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《化学试剂》2018年第10期中英文摘要

铑催化的三元碳环的开环/羰基环化反应研究进展

陈莹莹,毛国梁*,刘小兵,吴韦*

东北石油大学 化学化工学院 石油与天然气化工省重点实验室,黑龙江 大庆  163318

 

摘要:由于较大的环张力,三元环表现出较高的反应活性,在铑等过渡金属的催化作用下可以发生开环反应,与一氧化碳作用可实现羰基化等反应也为多种具有生物活性的化合物提供了简便的合成方法。主要综述了近年来铑催化的三元碳环衍生物和一氧化碳进行羰基化环化反应的研究进展、机理及其在有机合成中的应用。

关键三元碳环化合物;铑催化剂;羰基化反应;环化反应

中图分类号:O62                文献标识码:A        文章编号:0258-32832018

 

Progress in Ring-opening / Carbonyl Cyclization of Rh Catalyzed Ternary Carbon Ring CHEN Ying-ying, MAO Guo-liang*, LIU Xiao-bing, WU Wei* (Provincial Key Laboratory of Oil & Gas Chemical Technology, College of Chemistry and Chemical Engineering, Northeast Petroleum University, Daqing 163318, China), Huaxue Shiji, 2018, 40(10),

Abstract: Due to the larger ring tension, the three membered ring showed high reactive activity, and the ring opening reaction could occur under the catalysis of the transition metals such as rhodium. Carbonylation and other reactions can be realized with the role of carbon monoxide. It also provides a simple synthesis method for a variety of bioactive compounds. In this work, the research progress, mechanism and application in the organic synthesis of rhodium catalyzed carbonylation cyclization of three membered carbon ring derivatives and carbon monoxide are reviewed.

Key words: carbocyclic three-membered ring compounds; rhodium catalysts; carbonylation; cyclization

 

不同粒径立方纳米CeO2的可控合成

甘俊珍,张娟,冯雅楠,崔子祥*,薛永强

(太原理工大学 应用化学系,山西 太原  030024)

 

摘要:纳米CeO2具有优异的性能而广泛应用于催化剂、储氢材料、热电材料和气体传感器等领域;其优异的性能不仅与其本身的物理化学性质有关还取决于材料的粒径大小。因此可控合成不同粒径、形貌规则的纳米CeO2是研究其性能的先决条件。以Ce(NO3)3·6H2ONaOH为原料,通过水热法可控合成粒径范围为19.6  59.8 nm的立方纳米CeO2,并且研究了不同实验条件对其粒径的影响。研究结果表明,水热温度、NaOH的浓度和表面活性剂的种类是影响粒径的主要因素,随着水热温度的升高,粒径逐渐增大;随着NaOH浓度增加,纳米CeO2的粒径先呈增大的趋势,当NaOH的浓度过高时,纳米CeO2的粒径又呈减小的趋势;体系中加入不同的表面活性剂对粒径产生不同的影响:聚乙二醇-2000和柠檬酸钠使纳米CeO2的粒径明显减小,而聚乙二醇-400则产生相反的结果。

关键纳米CeO2;合成;水热法;粒径;影响因素

中图分类号O611.4O614.33+2     文献标A             文章编号:0258-32832018

 

Controlled Synthesis of Cubic Nano-CeO2 with Different Particle Size GAN Jun-zhen, ZHANG juan, FENG Ya-nan, CUI Zi-xiang*, XUE Yong-qiang (Department of Applied Chemistry, Taiyuan University of Technology, Taiyuan 030024, China), Huaxue Shiji, 2018, 40(9)

Abstract: Nano-CeO2 has been widely applied on catalysts, hydrogen storage materials, thermoelectric materials and gas sensors due to its plentiful excellent properties which not only depend on the physical and chemical properties but also on the particle size and the morphology. Therefore, the synthesis of nano-CeO2 with proper particle size and regular morphology is a prerequisite for investigating its properties. Using Ce(NO3)3·6H2O and NaOH as raw materials, the cubic nano-CeO2 with different average diameters (19.6  59.8 nm) was synthesized by hydrothermal method, and the influence regularities of different experimental conditions on the particle size of nano-CeO2 were investigated. The results indicated that the hydrothermal temperature, the concentration of NaOH and the variety of surfactants were the main effect factors on the particle size. The particle size increased with increase of the hydrothermal temperature. With the increase of the concentration of NaOH, the particle size of nano-CeO2 increased first. when the concentration of NaOH was too high, the particle size decreased. Adding different surfactants in the reaction fluid had different effects on the particle size: adding polyethylene glycol-2000 and sodium citrate could reduce the particle size significantly, while adding polyethylene glycol-400 was the opposite.

Key words: nano-CeO2; synthesis; hydrothermal method; particle size; influencing factors

2-甲氧基-3-异丁基吡嗪-(甲氧基-13C)的合成

徐建飞* ,卢伟京,刘占峰,雷雯,侯捷,杜晓宁

(上海化工研究院有限公司 国家同位素工程技术研究中心 上海稳定性同位素工程技术研究中心,上海 200062

 

摘要:近年来,稳定同位素示踪技术在代谢组学的研究中起到了重要作用。以亮氨酰胺盐酸盐为原料,与乙二醛环化反应得到中间体2-羟基-3-异丁基吡嗪,再氯化反应制备2--3-异丁基吡嗪,在碱性条件下和同位素标记甲醇-13C缩合反应得到2-甲氧基-3-异丁基吡嗪-(甲氧基-13C)。合成路线避免中间体由烯醇式变为酮式,避免得到目标产物的同分异构体,且操作简单,工艺流程短,副产物少,收率可达70%以上,13C同位素丰度稀释低。产物经HPLCMS1HNMR 13CNMR表征,结果表明:化学纯度>99%,同位素丰度>98.8 atom%13C

关键词:同位素标记;合成;2-甲氧基-3-异丁基吡嗪

中图分类号:O621.3      文献标识码:A       文章编号:0258-32832018

 

Synthesis of 2-Methoxy-3-isobutyl Pyrazine-(methoxy-13C) XU Jian-fei*, LU Wei-jing, LIU Zhan-feng, LEI Wei, HOU Jie, DU Xiao-ning (Shanghai Engineering Research Center of Stable Isotope, National isotope Engineering Technology Research Center, Shanghai Research Institute of Chemical Industry Co., Ltd, Shanghai 200062, China), Huaxue Shiji, 2018, 40(10),

Abstract: In recent years, stable isotope tracer technique plays an important role in metabonomics research. This work was designed to leucine amide hydrochloride as raw materials, and glyoxal cyclization reaction to obtain the intermediate 2-hydroxy-3-isobutyl pyrazine, then preparation of 2-chloro-3-isobutyl pyrazine by chlorination reaction, under alkaline conditions 2-methoxy-3-isobutyl pyrazine-(methoxy-13C) could be prepared by condensation reaction with isotope labeling of methanol-13C. The synthetic route could avoid the intermediate from enol to keto and obtain the isomer of the target product. It had the advantages of simple operation, short process flow, less side product, the yield of target compound was more than 70%, 13C labeled isotope abundance was not diluted. The product was confirmed by HPLCMS1HNMR and 13CNMR, the chemical purity was more than 99%, the deuterium enrichment was more than 98.8 atom%13C .

Key words: isotope labeling; synthesis; 2-methoxy-3- isobutyl pyrazine


2,6-二取代吡喃类化合物的合成

施梅*,陈昌云,陈红

(南京晓庄学院 环境科学学院,江苏 南京  211171

 

摘要:开发了一种构建2,6-二取代吡喃类骨架的新方法。以糠醛和炔丙基溴为原料,其加成产物分别与正辛醛、异丁醛、苯甲醛及对甲基苯甲醛先后经亲核加成、催化氢化及酸催化环合等反应,合成得62,6-二取代吡喃类化合物。经1HNMR13CNMRHR-MS和元素分析确证了目标化合物及反应中间体的结构。该方法高效、简便且收率高。

关键词:吡喃;2,6-二取代;合成;亲核加成;催化氢化;酸催化环合

中图分类号:O626.3文献标识码:A 文章编号:0258-3283201809

Synthesis of 2,6-Disubstituted Pyran Compounds SHI Mei*, CHEN Chang-yun, CHEN Hong (School of Environmental Science, Nanjing Xiaozhuang University, Nanjing 211171, China), Huaxue Shiji, 2018, 40(9)

Abstract: A novel approach was developed to construct 2, 6-disubstitutedpyran framework. Six new 2, 6-disubstituted pyran compounds were synthesized from the addition product of furfural and propargyl  bromide via three steps including nucleophilic addition, catalytic hydrogenation and acid-catalyzed cyclization. The target compounds and the key intermediates were confirmed by 1HNMR, 13CNMR, HR-MS and elemental analysis. This method is efficient, facile and high-yielding.

Key words: pyran; 2,6-disubstituted; synthesis; nucleophilic addition; catalytic hydrogenation; acid-catalyzed cyclization

 

CaF2-CR杂化吸附材料
对乙基紫的吸附性能研究

赵丹华*,陈锦诗,黄文海,蔡泽静,朱思丽,何东帆,郑丽璇,孙诗乐,曾嘉瑜

(广东第二师范学院 化学系,广东 广州  510303

 

摘要:利用有机染料配体刚果红(CR)与无机骨架材料CaF2进行杂化反应制备CaF2-CR杂化吸附材料。考察了CaF2-CR杂化吸附材料对染料乙基紫吸附过程的动力学、热力学、水体pH、温度、作用时间及离子强度等条件的影响。结果表明:pH为中性,温度为30 ℃,离子强度0.10 mol/L时,CaF2 -CR 加入量为1.05 mg/L、原水色度为 13 163 倍、COD 602 mg/L时,吸附10 min后,色度和COD去除率分别为70%95%CaF2-CREV的吸附过程符合二级吸附动力学方程(R2=0.9999)Langmuir 吸附等温模型能较好的描述该吸附过程,热力学参数ΔG0,表明该吸附是易于自发的过程。

关键词:杂化材料;吸附;动力学;热力学;染料

中图分类号:X703.1      文献标识码A      文章编号:0258-32832018

 

Adsorption of Ethylene Violet on Hybrid Adsorption Material of CaF2-CR ZHAO Dan-hua*, CHEN Jin-shi, HUANG Wen-hai, CAI Ze-jing, ZHU Si-li, HE Dong-fan, ZHENG Li-xuan, SUN Shi-le, ZENG Jia-yu (Department of Chemistry, Guangdong University of Education, Guangzhou 510303, China), Huaxue Shiji, 2018, 40(9)

Abstract: A new type of inorganic-organic hybrid material was designed and synthesized by hybrid reaction with activated calcium fluoride of low cost and dye - Congo Red (CR). The absorbent material endued of perfect effect of decolorization and got rid of COD to degradation actual dye waste water. The results show that the rate of decolorization of inclusion material adsorbent is over 95%, COD removal rate equals to above 70% when the adsorbent concentration was over 1.05 mg/L and adsorbed 10 min in the initial concentration of dye wastewater 13 163 times corlority and 602 mg/L initial COD. Equilibrium was well described by Langmuir isotherms and kinetics was found to fit pseudo-second order type adsorption (R2=0.9999). The results indicated that the adsorption was may be monolayer and physical in nature because of electrostatic force. Moreover, Thermodynamic constant values (ΔG<0) demonstrated that the adsorption reactions of EV onto CaF2-CR hybrid material were feasible and spontaneous. CaF2-CR hybrid material is a kind of efficient adsorbent for treatment of dye wastewater.

Key words: hybrid material; adsorption; kinetics; thermodynamics; dye

中药活性成分药物共晶的研究进展

庄冲,马晓琴,朱宝磊,陈其伟,林宁,陈清*

(广西中医药大学 药学院 广西壮瑶药工程技术研究中心,广西 南宁  530200) 

摘要:从中药中提取得到的有效成分往往具有较为广泛的药理活性,在疾病治疗中起到积极的治疗作用,但许多有效成分存在熔点高、溶解度低、稳定性差等问题,导致药物生物利用度低,不仅影响了药物疗效的发挥,更限制了其在临床上的研究与应用。本综述系统阐述了近年来共晶技术在改善中药及天然药物有效成分的各种性质中发挥的作用,尤其是在提高难溶性有效成分的理化性质和生物利用度等方面的研究进展,为药物共晶在医药领域的进一步拓展提供参考与借鉴。

关键词:药物共晶;中药活性成分;理化性质;生物利用度

中图分类号:R284       文献标识码:A      文章编号:0258-3283

 

Progress on Co-crystal of Active Ingredients of Chinese Materiamedica ZHUANG Chong, MA Xiao-qin, ZHU Bao-lei, CHEN Qi-wei, LIN Ning, CHEN Qing* (School of Pharmacy, Guangxi Zhuang Yao Medicine Center of Engineering and Technology, Guangxi University of Chinese Medicine, Nanning 530200, China), Huaxue Shiji, 2018, 40(10),

Abstract: Many effective ingredients extracted from traditional Chinese materiamedica has good activity and good effect in the treatment of diseases. However, many effective components have such characteristics as high melting point, low solubility and poor stability, which lead to low bioavailability of drugs. It not only affect the effectiveness of the drug, but also restrict its clinical application. In this work, the physicochemical properties and bioavailability of pharmaceutical co-crystal in improving the active ingredient of traditional Chinese medicine is summarized. This work provides a good reference for the application of pharmaceutical co-crystals in the field of medicine.

Key words: pharmaceutical co-crystals; active ingredients of traditional Chinese medicine; physicochemical properties; bioavailability


金核壳结构复合纳米颗粒在生物医学中的应用

吴睿*a,张强a,郝亮a,刘存芳a,宋娟a,田光辉a,熊海涛a,史娟a,魏布谊b

(陕西理工大学 a.化学与环境科学学院 陕西省催化基础与应用重点实验室b.管理学院,陕西 汉中  723000)

 

摘要:核壳结构纳米材料是一种新型复合材料。同时具有核和壳的性质以及独特的光学、电学、催化性能和良好的生物相容性,因此在生物、化学、医学等领域具有巨大的应用价值。基于文献分析,综述了金及其核壳结构纳米复合颗粒在生物及医学上的应用,包括蛋白质、DNA、细菌和病毒的检测,以及肿瘤热疗、生物成像、生物传感、药物传递与释放等。并对完善制备技术以便更好地应用于临床进行了展望。

关键词:金;核壳结构;纳米颗粒;生物医学;应用

中图分类号:O654.9   文献标识码:A   文章编号:0258-32832018

 

Core-shell Structure of Au Nanocomposites in the Application of Biology and Medicine WU Rui*a, ZHANG Qianga, HAO Lianga, LIU Cun-fanga, SONG Juana, TIAN Guang-huia, XIONG Hai-taoa, SHI Juana, WEI Bu-yib (a. Shanxi Key Laboratory of Catalysis and Application, College of Chemical and Environment Science, b.         , Shanxi University of Technology, Hanzhong 723000, China), Huaxue Shiji, 2018, 40(10),

Abstract: As new core-shell structure of composite nanoparticle, especially the precious metal Au, has the properties of the core and shell, as well as other excellent properties, unique optical, electrical and catalytic properties and good compatibility. So, it is widely used in the fields of biology, medicine and chemistry. Based on literature, this work mainly reviewed the applications of core-shell Au in biology and medicine, including the detection of protein, DNA, bacterial and virus, as well as tumor hyperthermia, bioimaging, biosensor, drug delivery and release. And it provided an outlook to improve the preparation technology to better application on the clinic.

Key words: Au; core-shell structure; nanoparticles; biomedicine; application

 

新型抗结核药物研究进展

刘洪涛*1,李文燕2,任炳楠1

(1.河北省人民医院药学部,河北 石家庄  050051

2.河北师范大学 化学与材料科学学院,河北 石家庄  050024

 

摘要:结核病导致全球每年180万患者死亡,是细菌性感染致死的主要因素。近年来随着HIV病毒引起的艾滋病协同感染的增加以及多药耐药菌的产生,迫切需要新型抗结核药物的出现。目前已有数个针对敏感和耐药结核分枝杆菌的化合物处于临床或临床前期研究,为耐药结核病的治疗带来希望。本文综述了目前正在使用和研发的抗结核药物的作用机制、体内、外药理活性及临床研究数据,为抗结核药物的研究提供参考。

关键词:抗结核药物;作用机制;临床研究

中图分类号:O626       文献标识码:A      文章编号:0258-3283(2018)

 

Progress of New Antituberculosis Drugs LIU Hong-tao*1, LI Wen-yan2, REN Bing-nan1 (1.Department of Pharmacy, Hebei General Hospital, Shijiazhuang 050051, China2.College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang 050024, China), Huaxue Shiji, 2018, 40(10),

Abstract: Tuberculosis is a major disease causing every year 1.8 million deaths on worldwide and represents the leading cause of mortality resulting from a bacterial infection. Since the progression of HIV leading to co-infection with AIDS and the emergence of drug resistant strains, the need of new anti-tuberculosis drugs was not overstated. Today, the pipeline of potential new treatments has been fulfilled with several compounds in clinical trials or preclinical development with promising activities against sensitive and resistant mycobacterium tuberculosis strains.

Key word: antituberculosis drugs; action mechanism; clinical trials

 

吡咯类化合物的傅克烷基化反应研究进展

矫鲁振,曹国锐*

(青岛科技大学 化工学院,山东 青岛  266042

 

摘要-碳键形成反应是重要的有机合成反应。傅克烷基化反应通过碳碳键的形成可以直接合成杂环化合物衍生物,是有机化学中形成碳碳键的高效方法。吡咯类化合物在众多天然产物中有着很重要的骨架构筑作用,近年来手性催化吡咯类化合物的不对称傅克烷基化反应成为有机合成化学家新的研究热点。根据手性催化剂的分类,综述了手性磷酸和金属配合物在吡咯类化合物傅克烷基化反应中的研究进展。

关键词傅克烷基化;手性磷酸;不对称合成;吡咯衍生物

中图分类号:0626.13     文献标识码:A      文章编号:0258-32832018

 

JIAO Lu-zhen, CAO Guo-rui* (College of Chemical EngineeringQingdao University of Science and Technology, Qingdao 266042, China), Huaxue Shiji, 2018, 40(9)

Abstract Carbon-carbon bond-forming reaction is an important reaction in organic synthesis. The Friedel-Crafts alkylation reaction is one of effective methods for carbon-carbon bond-forming in organic chemistry. Numerous natural products contain pyrrole skeleton, in recent years, the asymmetric Friedel-Crafts alkylation of pyrrole derivatives has become a new research topic in organic synthesis. Based on the classification of chiral catalysts, the research progress on the chiral phosphoric acid and metal complexes catalyzed Friedel-Crafts alkylation of pyrrole derivatives was reviewed.

Key words Friedel-Crafts alkylation; chiral phosphoric acid; asymmetric synthesis; pyrrole derivatives

 

不同有机物对氨氮测试的影响

谈意川1,李华昌2,朱国2,何海2,陈滢*1

1.四川大学 建筑与环境学院,四川 成都  610065

2.中国石油化工股份有限公司西南油气分公司采气二厂,四川 阆中  637400

 

摘要:本文研究了红糖、葡萄糖、木糖、甲醇和乙酸钠五种不同有机物对纳氏比色法和离子选择电极法测试氨氮的影响。结果表明,红糖、葡萄糖和木糖对纳氏比色法测试氨氮均会造成影响,使得测试结果偏大;在无铵根离子存在时,红糖质量浓度与氨氮的测试浓度线性相关、葡萄糖和木糖质量浓度与氨氮的测试浓度非线性相关;而甲醇和乙酸钠则对纳氏比色法测试氨氮没有影响。实验中采用三氯甲烷萃取+离心法、蒸馏法进行预处理都不能消除其对氨氮测试的影响。但是,采用离子选择电极法测试氨氮时,上述有机物对测试结果并无影响。并对离子选择电极法测试氨氮的测定结果运用SPSS 22.0进行了显著性分析,表明不同有机物种类、有机物浓度对离子选择电极法测试氨氮无显著影响。

关键词:有机物;氨氮测试;预处理;纳氏试剂法;离子选择电极法

中图分类号:X502    文献标识码:A    文章编号:0258-3283(2018)

 

Effects of Different Organic Compounds on Ammonia Nitrogen Test TAN Yi-chuan1, LI Hua-chang2, ZHU Guo2, HE Hai2, CHEN Ying*1 (1.College of Architecture and Environment, Sichuan University, Chengdu 610065,China; 2.The No.2 Gas Production Plant of Southwest Oil & Gas company of China Petroleum & Chemical Corporation, Langzhong 637400, China), Huaxue Shiji, 2018, 40(10),

Abstract: In this work, the effects of five different organic compounds, brown sugar, glucose, xylose, methanol and sodium acetate, on the determination of ammonia nitrogen by Nessler's colorimetric method and ion selective electrode method were investigated. The brown sugar, glucose and xylose could affect ammonia nitrogen testing by Nessler's colorimetric method, making the test results higher than the actual values. In the absence of ammonium ions, the concentration of brown sugar was linearly correlated with the test concentration of ammonia nitrogen. The concentration of glucose and xylose was not linearly related to the test concentration of ammonia nitrogen. The methanol and sodium acetate did not affect ammonia nitrogen test. The trichloromethane extraction+centrifugation and distillation as pretreatment both could not eliminate the influence on ammonia nitrogen test. When ammonia nitrogen was measured by ion selective electrode method, the above organic matters had no effect on the test results. The results of determination of ammonia nitrogen for the saliency analysis by SPSS 22 by ion selective electrode methodthe different types of organics and organic matter concentration had no significant effect on the test of ammonia nitrogen.

Key words: organic; ammonia nitrogen test; pretreatment; Nessler's reagent method; ion selective electrode method

 

抑制Fe2+-H2O2-孔雀石绿褪色光度法测定挂面中的丙二醛

雷禄,谢宇奇,马璐,黄雪秋,谭天宋,凌绍明*

百色学院 学与环境工程学院,广西 百色  533000

 

摘要Fe2+-H2O2在酸性介质中氧化孔雀石绿反应褪色,但丙二醛加入Fe2+-H2O2-孔雀石绿组成体系抑制褪色反应,且体系的吸光值随着丙二醛的含量增加呈现线性增长。据此原理建立可见光分光光度法测定溶液中的丙二醛的含量。在最优实验条件下,波长l=620 nm170 μL硫酸、40 μL硫酸亚铁、400 μL孔雀石绿,140 μL过氧化氢,反应时间为15 min、反应温度35 时,线性回归方程为:ΔA620nm=0.1971ρ0.0143 (ρμg/mL)线性范围为0.125 ~ 3.50 μg/mL,检出限3S/K)为0.068 μg/mL,该方法分析挂面中的丙二醛的含量,回收率在96 %  107 %之间,分析方法可行。

关键词光度法;挂面;孔雀石绿;丙二醛

中图分类号0656.3      文献标识码A       文章编号0258-32832018

 

Determination of Malondialdehyde in Noodle by Inhibiting Fe2+-H2O2- Malachite Green Fading Spectrophotometry LEI LuXIE Yu-qiMa LuTAN Tian-songLING Shao-ming*( College of Chemistry and Environmental Engineering, Baise University, Baise 533000, China), Huaxue Shiji, 2018, 40(10)

Abstract: The inhibition effect of malondialdehyde on the fading of malachite green oxalate solution by Fe2+-H2O2 oxidation was investigated in sulfuric acid medium. The absorbance value of solution increases with the concentration of malondialdehyde in solution.  A method for the determination of malondialdehyde in the liquid by spectrophotometry was established. The optimum experimental conditions are as follows: the maximum fading wavelength was located at 620 nm, the volume of sulfuric is 170 μL, the volume of ferrous sulfate is 40 μL, the volume of Malachite Green is 400 μL, the volume of perhydrol is 140 μL. The linear regression equation is ΔA620nm=0.1971ρ0.0143 (ρ: μg/mL), the linear range of 0.125 to 3.50 μg/mL, and the detection of limit is 0.068 μg/mL. The recovery of MDA was 96%  107% in the analysis noodles via this method, and this method is feasible.

Key words: spectropotometry; noodle; malachite green; malondialdehyde 

 

 

碱性高锰酸钾分光光度法测定盐酸肼屈嗪含量

牟城健a,王振b,许钟元b,马卫兴*b,李树安b

(淮海工学院 a.化学工程学院,b.药学院,江苏 连云港  22205

 

摘要:基于盐酸肼屈嗪在碱性条件与高锰酸钾发生氧化还原显色反应建立了碱性高锰酸钾分光光度法测定盐酸肼屈嗪的新方法,详细研究了该体系的反应条件,实验发现最大显色波长分别在420 nm600 nm处,最大褪色波长在530 nm处,在此三波长处测定的表观摩尔吸光系数分别是1.566×105 L/(mol·cm)3.40×105 L/(mol·cm)2.43×105 L/(mol·cm),盐酸肼屈嗪浓度均在0.010.07 mg/L范围内吸光度与浓度呈现线性关系,其线性回归方程分别是A=0.7904 C+0.0309A=1.2368 C+0.0624A=1.7311 C+0.1441,相关系数R分别是0.99950.99980.9994,测得的相对标准偏差分别1.11%1.02%0.96%,回收率分别在98.35%  101.9%98.65%  101.5%98.45%  102.0%之间。所拟方法成功地用于盐酸肼屈嗪片剂中盐酸肼屈嗪的含量测定,结果与硼酸催化茚三酮法所得结果一致。

关键词:盐酸肼屈嗪;高锰酸钾;分光光度法;显色反应

中图分类号:O657.32         文献标识码:A      文章编号:0258-32832018

 

Determination of Hydralazine Hydrochloride by Alkaline Potassium Permanganate Spectrophotometry MOU Cheng-jianaWANG ZhenbXU Zhong-yuanbMA Wei-xing*bLI Shu-anb (a.College of Chemical Engineering, b.College of Pharmacy, Huaihai Institute of Technology, Lianyungang 222005, China), Huaxue Shiji, 2018, 40(10),

Abstract: Based on the redox chromogenic reaction of hydralazine hydrochloride with potassium permanganate in alkaline conditions, a new method of alkaline potassium permanganate spectrophotometric determination of hydralazine hydrochloride was established. The reaction conditions of the system were investigated in detail. The maximum color developing wavelength was at 420 nm and 600 nm, respectively, and the maximum fading wavelength was at 530 nm. The apparent molar absorptivities measured at these three wavelengths were 1.566×105 L/(mol·cm), 3.40×105 L/(mol·cm) and 2.43×105 L/(mol·cm), respectively. Hydrazine hydralazine concentration in the range of 0.01  0.07mg/L absorbance and concentration showed a linear relationship, the linear regression equation were A=0.7904 C+0.0309, A=1.2368 C+0.0624 and A= 1.7311 C+0.1441, the correlation coefficients R were 0.9995, 0.9999 and 0.9994 respectively, the relative standard deviations were 1.11%, 1.02% and 0.96%, respectively. The recoveries were 98.35%  101.9% and 98.65%  101.5% and 98.45%  102.0%. The proposed method was successfully applied to the determination of hydralazine hydrochloride in hydralazine hydrochloride tablets. The results were consistent with that of boric acid catalytic ninhydrin method .

Key words: hydralazine hydrochloride; potassium permanganate; spectrophotometry; color development reaction

 

HPLC-MS/MS法检测2--2-脱氧-D-葡萄糖

方法优化及验证

袁艳娟,刘晶,乔红群*

(南京工业大学 江苏省药物研究所 江苏省药物安全性评价中心,南京 211800

 

摘要:建立了高效液相色谱-三重四极杆串联质谱( HPLC-MS/MS)检测2--2-脱氧-D-葡萄糖(ClDG)的分析方法。采用多反应监测( MRM) 负离子电喷雾模式进行HPLC-MS/MS分析。色谱柱为:Alltima Amino 100A 5μ(250×4.6mm),流动相为5mmol/L乙酸铵-乙腈(10:90);柱温:35 ;流速:1 mL /min;进样量:5 μLClDG浓度在0.5  37.5 μg/mL范围内与峰面积有良好的线性关系,检出限为0.15 μg/mL,定量限为0.5 μg/mL。方法回收率为92.6%  105.0%。方法选择性、重复性良好,灵敏度高,能用于2--2-脱氧-D-葡萄糖(ClDG)的痕量分析。

关键词:HPLC-MS/MS2--2-脱氧-D-葡萄糖;方法验证

中图分类号:TQ464.9  文献标识码:A   稿件编号:0258-32832018

 

Optimization and Verification for the Determination of ClDG Concentration by HPLC-MS/MS YUAN Yan-juan, LIU Jin, QIAO Hong-qun* (Jiangsu Provincial Institute Of Materia Medica, Jiangsu Center for Safety Evaluation of Drugs, Nanjing Tech University, Nanjing 211800, China), Huaxue Shiji, 2018, 40(10),

Abstract: A method for the determination of 2-chloro-2-deoxy-D-glucose (ClDG) by high performance liquid chromatography-triple quadrupole mass spectrometry (HPLC-MS/MS) was established. HPLC-MS/MS analysis was performed using multiple reaction monitoring (MRM) negative ion electrospray mode. The column was: Alltima Amino 100A 5μ(250×4. 6 mm), mobile phase :5 mmol/L ammonium acetate-acetonitrile (10:90); column temperature: 35°C; flow rate: 1 mL/min; injection volume: 5 μL. There was a good linear relationship between the concentration of ClDG and the peak area in the range of 0.5 to 37.5 μg/mL. The detection limit was 0.15 μg/mL and the limit of quantitation was 0.5 μg/mL. The recovery of the method was 92.6%  105.0%. The method has good selectivity, good repeatability and high sensitivity and can be used for the trace analysis of 2-chloro-2-deoxy-D-glucose (ClDG).

Key words: HPLC-MS/MS; ClDG; method validation

 

紫外光辐照下Oxone试剂催化降解水中典型抗生素

磺胺甲噁唑

李晓静1,郑宾国*2,姜灵彦2,张旭升2

(1.郑州工程技术学院 化工食品学院,河南 郑州  4500442.郑州航空工业管理学院 

土木建筑工程学院 郑州市环境功能材料重点实验室,河南 郑州  450015

 

摘要采用过硫酸氢钾(Oxone试剂)催化氧化降解水中微污染物磺胺甲噁唑。探究了磺胺甲噁唑初始浓度、溶液pH、反应温度、Oxone试剂用量、反应时间及水中有机物腐殖酸等对磺胺甲噁唑降解效果的影响,结合液相色谱质谱(LC-MS)分析阐明了磺胺甲噁唑的降解路径。结果表明:磺胺甲噁唑溶液初始质量浓度为15 mg/L、溶液pH9.3、反应温度为30 Oxone试剂用量为3.0 mmol、且紫外灯辐照下,反应3 h后,磺胺甲噁唑的降解率达到了93.4%

关键词过硫酸氢钾;紫外辐照;催化降解;抗生素;磺胺甲噁唑

中图分类号:X592    文献标识码A    文章编号0258-3283(2018)

 

Degradation of Antibioticsulfamethoxazole by Oxone/UV in Aqueous Solutions LI Xiao-jing1, ZHENG Bin-guo2, JIANG Ling-yan2, ZHANG Xu-sheng2 (1.School of Chemical Engineering and Food Science, Zhengzhou Institute of Technology, Zhengzhou 450044, China; 2. Zhengzhou Key Laboratory of Environmental Functional Materials, School of Civil Engineering, Zhengzhou University of Aeronautics, Zhengzhou 450015, China), Huaxue Shiji, 2018, 40(10),

Abstract: The oxidative degradation of sulfamethoxazole by oxone/UV in aqueous solutions was investigated in this work. The influencing factors on sulfamethoxazole degradation, including the initial concentration of sulfamethoxazole, solution pH, oxone dosage, temperature and humic acid, were discussed. The degradation path of sulfamethoxazole was also discussed. The degradation efficiency of sulfamethoxazole could reach 93.4% under conditions that the initial concentration sulfamethoxazole was 15 mg/L, pH value was 9.3, the dose of oxone was 3.0 mmol, the reaction temperature was 30℃, the reaction time was 3 h, and with the ultraviolet irradiation.

Key words: Oxone; UV; catalytic degradation; antibiotic; sulfamethoxazole

 

共轭二茂铁衍生物的合成及晶体结构

侯敬严,李玥,王梓航,张玉梅*,刘鹏

(河北科技大学 理学院,河北 石家庄  050018

 

摘要:在无溶剂条件下,以1,1-二氰基-2-二茂铁基丙烯和芳香醛为原料,肌氨酸为催化剂,通过微波辅助法合成D-π-A型共轭二茂铁衍生物:2-二茂铁基-1,1-二氰基-1,3-二烯衍生物利用核磁共振氢谱(1HNMR),  核磁共振碳谱(13CNMR)红外光谱(FT-IR)等对化合物进行了表征。通过单晶X-射线衍射确定了化合物的晶体结构。晶体属于单斜晶系P2(1)/c 空间群。

关键词:二茂铁衍生物;晶体结构;肌氨酸催化剂;微波辅助

中图分类号O629     文献标识码A      文件编号:0258-32832018

 

Synthesis and Crystal Structure of D-π-A Ferrocene Derivative HOU Jing-yan, LI Yue, WANG Zi-hang, ZHANG Yu-mei*, LIU Peng(College of Sciences, Hebei University of Science & Technology, Shijiazhuang 050018, China), Huaxue Shiji, 2018, 40(10),

Abstract: Microwave-assisted solvent-free synthesis of a new (D-π-A) chromogenes 2-ferrocenyl-1,1-dicyanobuta-1,3-diene derivative has been accomplished via the condensation of 2-(1-ferrocenylethylidene) malononitrile and aromatic aldehydes in moderate yield (43%), with sarcosine as the catalyst. The crystal structure was confirmed by 1HNMR, 13CNMR and FT-IR. Meanwhile, the target compound was determined by X-ray crystallography. The crystal belongs to monoclinic, space group P2(1)/c.

Key words: ferrocene derivative; crystal structure; sarcosine-catalyst; microwave irradiation

 

中间体6--5-甲氧基吲哚合成工艺研究

刘长春1,程进1,薛叙明1,李晓强*2

1.常州工程职业技术学院 化学与材料工程学院,江苏 常州  213164

2.江南大学纺织 服装学院,江苏 无锡  214122

 

摘要:3--4-甲氧基苯胺和水合氯醛、盐酸羟胺为原料,通过Sandmeyer异亚硝基乙酰替苯胺合成法制备得6--5-甲氧基靛红,再由硼氢化钠/三氟化硼乙醚体系还原制备得目标化合物。实验考察了酰胺化反应温度和反应时间、成环反应温度、还原体系种类及还原剂用量对反应收率的影响,较佳的酰胺化反应温度和反应时间为90 回流反应10 min,较优的成环反应温度为80  85 ℃,选用更加安全的硼氢化钠/三氟化硼乙醚体系作为还原剂,较优的还原剂物质的量比为n(硼氢化钠)n(三氟化硼乙醚)n(7-卤代靛红)=4.02.51.0。所有产物结构均通过1H NMR13CNMR和元素分析等进行了表征。由6--5-甲氧基靛红还原制备目标化合物的工艺,与现有目标化合物合成工艺相比,避免了使用剧毒品,具有更安全,反应条件温和,总收率较高(以3--4-甲氧基苯胺计为49.52%),成本较低等优点,适合批量制备目标化合物,具有广阔的工业应用前景。

关键词:3--4-甲氧基苯胺;6--5-甲氧基靛红;6--5-甲氧基吲哚;Sandmeyer异亚硝基乙酰替苯胺合成法;硼氢化钠/三氟化硼乙醚

中图分类号:TQ 251.3    文献标识码:A    文章编号:0258-3283(2018)

 

Synthesis of 6-Chloro-5-methoxy-1H-indole LIU Chang-chun1, CHENG Jin1, XUE Xu-ming1, LI Xiao-qiang*2 (1.College of Chemistry & Materials Engineering, Changzhou Institute of Engineering and Technology, Changzhou 213164, China; 2.College of Textile & Clothing, Jiangnan University, Wuxi 214122, China), Huaxue Shiji, 2018, 40(10),

Abstract:6-Chloro-5-methoxy-1H-isatin was prepared with Sandmeyer isonitrosoacetanilide isatin synthesis method by using 3-chloro-4-methoxyaniline. The chloral hydrate and the hydroxylamine hydrochloride were used as raw materials. The precursor was reduced to 6-chloro-5-methoxy-1H-indole via NaBH4/BF4-Et2O reduction system. The effects of amination reaction temperature and time, annulation temperature, reductant species and reductant dosage on the yields were investigated. The modified acetylation reaction temperature and time, annulation reaction temperature, better reductant were 90 ℃ (reflux) for 10 min, 80 ~ 85 ℃ and sodium borohydride/boron trifluoride etherate, respectively. The best molar ratio of sodium borohydride, boron trifluoride etherate, and 7-halogenated isatins was 4.0:2.5:1.0. The structure of all products was confirmed by 1HNMR, 13CNMR, elemental analysis and so on. The preparation for 6-chloro-5-methoxyindole through the reduction of 6-chloro-5-methoxyisatin was first reported. Compared with the existing synthesis process of 6-chloro-5-methoxyindole, the improved procedure is more convenient, safer with mild reaction conditions, low cost, higher total yield (49.52%, calculated by 3-chloro-4-methoxyaniline) and good prospects for industrial applications.

Key words: 3-chloro-4-methoxyaniline; 6-chloro-5-methoxy-1H-Isatin; 6-chloro-5-methoxy-1H-indole; sandmeyer isonitrosoacetanilide isatin synthesis; sodium borohydride/ boron trifluoride etherate

 

2-氨基-3-[(3-(苄氧基)-3-氧代丙基)]硫代丙酸的合成

金彪,张敬东,王思宏*

(延边大学 分析测试中心,吉林 延吉  133002

 

摘要:以苯甲醇、苯酚和8-羟基喹啉为原料,用丙烯酰氯酰化,与L-半胱氨酸进行巯基-双键反应,得到2-氨基-3-[(3-(苄氧基)-3-氧代丙基)]硫代丙酸,其结构经核磁共振谱、质谱和红外光谱确定,总收率89%

关键词:L-半胱氨酸;苯酚;苯甲醇;8-羟基喹啉;丙烯酰氯;巯基-双键反应;2-氨基-3-[(3-(苄氧基)-3-氧代丙基)]硫代丙酸

中图分类号:O627       文献标识码:A        文章编号:0258-3283(2018)

 

Synthesis of 2-Amino-3-[(3-(benzyloxy)-3-oxopropyl)thio]propanoic Acid JIN Biao, ZHANG Jing-dong, WANG Si-hong* (Analysis and Inspection Center, Yanbian University, Yanji 133002, China), Huaxue Shiji, 2018, 40(10),

Abstract: Benzyl alcohol, phenol and 8-hydroxyquinoline are used as raw materials, then acroleyl chloroacylation,furthermore, react with L-cysteine by means of thiol-ene reaction. Only 2-amino-3-[(3-(benzyloxy) -3-oxopropyl)thio]propanoic acid was obtained. The structure is confirmed by nuclear magnetic resonance spectrum, mass spectrometry and infrared spectrum. The total yield is 89%.

Key words: L-cysteine; phenol; benzyl alcohol; 8-hydroxyquinoline; acryloyl chloride; thiol-ene reaction;

2-amino-3-[(3-(benzyloxy)-3-oxopropyl)thio]propanoic acid

 

 

比拉斯汀关键中间体的合成

韩在祺,王森,崔佰吉,冯波,姚璐*,昌盛*

(吉林医药学院,吉林省 吉林市  132013

 

摘要:2-[1-(4-溴苯基)-1-甲基乙基]-4,5-二氢-4,4-二甲基噁唑为起始原料,通过与二溴乙烷的格氏反应得到4-[1-(5,5-二氢-4,4-二甲基-2-噁唑基-1-甲基乙基]-2-苯乙基溴,再与2-(4-哌啶基)-1H-苯并咪唑在碱性条件下经亲核取代得到比拉斯汀中间体2-(2-(4-(2-(4-(1H-苯并咪唑-2-)哌啶-1-)乙基)苯基)-2-)-4,4-二甲基4,5-二氢噁唑,总收率63%

关键词:比拉斯汀; 关键中间体; 合成

中图分类号:R976               文献标识码:A       文章编号:0258-32832018

 

Synthesis of Key Intermediates of Bilastine HAN Zai-qi, WANG Sen, CUI Bai-ji, FENG Bo, YAO Lu* , CHANG Sheng1 (Jilin Medical University, Jilin 132013, China), Huaxue Shiji, 2018, 40(10),

Abstract: 2-(2-(4-Bromophenyl)propan-2-yl)-4,4-dimethyl-4,5-dihydrooxazole was used as the starting material, 2-(2-(4-(2-bromoethyl)phenyl)propan-2-yl) was synthesized via Grignard reaction by reacted with 1,2-dibromoethane. The brominated product further reacted with 2-(piperidin-4-yl)-1H-benzo[d]imidazole in the presences of base to afford 2-(2-(4-(2-(4-(1H-benzo[d]imidazol-2-yl)piperidin-1-yl)ethyl)phenyl)propan-2-yl)-4,4-dimethyl-4,5-dihydrooxazoe the key intermediate of bilastine with an overall yield of 63%.

Key words: bilastine; the key intermediates; synthesis

 

/二甲基亚砜催化合成2-取代苯并咪唑

孙开进*朱驯

(盐城工业职业技术学院 化工系, 山东 盐城  224005)

摘要: 探索一种合成2-代苯并咪唑化合物的新方法。以醇和邻苯二胺为原料,采用一锅法合成多功能单体2-代苯并咪唑。通过单因素条件实验,确定了合成2-取代苯并咪唑的工艺及条件。以0.05倍物质的量的碘和5倍物质的量的二甲基亚砜为催化氧化体系,二甲苯为溶剂,n()n(邻苯二胺)=1.21.0,反应15 h该方法路线简单、原料易得、2-取代苯并咪唑收率高,适合工业化生产。

关键词: 碘;二甲基亚砜;2-代苯并咪唑;一锅法

中图分类号:O621.3   文献标识码:A     文章编号:0258-32832018

 

Synthesis of 2-Substituted Benzimidazole Compounds Catalyzed by I2-DMSO SUN Kai-jin*, ZHU Xun(         Yancheng Vocational Institute of Industry Technology, Yancheng 22400, China, Huaxue Shiji, 2018, 40(9)

Abstract: To establish a new way of preparation of 2-substituted benzimidazole compounds. 2-Substituted benzimidazole compounds are prepared from alcohol and o-phenylenediamine by one-pot reaction. The conditions of the synthesis of 2-phenyl benzimidazoles are as follows: 5mmol% iodine used as catalyst, 5 equivalent DMSO used as oxidant, toluene used as solvent. And material ratio of benzyl alcohol and phenyl amine is 1.21 under conditions of 100 oC, 15h. And the yield is high. The new route is simplesuit for a large scale and the raw materials are easily obtained

Key wordsiodine; dimethyl sulfoxide; 2-substituted benzimidazole compounds ; one-pot reaction

 

头孢西酮中间体的合成研究

                          赵艳平    

(呼伦贝尔职业技术学院 护理系,内蒙古 呼伦贝尔  021000

 

摘要:3,5-二氯吡啶为原料,经4步反应制得头孢西酮中间体3,5-二氯-4-吡啶酮乙酸。原料经硝化、还原、重氮化水解,缩合反应制得产物。对各步单元反应进行了条件优化,得到最优反应条件,4步反应收率为57.6%HPLC含量为97.5%。反应产物结构经1HNMR13CNMR确证,整个合成工艺简单、收率高,具有很好的工业应用前景。

关键词:头孢西酮;中间体;合成

中图分类号TQ45     文献标识码:A     文章编号:0258-32832018

 

Synthesis for Intermediate of Cefazedone ZHAO Yan-ping       , Hulunbuir Vocational Technical College, Hulunbuir 021000, China, Huaxue Shiji, 2018, 40(9) 

Abstract: The target compound 3, 5-dichloropyridine acetic acid as the important intermediate of Cefasidone can be prepared via 4 steps reactions from 3, 5-dichloropyridine , nitrification, reduction, diazo hydrolysis and condensation reaction. The optimum reaction conditions were obtained, the overall yield of four steps reaction was 57.6 % and the purity of final product was 97.5 %. The structure was confirmed by 1HNMR and 13CNMR. The smooth synthetic process with high yield made it suitable for industrial application.

Key words: Cefazedone; intermediate; synthesis


两个维生素B6有关物质的合成

刘自兵

浙江海正药业股份有限公司,浙江 台州 318000

 

摘要:为了对维生素B6进行质量控制,合成了英国药典(BP2013)和欧洲药典(EP8.0)中收录的两种有关物质,分别为1,3-二氢-6-甲基-呋喃并[3,4-c]吡啶-7-醇(有关物质A)和5-(羟甲基)-2,4-二甲基吡啶-3-醇(有关物质B)。所合成目标化合物的结构经1HNMR13CNMR和高分辨质谱确证,纯度经HPLC检测均在98.3%以上,可作为维生素B6质量控制的对照品。

关键词:维生素B6;有关物质;合成

中图分类号:TQ463    文献标志码:A    文章编号:0258-32832018

 

Synthesis of Two Pyridoxine Hydrochloride Related Substances LIU Zi-bing* (Zhejiang Hisun Pharmaceutical Co., Ltd, Taizhou 318000, China), Huaxue Shiji, 2018, 40(10),

Abstract: In order to control the quality of pyridoxine hydrochloride, two related substances  6-methyl-1,3-dihydrofuro[3,4-c]pyridin-7-ol (substance A) and 5-(hydroxymethyl)-2,4-dimethylpyridin-3-ol (substance B) which included in British Pharmacopoeia (BP2013) and European Pharmacopoeia (EP8.0) were synthesized. The target compound structures were confirmed by 1HNMR, 13CNMR and HRMS. The purity of above 98.3% were determined using HPLC, which can be used for quality control of pyridoxine hydrochloride.

Key words: pyridoxine hydrochloride; related substances; synthesis