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《化学试剂》2019年第8期中英文摘要

离子液体/γ-丁内酯阻燃性电解液在锂离子电池中的应用研究

蔡晓兰,张圣洁,方岩雄,刘全兵,谭伟*

(广东工业大学 轻工化工学院,广东 广州,510006

 

摘要:采用离子液体/γ-丁内酯(γ-BL)共混型电解液N-甲基-N-乙基乙基醚双氟磺酰亚胺(PYR1(2o2)TFSI)/γ-BL-LiTFSI作为锂离子电池电解液,研究了不同比例的PYR1(2o2)TFSIγ-BL的共混型电解液对电极材料的电化学性能和表面特性的影响。通过同步热分析、红外光谱仪、扫描电镜、充放电测试、倍率性能测试分析电解液的物理性质和电化学性质。添加10%体积分数的γ-丁内酯至PYR1(2o2)TFSI-LiTFSI电解液中,该电解液表现出优异的电化学性能和阻燃性能,0.2 C下循环50次后,Li/LiFePO4电池放电比容量能够保持在147 mAh/g,而且倍率性能明显优于其它3种电解液。

关键词:锂离子电池;离子液体;阻燃电解液

中图分类号: TQ15            文献标识码:A      文章编号:0258-32832019--

 

Application Research Of Ionic Liquid/γ-butyrolactone Flame Retardant Electrolyte In Li-ion Batteries CAI Xiao-lan, ZHANG Sheng-jie, FANG Yan-xiong, LIU Quan-bing, TAN Wei* (School of Light Industry and Chemical Engineering, Guangdong University of Technology, Guangzhou 510006, China), Huaxue Shiji, 41(8), ~

Abstract: By employing the blending electrolyte of ionic liquid/γ-butyrolactone PYR1(2o2)TFSI/γ-BL-LiTFSI as the Li-ion batteries electrolyte, the effect of various ratios of PYR1(2o2)TFSI and γ-BL on the electrochemical and surface properties of the electrode material was investigated. The physical properties and electrochemical properties of the electrolyte were analyzed by simultaneous thermal analysis, infrared spectrometer, scanning electron microscope, charge and discharge test, and rate performance test, respectively. When the volume ratio of PYR1(2o2)TFSI/γ-BL was 9:1, the electrolyte exhibited excellent electrochemical and flame retardant properties. The specific discharge capacity of Li/LiFePO4 battery can be maintained at 147 mAh/g after 50 cycles under 0.2 C. Moreover, the rate performance was significantly improved compared with other three electrolytes.

Key words: lithium ion battery; ionic liquid; flame retardant electrolyte

 

锰卟啉高价金属氧化物及氢氧化物对甲苯α-C-H键的活化

戴宇萍,王浩,于艳敏*,宋旭锋

(北京工业大学 化学化工系 绿色催化与分离北京市重点实验室,北京  100124)

 

摘要:锰卟啉作为仿生催化剂催化活化烃类饱和C-H键的反应中,锰卟啉高价金属氧化物和氢氧化物均有活化C-H键的能力。采用密度泛函理论对锰卟啉高价金属氧化物及氢氧化物活化甲苯α-C-H键进行研究,考察影响其活性的本质因素。结果发现,锰卟啉高价金属氧化物和氢氧化物的单重态由于没有氧自由基特征而不具备活化甲苯α-C-H键的能力。高自旋锰卟啉金属氧化物活化甲苯α-C-H键能力较强,金属氢氧化物的活化能力较弱。过渡态结构的形变能和结合能共同决定了活化能的大小,且形变能是影响其活性的关键因素。

关键词:锰卟啉;活化;C-H

中图分类号:O64    文献标识码:A     文章编号:0258-32832019

 

Activation of Toluene α-C-H Bond by Mn-oxo Porphyrin and Mn-hydroxo Porphyrin  DAI Yu-ping, WANG Hao, YU Yan-min*, SONG Xu-feng (Department of Chemistry and Chemical Engineering, Beijing Key Laboratory for Green Catalysis and Separation, Beijing University of Technology, Beijing 100124, China), Huaxue Shiji, 2019, 41(8

Abstract: In the catalytic oxidation of saturated C-H bond of hydrocarbons by manganese porphyrin as biomimetic catalyst, both high-valence Mn-oxo porphyrin and Mn-hydroxo porphyrin have the ability to activate C-H bond. The activation of toluene α-C-H bond by high-valence Mn-oxo porphyrin and Mn-hydroxo porphyrin were investigated using density functional theory, and the key factors affecting the activity were investigated. The results show that the singlet state structures of Mn-oxo porphyrin and Mn-hydroxo porphyrin have no ability to activate the C-H bond due to the absence of oxyl radical. The high spin states of Mn-oxo porphyrin have the higher activity and Mn-hydroxo porphyrin has the lower activity to activate toluene α-C-H bond. The activation energy was determined by interaction energy and distortion energy. Distortion energy is the key factor affecting the activity of Mn-oxo porphyrin and Mn-hydroxo porphyrin.

Key words: manganese porphyrin; activation; C-H bond

 

系列二烯丙基甲基烷基氯化铵的合成

陶贤平*1贾旭2张跃军2周君1张秀娟2

1.南通职业大学 化学与生物工程学院,江苏  南通  2260072.南京理工大学 化工学院,江苏  南京 210094

 

摘要:以不同碳链的N-甲基烷基胺(n 357)和氯丙烯为主要原料,合成了3种二烯丙基甲基烷基氯化铵(分别标记为C3C5C7),其最佳合成条件为:蒸馏水195 mL,原料物质的量比nN-甲基烷基胺):n(氯丙烯):n(氢氧化钠) 1.02.51.3,反应温度50 54 ℃,反应时间24 28 h,所得产物的收率分别为84.3%81.5%82.3%;用FTIR1HNMR对产物结构进行表征;测定C3C5C7的水溶性和絮凝性能,结果表明,季铵盐C3C5C7的低温水溶性好,对高岭土及硅藻土絮凝能力的强弱次序为C7C5C3

关键词:氯丙烯;季铵盐;二烯丙基甲基烷基氯化铵;合成

中图分类号:TQ423      文献标识码:A      文章编号0258-32832019--

 

Synthesis of a Series Diallymethylalkyl Ammonium Chloride TAO Xian-ping*1JIA Xu2ZHANG Yue-jun2ZHOU Jun1ZHANG Xiu-juan2 (1.College of Chemical and Biological Engineering, Nantong Professional Institute, Nantong 226007, China; 2.School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China, Huaxue Shiji, 2019, 41(8)

AbstractThree kinds of diallylmethylalkyl ammonium chloride(labeled C3,C5,C7) were synthesized by using N-methylalkylamine of different carbon chains(n=3,5,7) and allylchloride as the main raw materials. The optimum synthesis conditions were as followsDistilled water was 195 mL, molar ratio n(N-methylalkylamine)n(allylchloride)n(sodium hydroxide)= 1.02.51.3, reaction temperature 50 54 and reaction time 24 28 h.The product yields could achieve 84.1%, 81.5% and 82.3%, respectively. Structures of the products were confirmed by FTIR and 1HNMR. The water solubility and flocculation properties of C3, C5 and C7 were determined. The results show that the water solubility of quaternary ammonium salt C3, C5 and C7 are good at low temperature, and their flocculation capacity to kaolin and diatomite are in the order of C7>C5>C3.

Key wordsallylchloridequaternary ammonium saltdiallylmethylalkyl ammonium chloridesynthesis

 

一锅法和两步法合成磁性羟基磷灰石重金属吸附材料研究

高卫民*1,2,程寒飞1,2,詹茂华1,2,陈志刚1,2

(1.中冶华天南京工程技术有限公司,江苏 南京 2100192.中冶华天工程技术有限公司,安徽 马鞍山  243061)

 

摘要:分别采用一锅法和两步法工艺制备了磁性羟基磷灰石复合材料(HAP/Fe3O4复合磁性材料)。通过X射线衍射(XRD)对两种方法合成的HAP/Fe3O4复合磁性材料进行微观结构表征与分析。并研究了HAP/Fe3O4复合磁性材料对Cd2+的吸附性能。结果表明:羟基磷灰石均匀负载在Fe3O4微粒表面,HAP/Fe3O4复合磁性材料对Cd2+的吸附性能比HAP明显提高,且一锅法合成的HAP/Fe3O4复合磁性材料中HAPFe3O4表面分布更均匀,更牢固,且比表面积更大,较两步法的好,并具有更好的磁分离能力。随着Cd2+初始浓度由0.02 mg/L增大到0.1 mg/L,去除率均呈下降趋势,吸附量呈上升趋势,当Cd2+初始浓度为0.1 mg/L时,一锅法制得HAP/Fe3O4复合磁性材料对Cd2+的去除率在90%以上,其吸附量较HAP吸附量提高30%以上,两步法制得HAP/Fe3O4复合磁性材料对Cd2+的去除率在85%以上,其吸附量较HAP吸附量提高了20%以上。HAP/Fe3O4复合磁性材料在外加磁场的作用下具有良好的分离回收和循环利用性能,是一种潜在的重金属高效吸附材料。

关键词:羟基磷灰石;磁性;吸附;一锅法;两步法

中图分类号:O611.4    文献标识码:A     文章编号0258-32832019

 

Synthesis of Magnetic HAP for the Enrichment of Heavy Ions by One-pot and Two-step Ways GAO Wei-min*1,2, CHENG Han-fei1,2, ZHAN Mao-hua1,2, CHEN Zhi-gang1,2 (1.MCC Nanjing Huatian Engineering & Technology Corporation, Nanjing 210019, China; 2.MCC Huatian Engineering & Technology Corporation, Maanshan 243061China), Huaxue Shiji, 2019, 41(8),

Abstract: Magnetic HAP was synthesized by means of “one-pot” and “two-step ways. The microstructure of HAP/Fe3O4 was confirmed by X-ray diffraction (XRD). The adsorption properties of HAP/Fe3O4 on Cd2+ were also investigated. The results show that HAP is uniformly loaded on the surface of Fe3O4 particles. The adsorption capacity of Cd2+ after HAP/Fe3O4 increased significantly compared with that of HAP. And the HAP/Fe3O4 synthesized by one-pot method is more uniform and firm on the surface of Fe3O4, and the specific surface area is larger, better than the two-step method, and has better magnetic separation ability. With the initial concentration of Cd2+ increasing from 0.02mg/L to 0.1mg/L, the removal rate of Cd2+ decreases and the adsorption capacity increases. When the initial concentration of Cd2+ is 0.1mg/L, the removal rate of Cd2+ by the HAP/Fe3O4 synthesized by one-pot method is more than 90%, and the adsorption capacity of HAP/Fe3O4 is more than 30% higher than that of HAP. The removal rate of Cd2+ by the HAP/Fe3O4 synthesized by two-step method is over 85%, and its adsorption capacity is more than 20% higher than that of HAP. HAP/Fe3O4 has good separation, recovery and recycling properties under the action of applied magnetic field. It is a potential Heavy Ions adsorption material with high efficiency.

Key words: hydroxyapatitemagnetismadsorptionone-pot methodtwo-step method

 

克拉霉素掩味颗粒的制备及评价

杨慧杰,糜志远,张佳*

(湖北工业大学 生物工程与食品学院,湖北 武汉 430064

 

摘要:制备克拉霉素掩味颗粒并对其进行评价。通过流化床包衣和造粒工艺制备克拉霉素掩味颗粒。对样品在不同pH溶出介质的溶出度进行分析,通过傅里叶红外光谱、热分析、扫描电镜及X-射线粉末衍射对样品和物理混合物(克拉霉素+卡波姆+邻苯二甲酸羟丙甲基纤维素酯)进行分析,比较两者差异,通过自愿者对掩味效果进行评价。通过该工艺制备的克拉霉素颗粒体外释放度良好,掩味效果优异。制备的克拉霉素掩味颗粒的耐酸性较好,与美国市售制剂相比溶出度相似性较高,并且该工艺能应用于工业化生产。

关键词:克拉霉素;流化床;掩味

中图分类号R944.2       文献标识码A      文章编号0258-32832019--

 

Preparation and Evaluation of Taste Masked Clarithromycin Granules YANG Hui-jie, MI Zhi-yuan, ZHANG Jia*School of Bioengineering and Food, Hubei University of Technology, Wuhan 430064, China, Huaxue Shiji, 2019, 41( )

Abstract: Clarithromycin taste masked granules were prepared and evaluated. Clarithromycin taste masked granules were prepared by combination of fluid-bed coating procedure with palletization. The final products were evaluated by dissolution in different solution, FTIR(KBr), DSC, SEM, X-Ray diffraction, and taste evaluation. The Clarithromycin granules prepared by this process has good dissolution and excellent masking effect. Clarithromycin masking granules have better good resistance and high similarity for the in vitro dissolution compared with the commercial preparations in the United States, and the process can be applied to industrial production.

Key words: Clarithromycin; fluid-bed; taste mask

 

香豆素、萘酰亚胺双母体荧光染料光谱性质研究

刘涛*,李秋婷,潘滋涵,扈显琦

(承德石油高等专科学校 化学工程系,河北 承德  067000)

 

摘要:设计并合成了一例具有香豆素和萘酰亚胺双母体结构的荧光化合物N-(2-乙基己基)-4-7-二乙氨基香豆素-3-炔基)-1,8-萘酰亚胺,通过核磁共振1H谱、13C谱和高分辨质谱确证结构。研究其在不同溶剂以及混合溶剂中的光物理性质,结果表明目标化合物能够一定程度上改善香豆素类和萘酰亚胺类荧光染料波长短的缺陷,最大发射波长达604 nmTHF溶剂中)。并且目标化合物具有非常明显的溶致变色效应,随着溶剂极性的增大,其最大发射波长会发生129 nm的红移(从正己烷到THF),发光强度降低甚至不发光(DMFDMSO等较大极性溶剂中)。通过Lippert-Mataga公式计算得目标化合物分子基态与激发态偶极矩差值(Δμ)大约为16.32D,表明激发态拥有比基态大得多的偶极矩,并对其发射波长随溶剂极性红移的现象进行理论探究。

关键词:香豆素;萘酰亚胺;溶致变色;光谱性质

中图分类号:O621.2       文献标识码:A        文章编号: 0258-32832019--

 

Photophysical Properties of Fluorescent Dye Composed of Coumarine and  Naphthalimide 

LIU Tao*LI Qiu-tingPAN Zi-hanHU Xian-qi (Department of Chemical EngineeringChengde Petroleum CollegeChengde 067000 China), Huaxue Shiji, 2019, 41( )

AbstractA fluorescent compound (CN) constructed of coumarine and naphthalimide was synthesized. The structure was confirmed by 1HNMR, 13CNMR and HRMS. The photophysical properties in different solvents and mixed solvents showed that to an extent, CN could improve the wavelength of coumarine and naphthalimide dyes. For example, it emit maximally at 604 nm in THF. And an obvious slovatochromism was observed. With the increase of solvent polarity, its max emission wavelength emerged 129 nm red shift from hexane to THF. Meanwhile, its fluorescence intensity decreased and even disappeared in greater polar solvents such as DMF, DMSO and so on. By Lippert-Mataga equation, the difference of dipole moments between ground and excited states was 16.32D approximately illustrating that the dipole moment of excited state was much greater than that of ground state. This provided a theoretical explanation for the redshift of the emission wavelength with the increase of solvent polarity.

Key wordscoumarine; naphthalimide; slovatochromism; photophysical properties

 

雌酚酮-17-(靛红取代)腙衍生物的合成及抗肿瘤活性评价

卜明*1a,由丹2,张嵩1b,陈哲1c

(1.齐齐哈尔医学院 a.药学院,b. 基础医学院, c. 医药科学研究院, 黑龙江 齐齐哈尔 161006

2.齐齐哈尔第一医院,黑龙江 齐齐哈尔 161006)

 

摘要:为寻找高效的潜在抗肿瘤药物,设计合成系列雌酚酮衍生物并测定其抗肿瘤活性。以雌酚酮为原料,合成7个雌酚酮-17-(靛红取代)腙衍生物。所有合成化合物都通过MS1HNMR13CNMR结构表征。另外,分别选用人肝癌细胞(HepG2)、人宫颈癌细胞(Hela)和人肺癌细胞(A549)对化合物的抗增殖活性进行评价。结果表明,雌酚酮-17-(5--靛红)腙对HepG2细胞和Hela细胞具有显著抑制活性,IC50值分别为9.46 μmol/L7.30 μmol/L。可进一步拓展取代底物,更深入地探索该类化合物的构-效关系。

关键词:雌酚酮;甾体;甾腙;靛红;抗肿瘤活性

中图分类号:O626      文献标识码:A      文章编号:0258-32832019

 

Synthesis and Antitumor Activity Evaluation of Estrone-17-(iastin)-hydrazone Derivatives BU Ming*1a, YOU Dan2, ZHANG Song1b, CHEN Zhe1c (1a. School of Pharmacy, 1b. Basic Medical Science College, 1c. Research Institute of Medicine & Pharmacy, Qiqihar Medical University, Qiqihar 161006, China; 2 .The First Hospital of Qiqihar, Qiqihar 161006, China), Huaxue Shiji, 2019, 41(8)

AbstractObjective searching for effective potential antitumor drugs, a series of estrone derivatives were designed, synthesized and evaluated for their antitumor activity. Using estrone as staring material, seven estrone derivatives with different isatin side-chain structures had been synthesized, and their structures were characterized by MS, 1HNMR and 13CNMR. The antiproliferative activity of the compounds was evaluated against human liver carcinoma cells (HepG2), human cervical cancer cells (Hela) and human lung cancer cells (A549). The results showed that estrone-17-(5-bromo-istain)-hydrazone displayed significant inhibitory activity against HepG2 and Hela cell lines, IC50 were 9.46 μmol/L and 7.30 μmol/L respectively. The substituents can be further expanded and the structure-activity relationship of these compounds can be further explored.

Key wordsestronesterolhydrazoneisatinantitumor activity

 

水体中酚类化合物测定方法的研究进展

侯博*,张万智,韩永辉,张国龙

(青海省地质矿产测试应用中心,青海 西宁  810000)

 

摘要:酚类化合物作为周围环境水体中的有机污染物,因其严重的理化性质正逐渐影响以及危害着人类的生产与生活。改进和开发更高效、更便捷准确地测定水体中酚类化合物的方法亟不可待,且具有重要意义。测定酚类化合物的传统方法仅局限于可见光分光光度法、紫外分光光度法等。目前,分析工作者将色谱技术应用于水体中酚类的测定,实现了对酚类化合物的准确定性以及定量。从分光光度法和色谱法两个方面详述了酚类化合物在水体中测定方法的研究状况,为以后分析工作者开发新方法提供了重要的理论与实际经验。

关键词:酚类化合物;分光光度法;色谱法

中图分类号O652.1    文献标识码A    文章编号0258-32832019

 

Advances in the Determination of Phenolic Compounds in Water HOU Bo*, ZHANG Wan-zhi, HAN Yong-hui, ZHANG Guo-long (Qinghai Province Geological and Mineral Testing and Application Center, Xining 810000, China), Huaxue Shiji, 2019

Abstact: At present, phenolic compounds as organic pollutants in the surrounding water bodies are gradually affecting and endangering human production and life due to their serious physical and chemical properties. In order to protect human production and life and improve the normal, stable and sustainable development of the surrounding ecological environment, it is unavoidable and important to improve and develop more efficient, more convenient and accurate methods for the determination of phenolic compounds in water. The method for measuring a phenolic compound by a conventional method is limited to visible light spectrophotometry, ultraviolet spectrophotometry, and the like. At present, analysts apply chromatographic techniques to the determination of phenols in water, achieving quasi-determinism and quantification of phenolic compounds. In this paper, the research status of the determination method of phenolic compounds in water is detailed from the aspects of spectrophotometry and chromatography, which provides important theoretical and practical experience for future researchers to develop new methods.

Key words:Phenolic compound; Spectrophotometry; Chromatography

 

QuEChERS-SPE结合超高效液相色谱-质谱/质谱仪测定动物肝脏中的万古霉素和去甲万古霉素残留量

李欣1,马宁宁1,康明芹*2,宋丽丽1,刘洋2,李荣荣2

1.天津中医药大学,天津  3016172.长春海关(原吉林检验检疫局),吉林 长春  130012

 

摘要:建立了QuEChERS-SPE结合超高效液相色谱-质谱/质谱仪(UPLC-/MS/MS)测定动物肝脏中万古霉素和去甲万古霉素残留量的方法。肝脏样品采用0.1%甲酸水-乙腈溶液进行提取, PSA吸附剂和C18吸附剂初步净化,再用Strata-X-C固相萃取柱进行净化,UPLC-/MS/MS正离子模式扫描,多反应监测模式(MRM)测定,外标法定量。结果表明,QuEChERS-SPE双重净化可有效降低肝脏基质中杂质的干扰,万古霉素和去甲万古霉素在5.0100.0 µg/L浓度范围内线性关系良好(r均大于0.999),检出限为2.0 μg/kg,定量限为5.0 μg/kg,加标平均回收率在78.6%90.3%。该方法灵敏度高,准确度好,能满足对动物肝脏中万古霉素和去甲万古霉素定量分析的要求。

关键词QuEChERS;固相萃取;超高效液相色谱-质谱/质谱;万古霉素;去甲万古霉素;肝脏

中图分类号: O657.6    文献标识码: A     文章编号: 0258-32832019

 

Determination of Vancomycin and Norvancomycin Residue in Animal Liver by QuEChERS-SPE with Ultra Performance Liquid Chromatography-tandem Mass Spectrometry LI Xin1MA Ning-ning1KANG Ming-qin*2SONG Li-li1LIU Yang2LI Rong-rong2 (1. Tianjin University of Traditional Chinese MedicineTianjin 301617, China; 2. Changchun Customs (Former Jilin Inspection and Quarantine Bureau), Changchun 130012, China), Huaxue Shiji, 2019

Abstract: To establish a method for the determination of vancomycin and norvancomycin residue in animal liver based on QuEChERS-SPE by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The samples were extracted with mixed solution of 0.1% formic acid and acetonitrile, purified first by PSA and C18, then cleaned with solid phase extraction(Strata-X-C)determined by UPLC-MS/MS with positive electrospray ionization mode and multiple-reaction monitoring (MRM) and quantitatived by external standard method. The results showed that the double purification effectively reduce the matrix interferences in liver. The standard calibration curve showed good linear behavior in the range from 5.0 to 100.0 µg/L and the relative coefficient was more than 0.999. The limit of detection and the limit of quantitation of the method were 2.0 μg /kg and 5.0 μg /kg respectively. The spiked recoveries were 78.6% to 90.3%. The method is sensitive and accurate, which can be used for the demands of quantitative analysis of vancomycin and norvancomycin in animal liver.

Key words: QuEChERS; solid phase extraction; UPLC-MS /MS; vancomycin; norvancomycin; liver

 

桔梗不同器官中多糖的分布与动态积累研究

朱丽丽1,郭宣宣2,张玲*1,曹富3

1.安徽中医药大学 药学院,安徽 合肥  2300122. 亳州职业技术学院 药学院,安徽

亳州  2368003.安庆医药高等专科学校 药学院,安徽 安庆  246052

 

摘要:D-无水葡萄糖为对照品,采用蒽酮-硫酸比色法测定不同生长年限桔梗中总多糖的含量,研究桔梗一年生长过程中不同器官总多糖的分布和动态积累规律。结果表明,D-无水葡萄糖在0.00250.015 mg/mL范围内线性关系良好(r0.9996)。去皮桔梗药材中多糖含量高于不去皮桔梗。去皮桔梗药材中总多糖的含量随着生长年限的延长呈现下降再略上升的趋势,即24年不断降低,至第5年略有上升;不去皮桔梗药材中总多糖含量随着生长年限的增长呈现升升的变化趋势,5年生多糖含量最高。桔梗中多糖主要分布在根部,刚发芽时多糖含量最低,盛花期时多糖含量最高。该研究建立了桔梗中总多糖含量的测定方法,为桔梗资源的综合利用提供了一定的依据。

关键词:桔梗;多糖;器官;分布;动态积累

中图分类号R917    文献标识码A    文章编号0258-32832019

 

Distribution and Dynamic Accumulation of Polysaccharides in Different Parts of Platycodon Grandiflorum ZHU Li-li1, GUO Xuan-xuan2, ZHANG Ling*1, CAO Fu3 (1. School of Pharmacy, Anhui University of Chinese Medicine, Hefei 230012, China; 2. School of Pharmacy, Bozhou Vocational and Technical College, Bozhou 236800, China; 3.School of Pharmacy, Anqing Medical College, Anqing 246052, China), Huaxue Shiji, 2019, 41(8),

Abstract: To determine the content of polysaccharides and to explore the distribution and dynamic accumulation of polysaccharides in Platycodon grandiflorum at various growth ages and in different organs. Through adopting method, the content of total polysaccharide in P. grandiflorum samples at various growth ages and in different organs was determined with glucose as reference control. The glucose contents showed the fine linear relation in the range of 0.0025 0.015 mg/mL, the relevance modulus r=0.9996. The content of polysaccharide in unpeeled Platycodon is significantly lower than peeled polysaccharide. The content of total polysaccharide in the peeled p. grandiflorum decreased and then increased slightly, that is, it decreased continuously in 2 to 4 years, and increased slightly in the fifth year. In the peeled p. grandiflorum, the content of total polysaccharide accumulation was significantly increased and then gradually decreased, increased finally and the 5-year-old is the highest. The polysaccharides in P. grandiflorum are mainly distributed in the roots. The content of polysaccharides is the lowest when germination, and the highest in the flowering stage. This work established a method for determination of total polysaccharide content and determined the optimal harvesting period of P. grandiflorum, which provided a basis for the research and utilization of P.grandiflorum resources.

Key words: Platycodon grandiflorum; different parts; polysaccharid; distribution; dynamic accumulation

 

紫甘蓝花青素() 显色体系测定中药中铁的含量

韩毅丽,贺润丽*,冯玉琦

(山西中医药大学 中药学院,山西 晋中  030619

 

摘要:优化紫甘蓝花青素() 显色体系,利用该体系首次测定中草药中铁的含量。根据在pH 7.28.7中紫甘蓝花青素能与铁() 形成稳定的配合物,该配合物最大吸收波长为632.0 nm,与紫甘蓝花青素的最大吸收波长相差79.0 nm,采用甲醇作为花青素提取剂,以pH9.1825 ℃)的硼砂pH缓冲剂调节pH值,利用紫外-可见分光光度法,测定了不同产地黄芪和款冬花中铁的含量。该显色体系最佳显色时间为30 min,显色剂用量为10.0 mL,测得河北安国、甘肃陇西、山西应县、山西浑源黄芪及贵州大龙款冬花中铁的含量依次为83.781.655.554.9165.5 μg/g。该方法Fe()含量在2 10 μg/mL范围内与吸光度呈良好线性关系,线性相关系数R2 0.9991,加样回收率为99.91% 102.4%,可普遍用于植物中铁的含量测定。

关键词:花青素;铁;显色体系;紫外-可见分光光度法;黄芪;款冬花;含量测定

 

Determination of the contents of Ferrum in Chinese herbal medicine by the color rendering system of Fe() and anthocyanin in red cabbage extract HAN Yi-li, HE Run-li*, FENG Yu-qi (College of traditional Chinese medicine, Shanxi University of Chinese Medicine, Jinzhong  030619, China), huaxue shiji, 41(8),

Abstract: Objective: Optimize the color rendering system of Fe() and anthocyanin in red cabbage extract and this system was used to determine the contents of Ferrum in Chinese herbal medicine for the first time. Methods: Anthocyanin which extracted from the red cabbage could form a stable complex with Fe() in pH 7.2~8.7, the maximum absorption wavelength of the complex is 632.0nm and there is a difference of 79.0nm from the maximum absorption wavelength of anthocyanin. Methanol was used as anthocyanin extraction agent, the buffer solution of borax with pH of 9.18(25) was used to adjust the pH value and the content of Fe in Chinese herbal medicine was determined using this color rendering system by UV spectrophotometry. Results: The optimal color rendering time was 30min of stasis, the dosage of developer is 10.0 mL. By measuring, the content of Fe in Astragalus membranaceus which is from Anguo HebeiLongxi GansuYingxian Shanxi Hunyuan Shanxi and in Tussilago farfara which is from Dalong Guizhou is 83.781.655.554.9165.5μg·g-1 respectively. Conclusion: There was a well linear relationship between absorbance and Fe() of which contents is in the range of 210μg·mL-1, correlation coefficient R2 =0.9991, the optimum recoveries of  99.91%102.4% by addition of the standard solution of Fe in Chinese herbal medicine was obtained. This method is used in the determination of Fe in plants commonly.

Key words: Anthocyanin; Ferrum;mColor rendering system; mUV spectrophotometry; Astragalus membranaceus; Tussilago farfara; Content determination

 

一种戊二醛-壳聚糖非共轭荧光聚合物传感器检测水样中汞离子

张青1,刘春*2, 3,何洪昆2

(1. 重庆市綦江区生态环境监测站,重庆 4014202. 重庆师范大学,化学学院,重庆 4013313. 宜宾学院 过程分析与控制四川省高校重点实验室,四川 宜宾  644000)

 

摘要:开发了一种新型、快速的荧光传感器用于水样品中Hg2+的检测。合成了一种戊二醛-壳聚糖非共轭荧光聚合物(GCPF),在370 nm波长激发下,于455 nm波长处产生荧光。研究发现,汞离子(Hg2+)的存在能使GCPF荧光被猝灭。传感器对Hg2+的检测线性范围是0.8 30 μmol/L,检测限为85 nmol/L。该方法灵敏度高、线性范围宽、成本较低、操作方便、响应迅速(约1 min),对其他金属离子具有很好的选择性。将其应用于实际水样中Hg2+检测时也得到了令人满意的结果。

关键词:戊二醛-壳聚糖非共轭荧光聚合物(GCPF);Hg2+;荧光传感器;水样

中图分类号O655    文献标识码A   文章编号0258-32832019--

 

Fluorescent Sensor for Hg2+ Detection in Water Using Glutaraldehyde Cross-linked Chitosan Polymer Fluorophores ZHANG Qing1, LIU Chun* 2,3 , HE Hong-kun2 (1. Qijiang District Ecology Environmental Monitoring Station, Chongqing 401420, China; 2. College of Chemistry, Chongqing Normal University, Chongqing 401331, China; 3. Key Lab of Process Analysis and Control of Sichuan Universities, Yibin University, Yibin 644000, China), Huaxue Shiji, 2019, 418

Abstract: A novel fast fluorescence sensor using glutaraldehyde non-conjugated chitosan polymer fluorophores (GCPF) is developed for the detection of Hg2+ in water samples. GCPF emits fluorescence at 455 nm with an excitation wavelength of 370 nm. It is found that fluorescence of GCPF can be quenched by Hg2+. The proposed GCPF fluorescent sensor exhibits linear range for Hg2+ detection from 0.8 to 30 μmol/L, the limit of detection (LOD) of 85 nmol/L, with simple operation, wide detection range, fast response (about 1 min) and high sensitivity. The fluorescent sensor is also applied detecting Hg2+ in real water with satisfactory results.

Key words: Glutaraldehyde non-conjugated chitosan polymer fluorophores (GCPF); Hg2+; fluorescent sensor; real water

 

 

2018年无锡地区环境中铅含量的检测和结果分析

龚燕1, 2 孟元华*1, 2 徐志飞1 徐银菊1

1.无锡市疾病预防控制中心,江苏 无锡 214023 2. 江南大学公共卫生研究中心,江苏 无锡 214122

 

摘要:了解无锡地区铅的污染状况,并对污染现状进行评价。在无锡地区采集地表水、空气、土壤、蔬菜样品,测定其铅的浓度,通过单因子污染指数法和内梅罗综合污染指数法进行综合评价。通过对49份空气、7份土壤、49份地表水、28份蔬菜共计133份样品铅浓度的测定,发现检测的所有样品中的铅浓度都低于参考标准,土壤、空气和蔬菜的单因子污染指数都小于1,内罗梅污染指数都小于0.7,其中PN空气最大。结论 可以认为无锡地区目前未受到铅污染,但相比较而言铅对空气的影响比对土壤和蔬菜的影响要大。

关键词:铅;空气;土壤;水;蔬菜

中图分类号        文献标识码A     文章编号0258-32832019--

 

Detection and Result Analysis of Lead Content in Wuxi Area in 2018 GONG Yan1, 2, MENG Yuan-hua*1, 2, XU Zhi-fei1, XU Yin-ju1(1.Wuxi Center for Disease Control and Prevention, Wuxi 214023, China2. Public Health Research Center of Jiangnan University, Wuxi 214122, China), Huaxue Shiji, 2019, 41(8),

Abstract: To understand the pollution status of lead in Wuxi area and evaluate the pollution status. Surface water, air, soil and vegetable samples were collected in Wuxi area, and the concentration of lead was determined. The comprehensive evaluation was carried out by single factor pollution index method and menero comprehensive pollution index method. Through the determination of lead concentrations in 49 samples of air, 7 soils , 49 surface waters and 28 samples of vegetables in a total of 133 samples, it was found that the concentrations of lead in all samples tested were lower than the reference standard, and the Piaverage single factor pollution index for soil ,air and vegetables was less than 1. Neiluomei pollution index was less than 0.7, PN air is the biggest. It can be concluded that there is no lead pollution in Wuxi, but the effect of lead on air is greater than that on soil and vegetables.
Key words: lead
airsoilwatervegetables

 

不同离子对漆酶酶活的影响

付林俊a, b,刘海a, b,张晓晴a, b,张淑琴a, b,任大军*a, b

(武汉科技大学 a. 资源与环境工程学院,b. 冶金矿产资源高效利用与造块湖北省重点实验室,湖北 武汉  430081

摘要:设置一系列不同种类、不同浓度的离子溶液,探究其对漆酶酶活的影响。结果表明,阳离子中Fe2+Fe3+Cu2+对漆酶的抑制作用显著,并分析了离子浓度对漆酶的影响以及不同离子对漆酶的抑制机理。分析表明Fe2+可能是通过与2,2-联氮-(3-乙基-苯并噻唑-6-磺酸)二铵盐(ABTS)自由基结合影响漆酶酶活的,Fe3+可能是通过影响或置换漆酶中的部分铜离子影响漆酶活性的,Cu2+可能是通过与漆酶中的酸性氨基酸残基作用或通过影响漆酶的电荷平衡影响漆酶活性的。在常见的阴离子溶液中,CO32-抑制漆酶酶活,NO3-SO42-对漆酶有一定程度的激活,Cl-轻微抑制漆酶酶活。分析表明阴离子的抑制作用可能是通过与底物分子竞争Ⅱ铜中的某一个位点来实现的,激活作用可能是通过修饰漆酶氨基酸残基来实现的。还研究了不同类型离子的复配,结果显示不同类型的复配对漆酶的影响方式也不同,但主要是通过作用于漆酶活性位点来影响酶活的。

关键词:漆酶;抑制作用;激活作用;离子

中图分类号:Q936    文献标识码:A    文章编号:0258-3283(2019)

 

Effect of Different Ions on Laccase Enzyme Activity FU Lin-juna,b, LIU Haia,b, ZHANG Xiao-qinga,b, ZHANG Shu-qina,b, REN Da-jun*a,b (a. School of Resource and Environment Engineering, b. Key Laboratory of High-efficiency Utilization and Agglomeration of Metallurgical Mineral Resources in Hubei Province, Wuhan University of Science and Technology , Wuhan 430081, China, Huaxue Shiji, 2019, 41(8)

Abstract: This work sets up a series of different types and different concentrations of ionic solutions to explore their effects on laccase enzyme activity. The inhibitory effect of Fe2+, Fe3+ and Cu2+ on laccase was significant, and the effect of ion concentration on laccase was analyzed, and the inhibition mechanism of these ions was analyzed. The analysis indicated that Fe2+ may affect the laccase activity by binding to ABTS free radicals, Fe3+ may affect the laccase activity by affecting or replacing a portion of the copper ions of laccase, Cu2+ may affect laccase activity by acting with acidic amino acid residues in the laccase or by affecting the charge balance of the laccase. In common anion solutions, CO32- inhibits laccase activity, NO3- and SO42- have a certain degree of activation of laccase, and Cl- slightly inhibits laccase activity; analysis indicates that anion inhibition may through substrate The molecule competes for a site in II copper, and the activation may be achieved by modifying the laccase amino acid residues. The compounding of different types of ions was also investigated. The results showed that different types of complex affected laccases in different ways, but mainly affected the enzyme activity by acting on the laccase active site.

Key words: laccase; inhibitive effect; active effect; ions

 

B-降胆甾苯并咪唑化合物对金属离子识别性能研究

吴玉兰a, b, c,刘晓兰a, b ,c,展军颜a, b, c,黄晓彤a, b, c,黄燕敏a, b, c,甘春芳*a, b, c

(南宁师范大学 a. 北部湾环境演变与资源利用教育部重点实验室,b. 广西天然高分子化学与物理重点实验室,c. 化学与材料学院,广西 南宁  530001

 

摘要:苯并咪唑是优良的离子探针活性基团,以3种不同取代基结构的B-降胆甾苯并咪唑化合物作为金属离子受体,采用紫外光谱法和荧光光谱法对12种不同的金属离子(Co2+K+Na+Li+Pb2+Ca2+Zn2+Sr2+Ni2+Ag+Hg2+Cu2+)进行检测,结果表明这3种化合物对Cu2+离子具有高度的选择性,抗干扰能力好,可作为选择性光学传感器,检出限分别为7.31×10-8 mol/L7.99×10-8 mol/L5.85×10-8 mol/L,采用Job法测试,3种化合物与Cu2+的络合比为1:1

关键词:B-降胆甾苯并咪唑化合物;Cu2+;荧光传感器;金属离子识别

中图分类号O626.4    文献标识码A     文章编号0258-32822019

 

Recognition of Metal Ions via B-Norcholesteryl Benzimidazole Compounds WU Yu-lan a, b, c, LIU Xiao-lan a, b, c, ZHAN Jun-yan a, b, c HUANG Xiao-tong a, b, c, HUANG Yan-min a, b, c, GAN Chun-fang* a, b, c (a. Key Laboratory of Environment Change and Resource Use in Beibu Gulf, b. Guangxi Key Laboratory of Natural Polymer Chemistry and Physics, c. College of Chemistry and Materials, Nanning Normal University, Nanning 530001, China), Huaxue Shiji, 2019, 41(8),

Abstract: Benzimidazole is an excellent active group of ionic probe. Using three kinds of different groups substituted B-norcholesteryl benzimidazole compounds as metal ion acceptors, the recognition abilities towards various metal ions (Co2+, K+, Na+, Li+, Pb2+, Ca2+, Zn2+, Sr2+ Ni2+, Ag+, Hg2+, Cu2+) have been investigated via ultraviolet spectroscopy and fluorescence. The compounds showed high selectivity and good anti-interference ability to Cu2+, so it may be used as selective optical sensor. The detection limit was down to 7.31×10-8 mol/L7.99×10-8 mol/L and 5.85×10-8 mol/L respectively. The stoichiometric ratio of the complex between Cu2+ and compound were determined as 1:1 by Job method.

Key words:B-norcholesteryl benzimidazole; Cu2+; fluorescence sensor; metal ions recognition

 

新型多取代噁唑类化合物的合成

任传清*a, b,季建伟a, b,张强a, b,刘杰b

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

 

摘要:噁唑类杂环化合物具有广泛的生物活性,如杀菌、杀虫、抗植物病毒、除草等。目前,对该类化合物的合成与生物活性的研究是合成化学研究热点之一。由α-乙酰基环丙烷类化合物和异氰基乙酸乙酯在Cu2O催化下合成了一系列新型多取代噁唑类化合物,通过核磁共振、质谱分析对所得化合物进行了表征,并对该反应机理进行了探讨。该反应方法操作简单,在较温和的条件下合成了多取代噁唑类化合物。

关键词:杂环化合物;噁唑;催化;异氰基乙酸乙酯

中图分类号O626.2    文献标识码A    文章编号0258-32832019

 

Synthesis of Novel Polysubstituted Oxazole Compounds REN Chuan-qing*a, b, JI Jian-weia, b, ZHANG Qianga, b, LIU Jieb(a. Shaanxi Key laboratory of Catalysis, b. School of Chemical & Environmental Science, Shaanxi University of Technology, Hanzhong 723000, China), Huaxue Shiji, 2019, 41(8)

Abstract: Oxazdiazole derivatives contained wide biology activity in insecticidal, fungicidal, antiviral and herbicidal activities. At present, the research on synthesis and biological activity of these compounds are still one of the hot topics in synthetic chemistry. The synthesis of novel polysubstituted oxazole compounds were developed from α-acetyl cyclopropanes and isocyanoacetic acid ethyl ester, under the Cu2O catalyst, and the product was confirmed by NMR, IR, MS and elements analysis. Moreover, a mechanism for the reaction was proposed. The polysubstituted oxazole compounds were synthesized under mild conditions with simple process.

Key words: heterocycles; oxazole; catalysis; isocyanoacetic acid ethyl ester

 

 

5-甲氧基-2-(苯乙炔基)苯甲醛的合成


朱周静*1,2,刘斌1,2,陈革豫1,2,田航周1,2

1.陕西国际商贸学院 医药学院 陕西 西安  712046; 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-羟基苯甲醛为原料,经过羟基甲基化反应、Sonogashira偶联反应得到5-甲氧基-2-(苯乙炔基)苯甲醛。产物及中间体结构经1HNMR13CNMRESI-MS确证。并对Sonogashira反应条件进行研究,确定最佳反应条件为:n2--5-甲氧基苯甲醛)∶n(苯乙炔)= 11.2,催化剂Pd(PPh3)2Cl2用量为n (Pd(PPh3)2Cl2)n (2--5-甲氧基苯甲醛) = 0.051PPh3用量为n (PPh3)n (2--5-甲氧基苯甲醛) = 0.31CuI用量为n (CuI)n (2--5-甲氧基苯甲醛) = 0.11,反应溶剂为DMFTEA的混合溶剂(VDMF)∶VTEA))= 11,反应温度80 ℃,反应时间10 h,产物收率为74.5 %。按照最佳反应条件对6种取代苯乙炔底物进行拓展,均得到较高收率的5-甲氧基-2-(取代苯乙炔基)苯甲醛产物。

关键词:2-苯乙炔基苯甲醛;Sonogashira偶联反应;合成

中图分类号:TQ463        文献标识码:A            文章编号:0258-32832019

 

Synthesis of 5-Methoxy-2-(phenylethynyl)benzaldehyde ZHU Zhou-jing*1,2, LIU Bin1,2, CHEN Ge-yu1,2, TIAN Hang-zhou1,2 (1. School of Pharmacy, Shaanxi Institute of International Trade & Commerce, Xi’an 712046, China; 2. Collaborative Innovation Center of Green Manufacturing Technology for Traditional Chinese Medicine in Shaanxi Province, Xi’an 712046, China), Huaxue Shiji, 2019, 41(8)

Abstract:5-Methoxy-2-(phenylethynyl)benzaldehyde was synthesized from 2-bromo-5-hydroxybenzaldehyde via a-two step reaction. Involving hydroxymethylation reaction and Sonogashira coupling reaction. The structure of the products and intermediate were confirmed by 1HNMR, 13CNMR and ESI-MS. The optimal reaction conditions of Sonogashira coupling reaction were also investigated. Target compound was obtained in a yield of 74.5 % with the mole ratio of n(2-bromo-5-methoxybenzaldehyde) : n(phenyl acetylene) = 1 : 1.2. The amount of Pd(PPh3)2Cl2 is n (Pd(PPh3)2Cl2) : n (2-bromo-5-methoxybenzaldehyde) = 0.05 : 1. The amount of PPh3 is n (PPh3) :n (2-bromo-5-methoxybenzaldehyde) = 0.3 : 1. The amount of CuI is n (CuI) :n (2-bromo-5-methoxybenzaldehyde) = 0.1 : 1,  DMF and TEA(V(DMF)∶V(TEA))= 1∶1)as co-solvent, reacted at 80 ℃for 10 h. Six types of 5-methoxy-2-(substituted ethynyl) benzaldehydes were synthesized with high yield by this synthetic method.

Key words2-(phenylethynyl)benzaldehyde; Sonogashira coupling reaction; synthesis

 

1-(1-乙基丙基)-5,6-二甲基-7-硝基-1H-苯并咪唑的合成

龙丹1,2,吴清梅1,2,赵庆平1,2,周志旭* 1, 2

(1.贵州大学 药学院,贵州 贵阳  5500252.贵州省合成药物工程实验室,贵州 贵阳  550025)

 

摘要:苯并咪唑衍生物是一类具有重要应用价值的活性物质及药物合成中间体,其广泛应用于医药化工等领域。1-(1-乙基丙基)-5,6-二甲基-7-硝基-1H-苯并咪唑的合成方法暂无文献报道。以廉价易得的3,4-二甲基苯酚为起始原料,经硝化、甲酯化、取代、还原、环化5步反应合成目标产物,目标化合物的结构经1HNMR13CNMRMS确证。该方法成本较低、反应所需条件温和可控、后处理操作安全简单且收率较高,可用于工业生产。

关键词:1-(1-乙基丙基)-5,6-二甲基-7-硝基-1H-苯并咪唑;3,4-二甲基苯酚;合成

中图分类号:O626. 13       文献标识码A         文章编号:0258-32832019

 

Synthesis of 1-(1-ethylpropyl)-5,6-dimethyl-7-nitro-1H-benzimidazole LONG Dan1,2, WU Qing-mei1, 2 ,ZHAO Qing-ping1, 2, ZHOU Zhi-xu*1, 2 (1. School of Pharmaceutical Sciences, Guizhou University, Guiyang 550025, China; 2. Guizhou Engineering Laboratory for Synthetic Drugs, Guiyang 550025, China), Huaxue Shiji, 2019, 418

AbstractBenzimidazole derivatives are a class of active substances and drug synthesis intermediates with important utilization value, and are widely used in the fields of medicine and chemical industry. The synthesis method of 1-(1-ethylpropyl)-5,6-dimethyl-7-nitro-1H-benzimidazole has not been reported in the literature. This study is inexpensive and easy to obtain 3,4-dimethylphenol as a raw material, and the target product is synthesized by five steps of nitration, methylation, substitution, reduction and cyclization. The structure of the target compound was confirmed by 1H NMR, 13C NMR and MS. The method reported in this study has lower cost, mild and controllable reaction conditions, safe and simple post-treatment operation and high yield. The synthetic route is a synthetic route feasible in industrial production.

Key words: 1-(1-ethylpropyl)-5,6-dimethyl-7-nitro-1H-benzimidazole; 3,4-dimethylphenol; synthesis

 

沙坦联苯的高效合成

侯梦圆1,杨建华2,杨兰1,刘雷芳1,姜海斌1,李长旭1,李莹莹1,段璐瑶1,李文波*1

1. 德州学院 化学化工学院, 山东 德州 253023; 2. 山东省德州市第一中学 化学教研组, 山东 德州 253023

 

摘要:沙坦类药物是临床上备受关注的一类新型抗高血压药物。沙坦联苯是沙坦类药物的关键中间体。以邻氯苯氰和对甲基苯硼酸为原料,通过对反应溶剂、反应温度、反应时间、催化剂、碱等关键条件的优化,开发了一个合成沙坦联苯的催化体系。此催化体系以PEG400为反应介质,以Pd(OAc)2为催化剂,以K2CO3Na2CO3K3PO4为碱,在60 ℃下反应24 h,沙坦联苯的产率可达99%。该体系是一个绿色、简单、高效合成沙坦联苯的催化体系,为沙坦联苯的合成提供了一个有效的新方法。

关键词:沙坦联苯;合成;邻氯苯氰;对甲基苯硼酸

中图分类号O625.13         文献标识码:A          文章编号:0258-3283(2019)

 

Highly Efficient Synthetic Method for Sartan Biphenyl HOU Meng-yuan1, YANG Jian-hua 2, YANG Lan 1, LIU Lei-fang 1, JIANG Hai-bin 1, LI Chang-xu 1, LI Ying-ying 1, DUAN Lu-yao 1, LI Wen-bo*1 (1. College of Chemistry and Chemical Engineering, Dezhou University, Dezhou 253023, China; 2. Chemical Teaching and Research Group, Dezhou No. 1 Middle School, Dezhou 253023, China), Huaxue Shiji, 2019, 41(8)

Abstract: Sartan biphenyl is a key intermediate for sartan drugs. To develop a new and efficient synthetic method for sartan biphenyl, the effects of solvent, reaction time, catalyst and base on the reaction of o-chlorobenzonitrile and p-tolylboronic acid was investigated. By optimizing above reaction conditions, a green, simple and highly efficient catalytic system for the synthesis of sartan biphenyl was developed. Using PEG400 as solvents and Pd(OAc)2 as catalysts, sartan biphenyl could be obtained in 99% yield in the presence of K2CO3, Na2CO3or K3PO4 at 60oC for 24h.

Key words: sartan biphenyl; synthesis; o-chlorobenzonitrile; p-tolylboronic acid

 

瑞戈非尼有关物质的合成

李晓鹏1,钟文辉*2,孙元培2,贾小鹏2,池晓雷2,刘瑞鹏2,孙文涛2

1.河北省食品药品审评认证中心,河北 石家庄  050035

2.石药集团中奇制药技术(石家庄)有限公司,河北 石家庄  050035

 

摘要:为了控制瑞戈非尼产品质量,以瑞戈非尼合成路线为基础,制备4种有关物质:4-{2-{3-[4--3-(三氟甲基)苯基]脲基}-3-氟苯氧基}-N-甲基吡啶甲酰胺、4-{3--4-{[2-(甲基羰基)吡啶-4-]氨基}苯氧基}-N-甲基吡啶甲酰胺、4-{4-{3-[4--3-(三氟甲基)苯基]脲基}-3-{4-{3-[4--3-(三氟甲基)苯基]脲基}-3-氟苯氧基}苯氧基}-N-甲基吡啶甲酰胺和4-{4-{3-[4--3-(三氟甲基)苯基]脲基}-3-{4-{3-[4--3-(三氟甲基)苯基]脲基}-3-{4-{3-[4--3-(三氟甲基)苯基]脲基}-3-氟苯氧基}苯氧基}苯氧基}-N-甲基吡啶甲酰胺,并通过1HNMRMS确证结构,纯度经HPLC检测均在98%以上,可作为瑞戈非尼质量控制的对照品。

关键词:瑞戈非尼;有关物质;合成

中图分类号R914.5                      文献标识码A                 文章编号:0258-3283(2019)

 

Synthesis of Related Substances of Regorafenib LI Xiao-peng1, ZHONG Wen-hui*2, SUN Yuan-pei2JIA Xiao-peng2CHI Xiao-pei2LIU Rui-peng2SUN Wen-tao21.Hebei Center for Food and Drug Evaluation&Certification, Shijiazhuang 050035,China; 2.CSPC Zhongqi Pharmaceutical TechnologySJZCo.,Ltd., Shijiazhuang 050035,China),Huaxue Shiji2019,418

Abstract: To control the quality of regorafenib, four related substances were studied. They were prepared based on the synthetic route of regorafenib. These substances were 4-{2-{3-[4-chloro-3- (trifluoromethyl) phenyl)] ureido}-3-fluorophenoxy}-N-methy-l picolinamide (I), 4-{3-fluoro-4- {[2- (methylcarbamoyl)pyridin-4-yl] amino} phenoxy]-N-methylpic-olinamide (II), 4-{4-{3-[4- chloro-3-(trifluoromethyl) phenyl]ureido}-3-{4-{3- [4-chloro- 3-(trifluorom-ethyl)phenyl]ureido}-3-fluorophenoxy}phenoxy}-N-methylpicolinamide(III)and4-{4-{3-[4-chloro- 3-(trifluoromethyl)phenyl]ureido}-3-{4-{3-[4-chloro-3-(trifluoromethyl)phenyl]ureido}-3-{4-{3-[4-chloro-3- (trifluoromethyl)phenyl]ureido}-3-fluorophenoxy}phenoxy}phenoxy}-N-methylpicolinamide(IV). Their structures were confirmed by 1HNMR and MS and their purities were over 98% by the detection of HPLC. They can be used as the reference substances in the quality control of regorafenib.

Key words: regorafenib; related substance; synthesis

 

氟菌唑代谢物FM-6-1的合成与表征

韩世磊,郝明锋,徐浩,张磊*

(天津阿尔塔科技有限公司,天津  300457

 

摘要氟菌唑代谢物4--α, α, α -三氟-N-(1-氨基-2-丙氧基亚乙基)--甲苯胺(FM-6-1)的合成方法目前尚无文献报道,以2-氨基-5-氯三氟甲苯为原料,经氯化、缩合、氯化、胺化四步反应合成目标产物,四步反应总收率达60%。目标产物经1HNMR19FNMR13CNMRHRMS表征确认。该路线具有原料廉价易得、操作简单、后处理方便、收率较高等优点,通过高效液相色谱确认化学纯度达到99%以上,可以作为农残检测标准品用于食品安全检测和环境监测领域。

关键词:氟菌唑代谢物FM-6-1;标准品;农残检测         

中图分类号:TQ460.3              文献标识码:A             文章编号:0258-32832019

 

Synthesis and Characterization of Triflumizole Metabolite FM-6-1 HAN Shi-lei, HAO Ming-feng, XU Hao, ZHANG Lei* (Alta Scientific Co., Ltd., Tianjin 300457, China), Huaxue Shiji, 2019, 41(8

AbstractThe synthesis of triflumizole metabolite 4-chloro-α,α,α-trifluoro-N-(1-amino-2- propoxyethylidene)-o-toluidine (FM-6-1) hasn't been reported in the literature up to dateThis work disclosed its synthesis using 4-chloro-2-(trifluoromethyl)aniline as raw material in four steps, acid chlorination, amine acylation, amide chlorination, and amination, in 60% overall yield. The target product was confirmed by 1HNMR, 19FNMR, 13CNMR and HRMS. The synthetic route has the advantages of economic raw materials, simple operation, easy post-processing and high yield. In addition, the chemical purity was higher than 99% based on HPLC, which can be used as reference material for pesticide residue screening and testing for food safety and environmental monitoring industries.

Key wordstriflumizole metabolite FM-6-1; reference material; pesticide residue test

 

2-氨基-3--6-氯吡啶的合成工艺研究

秦玉梅a, b,朱雄a, b,龙丹a, b,乐意a, b,赵春深*a, b, c

(贵州大学 a.药学院,b.贵州省合成药物工程实验室,c.贵州发酵工程与生物制药重点实验室,贵州 贵阳  550025

 

摘要:标题化合物是一种重要的精细化工及医药中间体,可用于制备神经原纤维缠结显像剂、IRAK-4抑制剂及治疗退行性和炎症性疾病的化合物。对标题化合物的合成工艺路线进行了改进,以2-氨基-6-氯吡啶为起始原料,经氨基保护、溴代、脱保护基三步反应得到标题化合物,总收率为65.13 %。其结构经1HNMRMS确证。改进后的工艺具有原料成本低且商业可得、实验条件温和易控、操作及纯化过程简单、标题化合物纯度及收率较高的优点,可满足工业化生产需求。

关键词:2-氨基-3--6-氯吡啶;氨基保护;合成;工艺探讨

中图分类号:O626.1    文献标识码:A     文章编号:0258-3283(2019)

 

Study on the Synthesis of 2-Amino-3-bromo-6-chloropyridine QIN Yu-meia, b, ZHU Xiong a, b, LONG Dan a, b, LE Yi a, b, ZHAO Chun-shen* a, b, c (a. School of Pharmaceutical Sciences, b. Guizhou Engineering Laboratory for Synthetic Drugs, c. Key Laboratory of Guizhou for Fermentation Engineering and Biomedicine, Guizhou University, Guiyang 550025, China), Huaxue Shiji, 2019

Abstract: 2-Amino-3-bromo-6-chloropyridine is an important intermediate in fine chemicals and pharmaceuticals. In this work, the synthesis route of 2-amino-3-bromo-6-chloropyridine was improved. 2-Amino-6-chloropyridine was used as the starting material, and the target compound was synthesized by three steps of amino-protection, bromination and deprotection. The title compound was confirmed by 1H NMR and MS. The improved process has the advantages of low cost and commercially easy availability of raw materials, mild and easily controlled experiment conditions, simple operation and purification process, high purity and high yield of target products, and can meet industrial production demand. The total yield was 65.13 %.

Key words: 2-amino-3-bromo-6-chloropyridine; amino-protection; synthesis; process discussion

 

编辑MCM