the second-dimension column (Supersil ODS 2.5 mm，4.6 mm×150 mm) using valve-switching technique, methanol and 0.1% formic acid water solutions were used as mobile phase in gradient elution mode. Thus, they could be determined at 254 nm with a UV detector. The results showed that the linear ranges of gibberellin acid, 6-benzyladenine, 4-chlorophenoxyacetic acid and 2,4-dichlorophenoxyacetic acid were 0.004～2, 0.0001～0.2, 0.005～2 and 0.008～2 mg/mL, respectively; and their detection limits were 1.4, 0.03, 1.6 and 2.4 mg/mL, respectively. The RSD values were 2%～3% and the recoveries ranged from 95%～104%. When those plant hormone residues were purified by the first-dimension column, they could be successfully detected in mungbean sprouts at the level of 18 mg/kg for gibberellin acid and 6 mg/kg for 2,4-dichlorophenoxyacetic acid; It was also found that 2,4-dichlorophenoxyacetic acid was not detectable and 6-benzyladenine could not be accurately determined in these extracts. The method is accurate and reliable, and can be applied directly to the determination of gibberellins acid, 4-chlorophenoxyaceti acid, and 2,4-dichlorophenoxyacetic acid from the extracts of mungbean sprouts without further sample preparation, but not for 6-benzyladenine.
Key words: gibberellin acid; 6-benzyladenine; 4-chlorophenoxyaceti acid; 2,4-dichlorophenoxyacetic acid; 2D-LC; mungbean sprouts
基于多巴胺共振散射光谱法测定牛奶中的三聚氰胺
马璐，谢宇奇，雷禄，凌绍明*
(百色学院 化学与环境工程学院，广西 百色 533000)
摘要：在氢氧化钠介质中，氯金酸与多巴胺发生氧化还原反应生成金纳米粒子而使体系在519.4 nm处产生一个较强的共振散射峰。当加入三聚氰胺时，多巴胺和三聚氰胺通过氢键结合并形成稳定的多氢键化合物，使得结合的多巴胺还原能力降低而不能还原氯金酸，阻碍金纳米粒子的形成，导致体系519.4 nm处的共振散射峰强度降低。据此建立了检测三聚氰胺的共振散射光谱法。在优化的实验条件下，三聚氰胺的浓度(c)在8.33×10-7～1.67×10-5 mol/L范围内与该共振散射峰强度的降低值(ΔI519.4 nm)呈良好线性关系，其相关系数为0.9961，检出限为2.1×10-7 mol/L。将该共振散射光谱法用于牛奶制品中的三聚氰胺的测定，回收率为96.0%～108.0%，相对标准偏差为1.3%～2.7%。
关键词：多巴胺；金纳米粒子；氢键；共振散射光谱法；三聚氰胺
中图分类号：O656.3 文献标识码：A 文章编号：0258-3283（2019）
Determination of Melamine based on Nanogold Resonance Scattering Spectral MA Lu，XIE Yu-qi，LEI Lu，LING Shao-ming* (College of Chemical and Environmental Engineering, Baise University, Baise 533000, China), Huaxue Shiji, 2019, 41(1),
Abstract: In NaOH solution, gold nanoparticles that exhibited a strong resonance scattering peak at 519.4 nm were prepared via redox reaction between HAuCl4 and dopamine. When the melamine was added, dopamine interacted with melamine and formed a stable complex by hydrogen bonds, HAuCl4 could not be easily reduced by the interacted dopamine, the formation of gold nanoparticles was interrupted, resulting in the decrease of resonance scattering intensity. Based on this, a resonance scattering method was developed for the determination of melamine. Under the optimal conditions, the decreased resonance scattering intensity (ΔI519.4nm) was linear to melamine concentration (c) in the range of 8.33×10-7～1.67×10-5 mol/L, with a correlation coefficient of 0.9961 and a detection limit of 2.1×10-7 mol/L. This method was utilized to detect melamine in pretreated liquid milk products, with the recoveries of 96.0%～108.0% and relative standard deviations of 1.3%～2.7%.
Key words: dopamine; gold nanoparticle; hydrogen bond; resonance scattering; melamine
ICP-OES法测定粉煤灰中化学元素的4种前处理方法比较
丁海萍*，侯泽建，周筱
（锡林郭勒职业学院，褐煤粉煤灰工程技术研究院，内蒙古 锡林郭勒盟 026000）
摘要：采用HNO3-HF-HClO4湿法消解、HNO3-HF-HClO4微波消解、钠系碱法消解和偏硼酸锂融熔法分别处理粉煤灰标准品和某电厂粉煤灰样品，利用ICP-OES法测定各组样品中K、Na、Ca、Mg、Al、Fe、Si 7种元素的含量，对比4种前处理方法的优劣势，探讨简单、快捷、准确的测定粉煤灰中矿物质元素的前处理方法。研究表明，HNO3-HF-HClO4湿法消解法的回收率范围为101.00% ～ 108.20%，标准偏差（RSD）＜1.49%；HNO3-HF-HClO4微波消解法的回收率范围为103.00% ～ 109.80%，标准偏差（RSD）＜1.58%；钠系碱法消解法的回收率范围为102.34% ～ 108.62%，标准偏差（RSD）＜1.62%；偏硼酸锂融熔法的回收率范围为103.20% ～ 109.30%，标准偏差（RSD）＜1.68%。4种方法均具有较好的准确度和精密度，但HNO3-HF-HClO4湿法消解法测得的元素含量平均值普遍偏低。所以综合考虑，偏硼酸锂融熔法操作简单、耗时短，与湿法相比，可以避免使用大量酸造成对设备腐蚀和环境污染；与钠系碱法消解相比，可以避免对K、Na元素的电离效应和基体影响。因而，偏硼酸锂熔融法可作为测定粉煤灰矿物质元素含量较好的前处理方法。
关键词：粉煤灰；湿法消解；偏硼酸锂熔融；钠系碱法消解；微波消解；ICP-OES
中图分类号：0657.31 文献标识码：A 文章编号：0258-3283(2019)—
Comparison of Four Pretreatment Methods for Determination of Chemical Elements in Fly Ash by ICP-OES DING Hai-ping*, HOU Ze-jian, ZHOU Xiao (Lignite Fly Ash Institute of Engineering & Technology, Xilingol Vocational College, Xilinguole 026000, China), Huaxue Shiji, 2019, 41(1), ～
Abstract: The fly ash standard products and a fly ash sample of a power plant were treated with HNO3-HF-HClO4 wet digestion, HNO3-HF-HClO4 microwave digestion, sodium-based alkali digestion and lithium metaborate fusion method respectively. The contents of K, Na, Ca, Mg, Al, Fe, and Si in each group of samples were determined by OES method. The advantages and disadvantages of the four pretreatment methods were compared to the simple, quick, accurate determination and pre-processing method of minerals in fly ash. The results showed that the recoveries of HNO3-HF-HClO4 wet digestion ranged from 101.00% to 108.20% and the standard deviation (RSD) was less than 1.49%. The recoveries of HNO3-HF-HClO4 microwave digestion ranged from 103.00%～109.80%. The standard deviation (RSD) was less than 1.58%. The recoveries of the sodium-based soda digestion ranged from 102.34%～108.62% with a standard deviation (RSD) of less than 1.62%. The lithium metaborate melting method recovery range was 103.20%～109.30%, standard deviation (RSD) <1.68%. All four methods have good accuracy and precision; but the mean value of elemental content measured by HNO3-HF-HClO4 wet digestion method is generally low. Therefore, considering comprehensively, the lithium metaborate fusion method is simple to operate and takes a short time. Compared with the wet method, it can avoid corrosion of equipment and environmental pollution caused acid, and can avoid ionization interference during the determination of Na element content compared with Na alkali digestion. Therefore, lithium metaborate melting method can be used as a pretreatment method for determining the content of mineral elements in fly ash.
Key words: fly ash; wet digestion; lithium metaborate melting; sodium-based digestion; microwave digestion; ICP-OES
十二烷基苯磺酸钠与盐酸肼屈嗪作用的荧光光谱
分析研究及应用
牟城健a, b，王振b，李银华a, b，许钟元b,c，马卫兴*b，李树安b
（淮海工学院 a. 化学工程学院，b. 药学院，c. 海洋生命与水产学院，江苏 连云港 222005）
摘要：基于盐酸肼屈嗪与十二烷基苯磺酸钠在Clark-Lubs缓冲介质中发生反应，建立了荧光光谱法测定盐酸肼屈嗪的新方法，对实验条件进行充分优化，结果发现，荧光光谱法的激发波长和发射波长分别为233 nm和290 nm。该实验方法测得盐酸肼屈嗪浓度在0.5～4.0 mg/L范围内呈现线性关系，其线性回归方程为IF = 765.05 C + 161.07，相关系数R为0.9996，检测限为0.18 mg/L，回收率在99.08%～101.08%之间，该方法盐酸肼屈嗪含量测定与硼酸催化茚三酮分光光度法，所测结果相一致。
关键词：盐酸肼屈嗪；十二烷基苯磺酸钠；荧光光谱法
中图分类号：O657.39 文献标识码：A 文章编号：0258-3283（2019）
Fluorescence Spectroscopic Analysis and Application of Sodium Dodecylbenzene Sulfonate and Hydrazine Hydrochloride MOU Cheng-jiana, b，WANG Zhenb，LI Yin-huaa, b，XU Zhong-yuanb,c，MA Wei-xing*b，LI Shu-anb (a.College of Chemical Engineering, b.College of Pharmacy, c.Marine Life and Fisheries College, Huaihai Institute of Technology, Lianyungang 222005, China), Huaxue Shiji, 2019, 41(1)
Abstract: Based on the reaction between hydralazine hydrochloride and sodium dodecylbenzenesulfonate in Clark-Lubs buffer medium, a new fluorescence spectrometry method for the determination of hydralazine hydrochloride was established. The experimental conditions were fully optimized. The excitation and emission wavelengths of the fluorescence spectrum were 233 nm and 290 nm, respectively. The hydralazine hydrochloride concentration showed a linear relationship in the range of 0.5~4.0 mg/L, the linear regression equation was IF=765.05 C+161.07 with the correlation coefficient 0.9996, the detection limit was 0.18 mg/L. The recovery rate of is between 99.08% and 101.08%. The hydralazine hydrochloride content determination of this method is consistent with the results measured by Boric acid catalyzed ninhydrin spectrophotometry.
Key words: hydralazine hydrochloride; sodium dodecyl benzene sulfonate; fluorescence spectroscopy
5,17-二甲硫基-2,8,14,20-四氧杂苯[2]-嘧啶[2]杯芳烃衍生物的合成及其晶体结构
黄统辉*，王颖，徐猛，潘琳
(徐州医科大学 药学院，江苏 徐州 221004)
摘要：使用4,6-二氯-2-甲硫基嘧啶和相应的取代间苯二酚为原料，以碳酸铯为碱，N, N-二甲基甲酰胺为溶剂，在18-冠醚-6和碘化钾催化的条件下经缩合成环反应得到目标化合物。通过IR、1HNMR、13CNMR和HR-MS表征了化合物的结构，并通过X-射线衍射测定了目标化合物的单晶结构。结果表明目标化合物晶体属于单斜晶系，C2/c空间群，晶胞参数a = 14.5295(18) Å, b =12.9690(18) Å, c = 15.523(2) Å, α = 90. 00°, β = 112.935(4)°, γ = 90°，V = 2693.8(6) Å3, Z = 4, μ(MoKa) = 0.241 mm-1, F(000) = 1112。晶体结构分析结果表明，5,17-二甲硫基-2,8,14,20-四氧杂苯[2]-嘧啶[2]杯芳烃具有对称的环状结构，并通过分子间的π-π相互作用形成了二维网状结构。
关键词：合成；四氧杂苯[2]-嘧啶[2]杯芳烃；晶体结构
中图分类号：O626.4 文献标识码：A 文章编号：0258-3283（2019）
Synthesis and Crystal Structure of 5,17-Bis(methylsulfanyl)-2,8,14,20-tetraoxacalix[2] arene[2] pyrimidine Derivatives HUANG Tong-hui*, WANG Ying, XU Meng, PAN Lin (School of Pharmacy, Xuzhou Medical University, Xuzhou 221004,China), Huaxue Shiji, 2019, 41(1),
Abstract 5,17-Bis(methylsulfanyl)-2,8,14,20-tetraoxacalix[2]arene[2]pyrimidine derivatives was synthesized via a cyclization of 4,6-dichloro-2-(methylthio)pyrimidine and 1,3-benzenediol in N,N-dimethylformamide in the absence of cesium carbonate, 18-crown-6 and potassium iodide. Structures of the obtained compounds (3a and 3b) were comfirmed by IR, 1H NMR, 13C NMR, and HR-MS. Meanwhile, the crystal 3a was obtained and determined by X-ray single-crystal diffraction. The compound crystallizes in monoclinic crystal system and with space group C2/c with a = 14.5295(18) Å, b =12.9690(18) Å, c = 15.523(2) Å, α = 90. 00°, β = 112.935(4)°, γ = 90°, V = 2693.8(6) Å3, Z = 4, μ(MoKa) = 0.241 mm-1, F(000) = 1112. The molecule of 5,17-bis(methylsulfanyl)-2,8,14,20-tetraoxacalix[2] arene[2] pyrimidine was interconnected by π-π interactions to aggregate 2D framework.
一种光照诱导原位产生过氧亚硝酸根的新方法
张汉桥，肖娜，胡常杰，王军，糜志远，苏江涛*
（湖北工业大学 生物与食品工程学院，湖北 武汉 430068)
摘要：已证实体内过氧亚硝酸根离子与人体多种病理反应相关。采用S-亚硝基硫醇为一氧化氮供体化合物和水溶性优于核黄素的聚乙二醇化核黄素为光敏剂，在光照条件下各自分解出一氧化氮和超氧负离子，并迅速原位转化为过氧亚硝酸根离子。利用酪氨酸和牛血清白蛋白分别作为过氧亚硝酸根离子捕获剂，证实了这是一种体外产生过氧亚硝酸根的有效方法。
关键词：一氧化氮；超氧负离子；过氧亚硝酸
中图分类号：O621 文献标识码：A 文章编号：0258-3283（2019）
a New Method of Producing Peroxynitrite in-situ by Light Irradiation ZHANG Han-qiao，XIAO Na，HU Chang-jie，WANG Jun，MI Zhi-yuan，SU Jiang-tao* (Department of Biological and Food Engineering, Hubei University of Technology, Wuhan 430068, China), Huaxue Shiji, 2019, 41(1),
Abstract: Peroxynitrite in the body has been associated with various pathological changes in the body. In this work S-nitroso alcohol was used as the nitric oxide donor compound, and the PEGylated riboflavin which the water solubility was better than riboflavin as the photosensitizer. Under the light conditions, the nitric oxide and the superoxide anion were decomposed separately. It was rapidly converted into the peroxynitrite ion. The tyrosine and bovine serum albumin were used respectively as peroxynitrite ion capture agent to be proved an effective method for producing peroxynitrite in vitro.
Key words: nitric oxide(NO); superoxide anion; peroxynitrous acid
一维Zn(II)配合物{[Zn(Hpntc)2]·H2O}n的合成、结构及荧光性能研究
季甲，侯银玲*，韦胜艳，任晓玫，曾瑶
（凯里学院 大健康学院，贵州 凯里 556011）
摘要：以3,5-(4-羧酸苯基)-4-氨基-1,2,4-三氮唑为配体，六水合高氯酸锌为金属盐，通过水热合成法构筑了一例Zn配合物{[Zn(Hpntc)2]·H2O}n。单晶结构解析表明该配合物属于三斜晶系，P-1空间群，单胞参数a = 0.80079(12) nm，b = 1.13601(11) nm，c = 1.63691(16) nm，α = 78.070(8)°，β = 81.525(10)°，γ = 84.31(1)°。通过配体桥联，配合物形成一维链结构，再通过分子间氢键形成二维超分子结构。采用元素分析、红外光谱、粉末衍射对该配合物进行了基本表征，并研究了其室温下的固体荧光和乙醇溶液中的荧光性能。荧光结果表明，配合物具有较强的荧光发射，是一种潜在的荧光材料。
关键词：水热合成法；配合物；晶体结构；荧光
中图分类号： O614.24 文献标识码：A 文章编号：0258-3283(2019)
Synthesis, Structure and Luminescent Research of a 1D Zn-Compound {[Zn(Hpntc)2]·H2O}n JI Jia, HOU Yin-ling, WEI Sheng-yan, REN Xiao-mei, ZENG Yao (School of Life and Health Science, Kaili University, Kaili 556011, China), Huaxue Shiji, 2019, 41(1),
Abstract: A Zn-compound {[Zn(Hpntc)2]·H2O}n was constructed via hydrothermal synthesis method with 3,5-(4-carboxylic acid phenyl)-4-amino-1,2,4-triazole and zinc perchlorate hexahydrate. X-ray single crystal diffraction reveals that the compound crystalized in triclinic system, P-1 space group, unit cell parameters are a = 0.80079(12) nm, b = 1.13601(11) nm, c = 1.63691(16) nm, α = 78.070(8)°, β = 81.525(10)°, and γ = 84.31(1)°. The compound forms one dimension chains, and further interacts via hydrogen-bonds, giving a two dimensional supramolecular structure. The structure was characterized by elemental analysis, infrared spectroscopy and powder X-ray diffraction. The luminescence of solid-state and ethanol solution at room temperature was investigated, and the results show that the compound can emit strong luminescence, suggesting it is a potential luminescent material.
Key words: hydrothermal synthesis; compound; crystal structure; luminescence
稳定同位素标记卤代苯-D5的合成
杨超1, 2，杨维成*1, 2，潘洁1
（1.上海化工研究院技术开发中心；2.国家同位素工程技术研究中心-上海分中心，上海 200062）
摘要：以苯-D6为同位素标记起始原料，经卤代反应合成得到稳定同位素标记卤代苯-D5。以消耗的苯-D6计算，稳定同位素标记氯苯-D5、溴苯-D5、碘苯-D5的收率分别为80.3 %、82.1 %、84.3 %，产品结构经气相色谱（GC）、气质联用（GC-MS）及核磁（13CNMR）等仪器表征确定，色谱纯度高于99.0 %，同位素丰度大于99.0 % atom D，可作为稳定同位素标记化合物合成的基础试剂使用。
关键词：同位素标记；氯苯；溴苯；碘苯；中间体
中图分类号：TQ421.6 文献标识码：A 文章编号：0258-3283(2019)—
Syntheses of Stable Isotope Labeled Halogenated Benzene-D5 YANG Chao1, 2, YANG Wei-cheng*1, 2, PAN Jie1(1.Shanghai Research Institute of Chemical Industry, 2.Shanghai Engineering Research Center of Stable Isotope, Shanghai 200062, China) Huaxue Shiji, 2019, 41(1), ～
Abstract: This work presents an efficient synthesis of stable isotope labeled halogenated benzene-D5 with benzene-D6 as the precursor by halogenation. The yields of chlorobenzene-D5, bromobenzene-D5, iodobenzene-D5 were 80.3%, 82.1%, 84.3%, based on benzene-D6 consumed. The products were confirmed by GC, GC-MS, and 13CNMR. The chemical purities and isotopic enrichment are higher than 99.0 %. The above compounds could be used as basic reagent for stable isotope labeling compounds synthesis.
Key words：isotope labeling; chlorobenzene; bromobenzene; iodobenzene ; intermediate
3-氨基呋咱-4-羧酸的合成及表征
王彬，周彦水，李亚南*，王伯周
(西安近代化学研究所，陕西 西安 710065)
摘要：设计了3-氨基呋咱-4-羧酸（AFCA）新合成方法，以氰乙酰胺为起始原料，经亚硝化、加成、环化得到标题化合物，并利用红外光谱、核磁共振、质谱、元素分析等鉴定了产物结构；初步探讨了环化反应过程，确定反应的最适宜条件：采用冰醋酸为亚硝化反应的最佳催化剂，产率高达96%；加成反应中最佳投料比为n（2-肟基氰乙酰胺）:n（盐酸羟胺）=1:3，产率可达95%；环化反应反应时间为4 h，反应温度为65～70 ℃，产率为62%。结果表明，该方法具有能耗低、操作简便、收率高的优点。
关键词：有机化学；合成；3-氨基呋咱-4-羧酸；表征
中图分类号： O626.24 文献标识码：A 文章编号：0258-3283（2019）
Synthesis and Characterization of 3-Aminofurazan-4-carboxylic Acid WANG Bin, ZHOU Yan-shui, LI Ya-nan*, WANG Bo-zhou (Xi’an Modern Chemistry Research Institute, Xi’an 710065, China), Huaxue Shiji, 2019, 41(1),
Abstract: 3-aminofurazan-4-carboxylic acid was devised and synthesized from 2-cyanoacetamide via nitrosation ,addition and cyclization. The molecular structure was confirmed by IR, 1HNMR, 13CNMR, MS and elemental analysis. The cyclic reaction process was preliminarily discussed, and the optimum conditions were determined: glacial acetic acid was used as the best catalyst for nitrosation, with a yield of up to 96%. In addition reaction, the optimal feeding ratio is n (2-oxime cyanoacetamide) : n (hydroxylamine hydrochloride) =1:3, and the yield can reach 95%. Cyclization reaction time is 4 h, the reaction temperature is 65～70 ℃, the yield of 62%. The results showed that this method has the advantages of low energy consumption, simple operation and high yield.
Key words：organic chemistry; synthesis; 3-aminofurazan-4-carboxylic acid; characterization
3-溴-6-甲基吡啶甲酸甲酯的合成研究
邹国军1, 2，赵庆平1, 2，周志旭1, 2，黄筑艳*1, 2, 3
(1.贵州大学 药学院，贵州 贵阳 550025；2.贵州省合成药物工程实验室，贵州 贵阳 550003；
3.贵州省发酵工程与生物制药重点实验室，贵州 贵阳 550003)
摘要：3-溴-6-甲基吡啶甲酸甲酯是一种重要的医药化工中间体。对其合成路线进行了设计，以5-溴-2-甲基吡啶为原料，经氮氧化、氰化、醇解反应得到目标产物，并对合成路线进行了优化，目标化合物的结构经1HNMR、13CNMR和MS确证。该合成路线具有原料廉价易得、操作简单、后处理方便且收率较高等优点，适合工业化生产，总收率为33.7%。
关键词：5-溴-2-甲基吡啶；3-溴-6-甲基吡啶甲酸甲酯；合成
中图分类号：O626.13 文献标识码：A 文章编号：0258-3283(2019)
Synthesis of Methyl 3-Bromo-6-methylpicolinate ZOU Guo-jun 1, 2, ZHAO Qing-ping 1, 2，ZHOU Zhi-xu1, 2，HUANG Zhu-yan*1, 2, 3 (1. School of Pharmaceutical Sciences, Guizhou University, Guiyang 550025, China; 2. Guizhou Engineering Laboratory for Synthetic Drugs, Guiyang 550003, China; 3. Key Laboratory of Guizhou for Fermentation Engineering and Biomedicine, Guiyang 550003, China), Huaxue Shiji, 2019, 41(1)
Abstract:The synthesis method of methyl 3-bromo-6-methylpicolinate has never been reported in any literature. It is an important intermediate for pharmaceutical and chemical industry. The target compound was synthesized by nitrogen oxidation, cyanation and alcoholysis reaction with 5-bromo-2-methylpyridine as raw material. The synthetic route was optimized and the structure was confirmed by 1HNMR, 13CNMR and MS. The raw materials are cheap and easy to get in this method. It is easy to operate and control the reaction and the yield was higher in each step with the convenient post-processing, which is suitable for industrial production. The total yield was 33.7%.
Key words:5-bromo-2-methylpyridine；methyl3-bromo-6-methylpicolinate；synthesis
2-脱氧-D-葡萄糖的合成研究
孙昊，刘鹏，袁文蛟*
(天津现代职业技术学院，天津 300350)
摘要：2-脱氧-D-葡萄糖具有多种生物活性，被广泛地应用在药品和食品领域。在研究活化DMSO时，偶然发现在碘化钾存在下氯甲基甲基硫醚具有温和的路易斯酸性。因此，利用KI/CH3SCH2Cl体系，以3,4,6-O-三乙酰基-D-葡萄糖糖烯为起始原料，经催化水合和脱保护两步反应，便可高效地制得2-脱氧-D-葡萄糖（异构体比例为1︰2），总收率77.6%。该方法反应条件温和、反应收率较高，具有良好的工业应用前景。
关键词：2-脱氧-D-葡萄糖；CH3SCH2Cl；水合反应；葡萄糖糖稀
中图分类号：TQ463 文献标识码：A 文章编号：0258-3283（2019）
Synthesis of 2-Deoxy-D-glucose SUN Hao, LIU Peng, YUAN Wen-jiao* (Tianjin Modern Vocational Technology College, Tianjin 300350, China), Huaxue Shiji, 2019, 41(1),
Abstract：Due to various bioactivities, 2-deoxy-D-glucose is widely used in the field of medicine and food. It was discovered that CH3SCH2Cl demonstrated Lewis acidity in the presence of KI, when active DMSO was investigated. In this work, 3,4,6-tri-O-acetyl-D-glucal was transformed into 2-deoxy-D-glucose (α:β=1:2) via hydration reaction mediated by KI/CH3SCH2Cl and de-protection reaction with the 77.6% yield in total. These reaction conditions are mild and reaction yields are high, which shows potential in the industrial application.
Key words：2-deoxy-D-glucose; CH3SCH2Cl; hydration reaction; glucal
5-羟基苯并呋喃-6-甲酸的合成研究
刘斌*1,2，席孝贤1，仝红娟1,2，杜漠1,2，张彦民1,2
（1.陕西国际商贸学院 医药学院, 2.陕西省中药绿色制造技术协同创新中心，陕西 西安 712046）
摘要：以2,5-二羟基苯甲酸为原料，经酯化、取代、多聚磷酸催化傅克烷基化、酯水解四步反应制备目标化合物，四步反应总收率52.5%。其结构及中间体经1HNMR，13CNMR和ESI-MS确证。并分别对每一步影响产物收率的因素进行了研究。确定酯化条件：无水乙醇为溶剂；n（SOCl2）:n（2,5-二羟基苯甲酸）=1.5:1；回流条件下反应3 h；收率为93%。取代反应条件：K2CO3为碱；n（化合物3）:n（化合物2）=1.3:1；反应在丙酮溶剂中回流12 h；化合物4最高收率为78%。傅克烷基化反应条件：甲苯为溶剂；n（PPA）:n（化合物4）=0.5:1；反应在80 oC下进行2 h；收率为77%。水解条件：甲醇/水混合溶剂；n（NaOH）:n（化合物5）= 3:1；50℃时反应4 h；收率为94%。
关键词：苯并呋喃；5-羟基苯并呋喃-6-甲酸；傅克烷基化；合成
中图分类号：TQ463 文献标识码：A 文章编号：0258-3283（2019）
Synthesis of 5-Hydroxybenzofuran-6-carboxylic Acid LIU Bin*1, 2, XI Xiao-xian1, TONG Hong-juan1, 2, Du Mo1, 2, ZHANG Yan-min1, 2 (1.School of Pharmacy, Shaanxi Institute of International Trade & Commerce, 2.Collaborative Innovation Center of Green Manufacturing Technology for Traditional Chinese Medicine in Shaanxi province, Xi’an 712046, China), Huaxue Shiji, 2019, 41(1),
Abstract: Ethyl 5-hydroxybenzofuran-6-carboxylic acid was synthesized form 2,5-dihydroxybenzoic acid via 4 steps in a total yield of 52.5 % by esterification reaction, substitution reaction, Friedel-Crafts alkylation in the presence of polyphosphoric acid and hydrolysis of ester. The structures of intermediates and the product were confirmed by 1HNMR, 13CNMR and ESI-MS. The effect of the reaction conditions on the yields of each step was investigated respectively. The optimal esterification reaction conditions were absolute ethanol as solvent, n (SOCl2) : n (2,5-dihydroxybenzoic acid) =1.5:1, reflux for 3 h, the yield is 93%; The optimal substitution reaction were K2CO3 as base, n (compound 3) : n (compound 2) =1.3:1, compound 4 was obtained in 78% yield with the reaction reflux for 12 h in acetone; The optimal Friedel-Crafts alkylation reaction conditions were toluene as solvent, n (PPA) : n (compound 4) = 0.5:1, at 80℃ for 2 h, the yield is 77%; The optimal hydrolysis of ester reaction conditions were methanol/water as solvent, n (NaOH) : n (compound 5) = 3:1, at 50℃ for 4 h, the yield is 94%.
Key words: benzo[b]furan; 5-hydroxybenzofuran-6-carboxylic acid; Friedel-Crafts alkylation; synthesis
