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《化学试剂》2018年第11期中英文摘要

三氟乙亚胺酰卤合成2-三氟甲基喹啉的应用进展

李珊*,凌绍明,游歌云,梁俭,蒙君荣,刘真珍

 

(百色学院 化学与环境工程学院 桂西区域生态环境分析与污染控制重点实验室,广西 百色 533000)

摘要2-三氟甲基喹啉具有显著的药理活性而广泛应用于医药研发。直接氟化法制备2-三氟甲基喹啉缺乏普遍性及实用性,采用含氟砌块法可以实现含氟基团的精准定位及目标化合物的大剂量合成。N-芳基三氟乙亚胺酰卤是一种重要的含氟砌块,因其活泼的化学性质而广泛应用于含氟含氮杂环化合物的合成。综述了近年来以N-芳基三氟乙亚胺酰卤及其衍生物如氨基烯基酮、炔基亚胺等为原料合成2-三氟甲基喹啉的研究进展概况,系统叙述了每种方法的研究过程及可能的反应机理,并对每种方法的优势及缺点进行了简单的论述。最后,结合当前有机合成的发展趋势对进一步发展2-三氟甲基喹啉的合成方法进行了展望。

关键词2-三氟甲基喹啉;含氟砌块;N-芳基三氟乙亚胺酰卤;氨基烯酮;炔基亚胺

中图分类号:O627.7   文献标识码:A   文章编号: 0258-3283(2018)11--

 

Application of Trifluoroacetimidoyl Halide in Synthesis of 2-Trifluoromethyl Quinolines LI Shan*, LING Shao-ming, YOU Ge-yun, LIANG Jian, MENG Jun-rong, LIU Zhen-zhen (Key Laboratory of Regional Ecological Environment Analysis and Pollution Control of West Guangxi, College of Chemistry and Environment Engineering, Baise University, Baise 533000, China), Huaxue Shiji, 2018, 40(11),

AbstractThe skeleton of 2-trifluoromethyl quninolines is omnipresent in pharmaceuticals for its remarkable pharmacological activity. Varity of fluorination methods which introduce a trifluoromethyl into quninolines directly were developed but still lack generality and practicality. In that case, the application of fluorinated building block to construct quinolines with the trifluoromethyl at the special location and in a large scale is a good alternative. N-aryl trifluoroacetimidoyl halide is an important trifluoromethylated building block, and is used in synthesis of fluorinated azaaromatics widely for its lively chemical activity. In this paper, the recent progress in synthesis of 2-trifluoromethyl quinolines from N-aryl trifluoroacetimidoyl halide and its derivatives such as enaminoketone, alkynyl imine was summarized. The research progress and mechanism of each one of methodologies were described in details, and a comment about the merits and demerits was carried out. In the context of the trends of organic synthesis, an expectation for synthesizing 2-trifluoromethyl quinolines in future was given at last.

Key words: 2-trifluoromethyl quninolines; fluorinated building block; N-aryl trifluoroacetimidoyl halide; enaminoketone; alkynyl imine

 

两种新型吡哆醛异烟酰腙氧钒(IV)配合物的合成及抗肿瘤活性研究

付强强1,张咏莉2,唐敬1,陆家政*1

(广东药科大学 1.药学院,2.基础学院,广州  510006

 

摘要:设计合成了两种含吡哆醛异烟酰腙Schiff碱配体的新型氧钒(IV)配合物[VO(PIH)(FPIP)]1)(PIH=吡哆醛异烟酰腙,FPIP=2-4-氟苯基)咪唑[4,5-f][1,10]菲啰啉)和[VO(PIH)(ClPIP)]2)(ClPIP=2-4-氯苯基)咪唑[4,5-f][1,10]菲啰啉),通过元素分析、IRESI-MS1HNMR等方法表征其结构。采用MTT法检测配合物对人肝癌细胞株(HepG2)、人肺癌细胞株(A549)及人宫颈癌细胞株(Hela)的抑制作用。结果显示,这两种配合物对HepG2A549Hela细胞的生长均具有较强的抑制作用,其中对Hela细胞的抑制作用最明显。此外,运用流式细胞术和荧光显微镜对抑制机理进行初步探讨。实验表明,这两种配合物都可诱导肿瘤细胞发生凋亡,阻滞肿瘤细胞分裂周期均停滞在G0/G1期。这两种配合物都使肿瘤细胞的活性氧水平升高,线粒体膜电位降低,这提示这些配合物可能是通过ROS介导的,并伴随着线粒体功能障碍途径诱导细胞发生凋亡。

关键词:吡哆醛异烟酰腙;氧钒配合物;抗肿瘤;细胞凋亡

中图分类号:R914.3    文献标识码:A      文章编号:0258-32832018

 

Synthesis and  Antitumor Activity of Two novel Oxovanadium(IV) Complexes of Schiff Base and pyridoxal isonicotinoyl hydrazone FU Qiang-qiang1, ZHANG Yong-li2, TANG Jing1, LU Jia-zheng*1 (1.School of Pharmacy, 2.School of Basic Courses, Guangdong Pharmaceutical University, Guangdong 510006, China), Huaxue Shiji, 2018, 40 (11),

AbstractTwo novel oxovanadiumIV complexes [VO(PIH)(FPIP)]1)(PIH=pyridoxal isonicotinoyl hydrazoneFPIP=2-(4-fluorine phenyl) imidazole [4,5-f][1,10] phenanthroline and [VO(PIH)(ClPIP)]2)(ClPIP=2-4-Chlorine phenylimidazole [4,5-f][1,10] phenanthroline containing Schiff base ligands containing pyridoxal isonicotinoyl hydrazone were synthesized and characterized by elemental analysis, IR, ESI-MS and 1HNMR. The inhibitory effect of complexes on human hepatocellular carcinoma cell line (HepG2), human lung cancer cell line (A549) and human cervical cancer cell line (Hela) was detected by MTT assay. The results showed that these two complexes had strong inhibitory effects on the growth of HepG2, A549 and Hela cells, of which Hela cells had the most significant inhibitory effect. In addition, the inhibitory mechanism was preliminary investigated by flow cytometry and fluorescence microscopy. Experiments show that these two complexes can induce apoptosis of tumor cells, blocking the cell cycle of tumor cells are arrested in the G0/G1 phase. All these two complexes increased the reactive oxygen species and decreased mitochondrial membrane potential in tumor cells, suggesting that these complexes may be mediated by ROS and apoptosis was induced along with mitochondrial dysfunction pathway.

Key wordspyridoxal isonicotinoyl hydrazone; oxovanadium complexes; anti-tumor; apoptosis

 

双核Pd-NHC络合物的合成及其催化Heck偶联反应

马学林,张骁勇,段丽萍*

(包头师范学院 化学学院 材料物理与化学重点实验室, 内蒙古 包头  014030

 

摘要:1, 4–二溴甲基苯和1,2,4-1H-三氮唑合成N-取代苄基三氮唑盐,通过PdCl3N-取代苄基三氮唑盐与吡啶耦合,合成了一种新型苄基型双核Pd-NHCPd-NHC)催化剂。产物通过IR1HNMR13CNMR和元素分析等进行了表征。综合考察了催化剂对Heck偶联反应的催化性能。结果表明,这种新型苄基型双核Pd-NHC催化剂对Heck偶联反应表现出较高的催化产率和选择性。最佳工艺条件为:摩尔分数0.5% Pd-NHC催化剂,4 mL DMF溶剂,3 mmol K3PO4碱性介质,温度控制在100 ℃,反应时间为4 h。催化产率可达89%,顺反异构选择性可控制在17:1

关键词:双核氮杂环卡宾; Pd-NHC催化剂; Heck偶联反应

中图分类号:O621.2          文献标识码: A     文章编号:0258-32832018

 

Synthesis of Binuclear Pd-NHC Complex and Catalysted for Heck Coupling Reaction MA Xue-lin, Zhang Xiao-yong, Duan Li-ping* (Key Laboratory of Materials and Physical Chemistry, department of Chemistry, Baotou Normal College, Baotou 014030, China), Huaxue Shiji, 2018, 40(11),

Abstract The N-substituted benzyl triazole salt was synthesized with 1,4-methyl benzene and 1,2,4-1H-triazole. A new catalyst of N-Heterocyclic carbene (NHC) binuclear Pa-complexes has been successfully prepared by Coupling-ligand with PdCl3, N-substituted benzyl triazole salt and pyridine in good yields. The products were characterized by means of IR, 1HNMR, 13CNMR and elemental analysis. The catalyst was investigated comprehensively which was applied to Heck coupling reaction. The results show that the new Pd-NHC catalyst has higher catalytic yield and selectivity for Heck coupling reaction. The best process: 0.5% mmol the amount of Pd-NHC catalyst, 4mL DMF, 3mmol K3PO4, 100 , reaction for 4 h, the catalytic yield is up to 89%, and the cis and trans isomerization can be controlled in 17:1.

Key words: Binuclear N-heterocyclic carbene; Pa-NHC catalyst; Heck coupling reaction

 

基于抗肿瘤活性的含氮取代青蒿醚类衍生物的设计与合成

刘涛1曾昌广2周玥1钟杭*1

(1.贵州大学 药学院,贵州 贵阳 550025

2.德阳市公安局刑事侦查支队技术科,四川 德阳 618000)

摘要:以二氢青蒿素为先导化合物,进行结构修饰以提高青蒿素类化合物的抗肿瘤活性,经三氟乙酸酯法合成含氮取代的青蒿醚类衍生物。结合Mitsunobu反应通过HPLC法考察C-10位的立体选择性。并通过MTT法测试新化合物对乳腺癌细胞的生长抑制活性。合成14个未见文献报道的10β-型胺取代青蒿素类化合物,新化合物活性均较DHA显著提高,且对耐药乳腺癌表现出选择性抑制作用。

关键词:含氮取代青蒿醚类衍生物;乳腺癌;生长抑制活性

中图分类号O622.31   文献标识码:A   文章编号:0258-3283(2018)11--

 

Design and Synthesis of N-contained Substituting Artemisinin Ether Derivatives Based on Their Anti-tumor Effects LIU Tao1, ZENG Chang-guang2, ZHOU Yue1, ZHONG Hang*1 (1.School of pharmaceutical science, Guizhou University, Guiyang 550025, China; 2.Technical department of criminal investigation branch, Deyang police office, Deyang 618000, China) Huaxue Shiji, 2018, 40(11),

AbstractAs a lead compound, dihydroartemisinin was structurally modified for enhanced antitumor effects of artemisinins. A trifluoroacetate method was used to synthesis of N-contained substituting artemisinin ether derivatives, then the C-10 stereoselectivities of artemisinin ether was studied by HPLC, combined with Mitsunobu reaction. Finally, antitumor effects of newly synthetic compounds were tested in breast cancer cells, using a MTT method. Fourteen previously unreported 10β-artemisinin ether derivatives were synthesized herein, novel compounds exhibited improve inhibitory activities compared with DHA, as well as selective effects towards drug resistant breast cancer.

Key words: N-contained substituting artemisinin ether derivatives; breast cancer; antiproliferative effects

 

一个新的双核含铜配合物[Cu2(bbbm)2(SCN)4(CH3OH)2]

的合成及晶体结构和性能研究

王利平,刘艳丽,李会娜,李坤,周晓莉*

(郑州工程技术学院 化工食品学院,河南 郑州  450044

 

摘要:1,1′-(1,4-丁基)--(1-H-苯并咪唑)为柔性双齿配体,与金属Cu(II)离子配位,反应得到了一个铜配合物[Cu2(bbbm)2(SCN)4(CH3OH)2]。通过X-射线单晶衍射测定了配合物的晶体结构。其晶体属三斜晶系,Pī空间群,晶胞参数为a = 8.6951(17) Å, b =10.116(2) Å, c = 13.818(3) Å, a = 75.64(3)°, β = 82.52(3)°, g = 72.98(3)°, V = 1123.7(5) Å3, Z = 1, Dc = 1.481 mg/m3, F(000) = 516, R1 [I > 2σ (I)] =0.0423, ωR2 = 0.1353X-射线单晶衍射分析结果表明:该配合物是一个双核结构,固体状态下,依靠C—H···S分子间氢键和π-π堆积作用,配合物的双核分子被连接形成了一个三维网状超分子结构。此外,测试了该配合物在2,6-二甲基苯酚偶联反应中的催化活性及其电化学性能。

关键词:柔性配体;配合物;晶体结构;2, 6-二甲基苯酚;氧化偶联反应;电化学性能

中图分类号:O627.12    文献标识码:A    文章编号:0258-32832018

 

Synthesis, Crystal Structure and Properties of New Copper(II) Complex [Cu2(bbbm)2(SCN)4(CH3OH)2] WANG Li-ping, LIU Yan-liLI Hui-na, LI KunZHOU Xiao-li* (College of Chemical Engineering and Food Sciences, Zhengzhou Institute of Technology, Zhengzhou 450044, China), Huaxue Shiji, 2018, 40 (11),

AbstractA new copper(II) complex [Cu2(bbbm)2(SCN)4(CH3OH)2] has been synthesized by self-assembly of flexible ligand 1,1′-(1,4-butanediyl)-bis-l-H-benzimidazole (bbbm) and Cu(II) cations. The crystal structure of the complex was determined by X-ray single crystal diffraction. The crystal structure belongs to triclinic system with space group Pī. The cell parameters were as follows: a = 8.6951(17) Å, b =10.116(2) Å, c = 13.818(3) Å, a = 75.64(3)°, β = 82.52(3)°, g = 72.98(3)°, V = 1123.7(5) Å3, Z = 1, Dc = 1.481 mg/m3, F(000) = 516, R1 [I>2σ(I)] = 0.0423, ωR2=0.1353. X-Ray single crystal diffraction indicates that the complex was a discrete binuclear structure. In solid phase, a 3-D net supramolecular structure was fabricated by C―H···S intermolecular hydrogen bonds and π-π stacking interactions. Additionally, the catalytic activities of the complex in the oxidation coupling reaction of 2, 6-dimethylphenol and electrochemical properties of the complex were tested.

Key words: flexible ligand; complex; crystal structure; 2,6-dimethylphenol; oxidative coupling reaction; electrochemical property

 

过渡金属催化异喹啉-1-酮的合成研究进展

邹帅 耿舒 陈丽娜 黄锋*

(国民核生化灾害防护国家重点实验室,北京 102205

摘要:异喹啉-1-酮类化合物具有多种生物活性及药理活性,如消炎、杀菌、抗病毒等,且广泛存在于天然产物及药物分子中。由于它在药物研究和制药领域扮演的重要角色,其合成方法一直受到有机合成化学家和药物合成化学家的特别关注。近年来过渡金属催化C-H键活化领域的快速发展,为异喹啉-1-酮类化合物的合成提供了一种高效手段,极大地丰富了其合成方法。对多种过渡金属催化合成异喹啉-1-酮类化合物的方法进行总结,并简单介绍了反应特点及机理。

关键词:过渡金属催化;异喹啉-1-酮;合成

中图分类号O626.3             文献标识码A           文章编号0258-3283(2018)11--

 

Progress in Transition Metal-Catalyzed the synthesis of Isoquinolin-1-one ZOU Shuai, GENG Shu, CHEN Li-na, HUANG Feng*(State Key Laboratory of Civil Nuclear, Biological and Chemical Defense, Beijing 102205, China) Huaxue Shiji, 2018, 40(11),

Abstract: Isoquinolin-1-one compounds have various biological activities and pharmacological activities, such as anti-inflammatory, bactericidal, anti-viral, etc., and they are widely present in natural products and drug molecules. Due to its important role in drug research and pharmaceutical field, its synthetic methods have received special attention from organic synthetic chemists and drug synthesis chemists. The rapid development of transition metal catalyzed C-H bond activation in the past decade has provided an efficient means for the synthesis of isoquinolin-1-ones, which greatly enriched its synthesis method. A variety of transition metal catalyzed methods for the synthesis of isoquinolin-1-one compounds are summarized, and the characteristics and mechanisms of these reactions are briefly introduced.

Key words: transition metal catalysis; isoquinolin-1-one; synthesis

 

微反应器在硝化反应中的应用

曾丽媛,毛明珍,王威,王伦,张建功,宁斌科*

(西安近代化学研究所 氟氮化工资源高效开发与利用国家重点实验室,陕西 西安  710065

 

摘要:硝化反应在农药、炸药、染料、香水以及活性药物中间体等的合成中占有重要地位,但目前工业上普遍采用间歇式操作,其生产过程中存在放热量大、选择性低、危险性高、环境污染、资源浪费等问题。微反应器作为高效、安全、环保、操作性强的新型反应设备,可凭借其良好的传质、传热性能解决以上问题,并可通过增加反应器数量进行放大,节省放大时间和成本。因此,对微反应器的特点进行了简单介绍,并针对微反应器在硝化反应中的具体应用研究做出简要概述。

关键词:硝化反应;微反应器;传质传热

中图分类号:O6-33         文献标识码:A       文章编号:0258-32832018

 

The Application of Microreactors in Nitration ZENG Li-yuan, MAO Ming-zhen, WANG wei, WANG Lun, ZHANG Jian-gong, NING Bin-ke* (State Key Laboratory of Fluorine & Nitrogen Chemicals, Xi’an Mordern Research Institute, Xi’an 710065, China), Huaxue Shiji, 2018, 40(11),

Abstract: Nitration plays an important role in the synthesis of fine chemicals and pharmaceutical intermediates, but it has some problems such as large heat release, high risk, low selectivity and environmental pollution. Microreactor is an emerging chemical reacting equipment with high efficiency, safety, high maneuverability, and environmental friendliness. It can solve these problems with its good mass transfer and heat transfer performance. This article introduced the microreactor and gave a brief overview of the application of microreactors in nitration.

Key words: nitration; microreactor; mass transfer and heat transfer

 

过渡金属催化N-烷氧基芳香酰胺邻位碳氢键官能团反应的研究进展

岳新珠,秦育红,常宏宏,魏文珑,李兴*

(太原理工大学  化学化工学院,山西  太原  030024)

 

摘要:过渡金属催化的CH键活化/官能团化反应一直是有机合成领域的研究热点之一,而N-烷氧基酰基(CONHOR)作为一种有效的导向基团已被广泛应用于CH键活化/官能团化反应中,大大拓展了CH键活化反应的应用范围。按照不同种类的金属催化剂和反应类型进行分类,针对近几年N-烷氧基酰胺作导向基的情况,对芳香酰胺邻位碳氢键活化/官能团化的研究进展进行了综述。

关键词N-烷氧基芳香酰胺;导向基团;CH键活化;过渡金属

中图分类号:0626    文献标识码:A    文章编号:0258-3283

 

Progress in Transition-metal-catalyzed Ortho CH Functionalization of N-Alkoxy Aromatic Amides YUE Xin-zhu, QIN Yu-hong, CHANG Hong-hong, WEI Wen-long, LI Xing* (College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China), Huaxue Shiji, 2018, 40(10),

Abstract: Transition-metal-catalyzed C―H activation/functionalization has been one of the hot topics in organic synthesis. The ―CONHOR as an efficient directing group has been widely used in C―H activation/functionalization reactions, which greatly expanded the scope of C―H activation reactions. Based on the different metal catalysts and reaction types, the recent research progress in the ortho C―H activation/ functionalization of N-alkyloxy aromatic amides in the case of ―CONHOR as a directing group has been summarized in this work.

Key wordsN-alkoxy aromatic amides; directing groups; C―H activation; Transition metals

 

锂离子电池用硅碳复合材料的研究进展

刘贵龙*,赵运霞,黄消消,张帅,李晓蕊,崔璐,靳雪阳

(洛阳师范学院 化学化工学院,河南 洛阳  471934

 

摘要硅存在导电性、溶解性差、充放电过程中颗粒收缩与膨胀等问题,影响硅作为锂离子电池负极材料的发展。通过纳米化、复合化和形成多孔结构等方法,可缓解硅的体积变化。目前,解决容量衰减问题的方式主要有:通过亚纳米硅和石墨烯混合方式的调控,制备出硅被石墨烯片层均匀包夹的复合材料;使用气相沉积使气相与固相接触,对硅表面进行均匀的包覆,形成包覆型复合材料;利用溶胶凝胶法-刻蚀法制备多孔的纳米纤维碳与硅复合的材料。本文综述了硅碳复合材料在锂离子电池负极材料中的应用进展。

关键词锂离子电池;硅碳;复合材料;负极材料

中图分类号TQ152     文献标识码A      文章编号0258-3283(2018)

 

Progress on Silicon-carbon Composite Materials for Lithium Ion Battery LIU Gui-Long*, ZHAO Yun-Xia, HUANG Xiao-Xiao, ZHANG Shuai, LI Xiao-Rui, CUI Lu, JIN Xue-Yang (College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471934, China), Huaxue Shiji, 2018, 40(10),

Abstract: There are several drawbacks of silicon-based anode materials for Li-ion battery, including poor conductivity and solubility, severe volume expansion and contraction during charge and discharge. Currently, to tackle with the above mentioned problems, many effective strategies were developed, for instance, (1) compositing silicon with graphene in a sandwich structure, (2) uniformly coating silicon with a robust carbon layer, and (3) wrapping silicon with carbon nanofiber via modified sol-gel methods. In this work, the applications of silicon/carbon composites as anode materials for lithium-ion batteries are summarized.

Key words: lithium-ion battery; silicon carbon; composite material; anode material

 

基于质谱技术的二次化学衍生标记新方法的构建与研究

马建峰1,2郑淑珍*1

(1.临沂大学 化学化工学院,山东 临沂 276000

2.高性能土木工程材料国家重点实验室 江苏苏博特新材料股份有限公司,江苏 南京 211100)

摘要:采用具有双官能团活性马来酸酐作为新的标记试剂,创新性的采用轻重马来酸酐和轻重巯基乙醇对多肽进行二次化学衍生化,利用LC-MS/MS对一次和二次标记产物进行色谱和质谱分析。通过对比标记产物色谱行为发现,马来酰化衍生明显增加了肽段的疏水性,延长了多肽在色谱柱上的保留时间,保留时间从15.16 min延长到23.78 min。质谱结果表明,经巯基乙醇二次标记后,衍生化产物b1为一分子苯丙氨酸(F)、一分子马来酸酐(MA)和一分子β-巯基乙醇(β-Me)的分子量之和,说明标记位点发生在N端氨基上并成功实现了双分子标记。利用该方法,我们成功实现了对某细胞全蛋白酶解多肽进行多重标记,通过对肽段性质研究表明,95%肽段是C端为精氨酸(R)的肽段,5%肽段是C端为赖氨酸(K)的肽段。

关键词: 质谱;化学衍生标记;蛋白修饰

中图分类号:O622.2    文献标识码:A   文章编号: 0258-3283(2018)--

 

Construction of New Labeling Method Using Continuous Two Chemical Derivatization Based on Mass Spectrometry MA Jian-feng1,2, Zheng Shu-zhen*1(1. College of Chemistry and Chemical Engineering, Linyi University, Linyi 276000, China; 2. Jiangsu SoBute New Materials Co., Ltd., State Key Laboratory of High Performance Civil Engineering Materials, Nanjing 211100, China) Huaxue Shiji, 2018, 40(11), ~

Abstract: Maleic anhydride which has bifunctional reactive was used as a new kind of labeling reagent. Isotopic maleic anhydride and isotopic mercapto ethanol were innovatively used for two chemical derivatization, and the first and second labelled products were analyzed by Chromatograph and mass spectrometry(LC-MS/MS). The result of the chromatographic behavior indicated that the hydrophobicity of the peptide was significantly increased by the maleic derivatization, thus the retention time of the peptide on the chromatographic column was prolonged, as a result, the retention time was extended from 15.16 min to 23.78 min. The mass spectrometry showed that the derivative product b1 was a sum of molecular weights of phenylalanine (F), a molecule of maleic anhydride (MA) and a molecule of beta mercapto ethanol (β-Me), which indicated that the labeling occurred on the N terminal amino group and successfully realized the double molecular labeling. Total protein modification of Hela cell were successfully realized by using this method. The results of peptide analysis showed that 95% of the peptides detected were C terminal R peptide and 5% C terminal K peptide.

Key words: Mass spectrometry; Chemical derivatization labeling; Protein modifications

 

荧光探针法测定十六烷基三甲基溴化铵临界胶束浓度

李焘君,李栋,李平*

(天津理工大学  化学化工学院  天津  300384

摘要: 阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)是一种具有长链烷基的季铵盐,可用于纳米粒子合成、DNA提取与家庭洗护等。临界胶束浓度(CMC)是表面活性剂溶液性质发生显著变化的分水岭,准确测量其临界胶束浓度有助于更好的发挥该化合物增溶、杀菌等作用。将4H,4'H-2,2'-双色烯-4,4'-二酮(BCDO)作为荧光探针,建立了以荧光探针法测定表面活性剂的临界胶束浓度的新方法,测定了典型阳离子表面活性剂十六烷基三甲基溴化铵的临界胶束浓度。探针用量8.70×10-6 g下,配制11个浓度分别为0.100.200.300.400.500.600.700.800.901.001.10 mmol/LBCDO-CTAB样品溶液,分别测定样品溶液的荧光光谱。BCDO-CTAB样品荧光强度-浓度曲线可知,曲线出现拐点时对应的浓度为0.80 mmol/L,此浓度与CTAB临界胶束浓度的文献值一致,表明BCDO作为荧光探针测定CTABCMC是可行的。

关键词: 4H,4'H-2,2'-双色烯-4,4'-二酮;荧光探针法;十六烷基三甲基溴化铵;表面活性剂;临界胶束浓度

中图分类号:TQ207       文献标识码:A         文章编号:0258-3283(2018)--

 

Determination of Critical Micelle Concentration of Cetyl Trimethyl Ammonium Bromide by Fluorescence Probe Method LI Tao-Jun, LI Dong, LI Ping*(Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300384,China) Huaxue Shiji, 2018, 40(11),

Abstract:  The cationic surfactant cetyl trimethyl ammonium bromide (CTAB) is a quaternary ammonium salt with a long-chain alkyl group. Thus it was used for nanoparticle synthesis, DNA extraction and household washing. When the concentration of surface active agent is close to critical micelle concentration (CMC), the qualities of surface active agent will change strikingly. Accurate measurement of compound’s critical micelle concentration helps in solubilization and sterilization etc.. In this paper, using 4H,4'H-2,2'- bichromene -4,4'-dione (BCDO) as a fluorescent probe, a novel fluorescence probe method was established for determination of critical micelle concentration of a typical cationic surfactant CTAB. Including only 8.70×10-6 g fluorescent probe, 11 sample solutions of BCDO-CTAB were prepared with the concentration of 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.90, 1.00, 1.10 mmol/L separately to obtain their fluorescence spectrometries. From the BCDO-CTAB sample fluorescence intensity-concentration curve, the corresponding concentration at the inflection point of the curve was 0.80 mmol/L. This concentration was consistent with the literature value of the critical micelle concentration of CTAB. It indicated that BCDO as a fluorescent probe for the determination of CMC of CTAB was possible.

Key words: 4H,4'H-2,2'-bichromene-4,4'-dione; fluorescence probe method; cetyl trimethyl ammonium bromide; surfactant; critical micelle concentration

 

云南烟草提取物主要中性香味成分的对比研究

张博1,李小兰2,黄善松2,黄世杰2,朱远洋1,黄贵元1,彭周舟1,张峻松*1

1.郑州轻工业学院 食品与生物工程学院,郑州  450002

2.广西中烟有限责任公司技术中心,南宁  530001

摘要:为比较烟草浸膏、烟草净油、烟草净油轻组分、烟草净油重组分主要中性香味成分的差异,采用超声萃取的方式对四种烟草提取物进行萃取,将萃取液进行中性香味成分的分离,结合气相色谱质谱分析检测。结果表明:四种烟草提取物共检测出主要中性香味成分29种,其中浸膏、净油、轻组分、重组分分别检测出主要中性香味成分14种、21种、24种、16种;对于酯类、醇类、烃类香味成分的数量,轻组分最多,之后依次为净油、重组分、浸膏;相较于净油,重组分检测出茄酮;四种烟草提取物中轻组分检测出中性香味成分含量最多,之后依次为净油、重组分、浸膏;对于酯类、酮类、醇类、烃类香味成分的含量,轻组分最高,之后依次为净油、重组分、浸膏;因此,从中性香味成分的数量和含量上看,轻组分效果最佳,之后依次为净油、重组分、浸膏。

关键词烟草浸膏;烟草净油;轻组分;重组分;气相色谱质谱联用(GC/MS

中图分类号:O0657.7+1              文献标识码:A                 文章编号:0258-32832018    

 

Comparison of Main Neutral Aroma Components from Yunnan Tobacco Extracts ZHANG Bo1, LI Xiao-lan2, HUANG Shan-song2, HUANG Shi-jie2, ZHU Yuan-yang1, HUANG Gui-yuan1, PENG Zhou-zhou1, ZHANG Jun-song*1 (1.School of Food and Bioengineering, Zhengzhou University of Light Industry, Zhengzhou 450002, China; 2.Technology Center of Guangxi Tobacoo Industry Co., Ltd., Nanning 530001, China), Huaxue Shiji, 2018, 40(11),

Abstract: To compare the differences in neutral aroma components of tobacco extracts, tobacco absolute oils, light distilled components of tobacco oil, and heavy distilled components of tobacco oil, four types of tobacco extracts were extracted using ultrasonic extraction. Separation of neutral aroma components from the extract, combined with gas chromatography mass spectrometry detection. The results show: Total of 29 neutral aroma components detected in four tobacco extracts. Among them, 14 kinds, 21 kinds, 24 kinds, and 16 kinds of main neutral aroma components were detected in tobacco extract, tobacco absolute oil, light distilled components of tobacco oil, and heavy distilled components of tobacco oil. For the amount of esters, alcohols, hydrocarbons, light distillated components were the most, followed by tobacco absolute oil, heavy distilled components, and tobacco extract; Compared to tobacco absolute oil, heavy distilled components detected solanone. Among the four types of tobacco extracts, light distilled components detected the highest content of neutral aroma components, followed by tobacco absolute oil, heavy distilled components, and tobacco extract. For the content of aroma components of esters, ketones, alcohols, and hydrocarbons, light distilled components were the highest, followed by tobacco absolute oil, heavy distilled components, and tobacco extract. Therefore, from the point of view of the amount and content of neutral aroma components, light distilled components were the best, followed by tobacco absolute oil, heavy distilled components, and tobacco extract.

Key words: Tobacco extract; Tobacco absolute oil; Light distilled components; Heavy distilled components; Gas chromatography-mass spectrometry

 

氟虫腈及其三种衍生物的纯度标准物质高效液相色谱定值分析

马瑞安1,黄挺2,全灿2,张伟2,杨屹*1,苏萍*1

(1 北京化工大学 理学院,北京  100029; 2 中国计量科学研究院 化学计量与分析科学研究所,北京  100029)

摘要:氟虫腈是一种广谱杀虫剂,适用于水稻、玉米、棉花等作物的除虫。但其具有高毒性,氟虫腈及其代谢物(氟甲腈、氟虫腈砜、氟虫腈硫化物)是氟虫腈残留的主要被测组分。现有的液相色谱检测文献主要集中于基体中的痕量分析,这种方法不能用于对纯度标准物质的定值。对氟虫腈及其3种衍生物的高效液相色谱分析条件进行了研究,计算了不同流动相条件下的4个峰的分离度,得到了一种可将混合标准溶液中4种物质的峰完全分离且分离度足够大(四者的最小分离度达到3.05),可对氟虫腈及其3种衍生物的纯度标准物质进行定值分析的液相方法。

关键词:高效液相色谱;氟虫腈;纯度标准物质

中图分类号:TQ421.3            文献标识码:A        文章编号:0258-32832018

 

Determination of the reference material of fipronil and its metabolites with high performance liquid chromatograghy MA Rui-an1, HUANG Ting2, QUAN Can2, ZHANG Wei2, YANG Yi*1, SU Ping*1 (1 College of Science, Beijing University of Chemical Technology, Beijing 100029, China; 2 Division of Metrology in Chemistry, National Institute of Metrology, Beijing 100029, China), Huaxue Shiji, 2018, 40(11),

AbstractFipronil is a broad-spectrum insecticide suitable for the extermination of crops such as rice, corn and cotton, but it is highly toxic. The European “poison egg” incident in 2017 was caused by millions of eggs that were contaminated with the insecticide fipronil. Fipronil and its metabolites (fipronil desulfinyl, fipronil sulfone, and fipronil sulfide) are the main tested components of fipronil residues. The study of the purity reference material of fipronil and its metabolites is of great significance to the accuracy and comparability of its detection. The existing literature on liquid chromatography detection mainly focuses on the trace analysis in the matrix, which cannot be used to determine the purity of a reference material. In this paper, high performance liquid chromatography (HPLC) conditions for the analysis of fipronil and its three derivatives were studied. The separation degree of the four peaks under different mobile phase conditions was calculated. A liquid-phase method that can completely separate the four substances in the mixed standard solution and has a sufficient degree of separation (the minimum separation degree was 3.05) can be used to perform fixed-value analysis on the purity determination of the reference material of fipronil and its three derivatives.

Key wordsHigh performance liquid chromatography (HPLC); fipronil; purity reference material

 

新型小分子席夫碱离子液晶的合成及液晶性能研究

付双*,王占乐,陈颂,李爽

(齐齐哈尔医学院 药学院,黑龙江 齐齐哈尔  161006 

摘要:以对氨基苯酚和对硝基苯甲醛合成4-硝基-4′-羟基对苯席夫碱;再由4-硝基-4′-羟基对苯席夫碱与1,10-二溴癸烷合成4-硝基-4'(10-溴癸烷氧基)对苯席夫碱;最后与咪唑反应,合成目标产物4-硝基-4′(10溴咪唑癸烷氧基)二苯席夫碱离子液晶化合物。通过IR1HNMR13CNMR、元素分析等方法对化合物结构进行了表征。通过DSC和偏光显微镜研究了化合物的液晶性能。结果表明该物质具有热致液晶性,是新型席夫碱离子液晶化合物。

关键词:新型;小分子;席夫碱型;热致液晶

中图分类号:O625       文献标识码:A       文章编号:0258-32832018

 

Synthesis and Character of p-Benzene-4-nitro-4'(decylalkoxy 10-bromide) Schiff Base FU Shuang1, WANG Zhan-le1, CHEN Song1, LI Shuang (College of Pharmacy, Qiqihar Medical University, Qiqihar 161006, China), Huaxue Shiji, 2018, 40(10),

Abstract: In this work, the Schiff base type ionic liquid crystalline intermediate p-benzene-4-nitro-4'(decylalkoxy 10-bromide) Schiff base had been synthesized. Using p-aminophenol and p-nitrobenzaldehyde as monomer, p-benzene-4-nitro-4′-hydroxy Schiff base was synthesized, and then 4-nitro-4′-bromine decyl alkyl ether of benzene Schiff base was synthesized by p-benzene-4-nitro-4′-hydroxy Schiff base and 1,10-dibromo decane. The structures of compounds were confirmed by IR, 1HNMR, 13CNMR. The p-benzene-4-nitro-4' (decylalkoxy 10- bromide) Schiff base is the important intermediate for the synthesis of the Schiff base type ionic liquid crystalline.

Key words: synthesis; p-benzene-4-nitro-4' (decylalkoxy 10-bromide) Schiff base; Schiff base type ionic liquid crystalline; intermediate

 

新型DNA巯基化修饰试剂的制备方法及应用

孙立梅,孙亚伟*

(中国石油大学 化学工程学院,山东 青岛  266580)

 

摘要:我们以α-硫辛酸为起始原料,以硼氢化钠和碘作为复合还原剂将其中的羧基进行选择性还原得到α-硫辛醇,再将其与2-O-氰乙基-N,N-二异丙基氯代亚磷酰胺进行酯化反应,得到2-O-氰乙基-N,N-二异丙基-硫辛醇亚磷酰胺硫辛醇酯。该化合物制备过程不需要使用高腐蚀性和易燃易爆的试剂,后处理方法简单。该试剂可通过固相合成在DNA5'端基高效引入含硫单元,在DNA的分离和使用过程中也不需要引入额外操作,为DNA5'端基官能化修饰提供了新的选择。

关键词2-O-氰乙基-N,N-二异丙基-α-硫辛醇亚磷酰胺硫辛醇酯;DNA端基修饰试剂;α-硫辛酸;α-硫辛醇

中图分类号:O629.74    文献标识码:A    文章编号:0258-3283(2018)

 

Synthesis and Application of a New Disulfide Modification Reagent of DNA SUN Li-mei, SUN Ya-wei* (College of Chemical Engineering, China University of Petroleum, Qingdao 266580, China), Huaxue Shiji, 2018, 40(10),

Abstract: A new disulfide containing phosphoramidite reagent was synthesized and applied in DNA terminus functionalization. The α-lipoic acid was selective reduced to α-lipoic alcohol with NaBH4 and I2, and the α-lipoic alcohol was allowed to react with 2-O-cyanoethyl-N,N-diisopropylchlorophosphoramidite to obtain the desired product. This reagent give good performance in 5-terminus modification of DNA on automatic DNA synthesizer. As no post-processing operations is required after DNA terminus modification, this reagent exhibited potential application in functional nucleic acids preparation.

Key words: 2-O-cyanoethyl-N,N-diisopropyl-α-lipol-phosphoramidite; DNA modificationα-lipoic acid; α-lipoic alcohol

 

荧光光谱法研究富电子氨基酸与四苯乙烯-吡啶盐的相互作用

徐洲,梅高接,李亿保*,范小林

(赣南师范大学化学化工学院江西省有机药物化学重点实验室,赣州341000

 

摘要:设计了一种新型生物分子传感材料水溶性四苯乙烯-吡啶盐(Tpp4+)分子。为了模拟生物环境,将溶液酸碱度调至pH7.4,用荧光光谱法研究了L-苯丙氨酸、L-色氨基酸、L-异亮氨酸、L-组氨酸与Tpp4+分子相互作用。研究结果发现,L-色氨酸对Tpp4+分子荧光有猝灭效应;根据不同温度下的Stern-Volmer曲线拟合得到,在T=298K时,猝灭常数为355.2L/mol,而在T=308K时,猝灭常数为825.2L/mol;随着温度的升高,猝灭常数增大,由此判断猝灭机制为动态猝灭。

关键词:荧光光谱法;富电子氨基酸;荧光猝灭;四苯乙烯-吡啶盐

中图分类号:O651文献标识码:A文章编号:

 

Study on the Interaction between Rich Electronic Amino Acids andTetraphenyletthene-PyridiniumSalts by Fluorescent SpectrometryXU Zhou, MEI Gao-jie, LI Yi-bao*, FAN Xiao-lin(College of chemistry and chemical engineering, Gannan Normal University , Key Laboratory of organic chemistry of drug Jiangxi Province, Gan Zhou341000)

Abstract: we are report a new novel of biological molecular sensing materials. In order to simulate the biological environment, we adjusted the pH of the solution to pH=7.4; the interaction between L-Phenylalanine, L-Tryptophan, L-Isoleucine, L-Histidine and Tpp4+molecule were studied by fluorescence spectroscopy.The results showed that L-Trp has a quenching effect on the molecular fluorescence of Tpp4+.According to the Stern-Volmer curves fitting at different temperatures, the quenching constant were355.2L/mol(T=298K) and 825.2L/mol(T=308K), respectively; The quenching constant increases with the increase of temperature, and the quenching mechanism was dynamic quenching.

Keywords:fluorescence spectrometry;rich electron amino acids;fluorescence quenching;tetraphenyletthene-pyridinium salts

 

二甲基十二烷基烯丙基氯化铵的合成、防膨性能及机理

郭兴午1,梁爽2,肖勇军3,都伟超*4

(1.中国石油 西南油气田页岩气研究院,四川 成都  6100212.中国石油 西南油气田川中油气矿,四川 遂宁  6290003.四川长宁天然气开发有限责任公司,四川 成都  6100004.西安石油大学 化学化工学院,陕西 西安  710065)

 

摘要:为保护油气储层,以二甲胺、氯代十二烷、烯丙基氯为原料,开发出一种表面活性剂型烯类阳离子粘土防膨剂:二甲基十二烷基烯丙基氯化铵(DDAAC)。采用正交试验确定了产物的最优合成方案,该方案为:反应温度35 ℃;反应时间12 hpH 9n(二甲胺):n(氯代十二烷):n(烯丙基氯)=1.6:1.0:1.6。当DDAAC加量为0.5wt%时,防膨率达68.31%。采用XRDFT-IR等手段对DDAAC防膨机理进行研究,XRD表明DDAAC可插层进入Na-MMT晶层间,0.5wt%DDAAC可将干态Na-MMT晶层间距由1.28 nm撑至1.57 nmFT-IR表明DDAAC可与Na-MMT发生强烈吸附作用。

关键词:二甲基十二烷基烯丙基氯化铵;表面活性剂;季铵盐;粘土防膨剂

中图分类号:O623.7    文献标识码:A      文章编号:0258-32832018

 

Synthesis, Clay Anti-Swelling Property and Mechanism of Dimethyl Dodecyl Allyl Ammonium Chloride GUO Xing-wu1, LIANG Shuang2, XIAO Yong-jun3, DU Wei-chao*4 (1.Shale Gas Research Institute, PetroChina Southwest Oil & Gas Field Company, Chengdu 610021, China; 2.Central Sichuan Oil & Gas Field District, PetroChina Southwest Oil & Gas Field Company, Suining 629000; 3.Sichuan Changning Gas Development Co., Ltd., Chengdu 610000, China; 4.College of Chemistry and Chemical Engineering, Xi’an Shiyou University, Xi’an 710065, China), Huaxue Shiji, 2018, 40 (11),

Abstract: In order to protect the oil&gas reservoirs, a surfactant vinyl cationic clay (Na-MMT) anti-swelling agent dimethyl dodecyl allyl ammonium chloride (DDAAC) was prepared from dimethylamine, chlorododecane and allyl chloride as raw materials. The single-factor orthogonal test was used to determine the optimal synthesis scheme for DDAAC: reaction temperature 35 °C; reaction time 12 h; pH 9; n (dimethylamine): n(chlorododecane): n(allyl chloride) = 1.6:1.0:1.6. The experimental results showed that the anti-expansion rate of 0.5wt% DDAAC can reach to 68.31%. XRD and FT-IR were utilized to study its anti-expansion mechanism. XRD indicated that DDAAC could intercalate and enter the interlayer of Na-MMT, 0.5wt% DDAAC could support the dry Na-MMT layer spacing from 1.28 nm to 1.64 nm, FT-IR showed that physicochemical adsorption between DDAAC and Na-MMT occurs.

Key words: dimethyl dodecyl allyl ammonium chloride;surfactant;quaternary ammonium salt; clay anti-swelling agent

 

硬巢大须球白蚁巢黄酮、多酚的同步提取工艺优化

及抗氧化活性

杨新周1,2,郭云胶1,3,田孟华4,杨子仙2,马艳粉1,3,田先娇1,3

(德宏师范高等专科学校 1.民族医药研究所,2.理工系,3.生命科学系,云南 德宏  6784004.昭通市天麻研究院,云南 昭通  657000

 

摘要: 本文建立了同步提取硬巢大须球白蚁巢中黄酮和多酚的方法。为硬巢大须球白蚁巢的资源开发和综合评价提供科学依据。利用回流提取法,通过单因素考察乙醇体积分数、液料比、温度和提取时间对硬巢大须球白蚁巢中黄酮、多酚含量的影响,并在此基础上进行正交试验。利用清除DPPH·自由基、·OH自由基活性方法,测试硬巢大须球白蚁巢提取液抗氧化活性。通过实验得出硬巢大须球白蚁巢中黄酮和多酚提取的最优工艺为:乙醇溶液浓度50%,料液比为1:40,提取温度为80 ℃,提取时间为2 h。在此条件下同时提取硬巢大须球白蚁巢中黄酮、多酚,工艺稳定性好、结果准确可靠,工艺简单、可操作性强。硬巢大须球白蚁巢中黄酮和多酚含量分别为11.27 mg/g11.19 mg/g。抗氧化活性测试表明硬巢大须球白蚁巢提取液对DPPH·IC500.75 mg/mL,对·OHIC502.66 mg/mL。结果表明水浴-回流法能够同步提取硬巢大须球白蚁巢中黄酮、多酚类物质。白蚁巢提取液具有一定的抗氧化活性。

关键词: 硬巢大须球白蚁;黄酮;多酚;抗氧化

中图分类号:R284.2    文献标识码:A    文章编号:0258-32832018

 

Optimized Methodology for the Simultaneous Extraction of Flavonoids, Phenolic Compounds and Antioxidant Capacity from Hospitalitermes Majusculus YANG Xin-zhou1, 2, GUO Yun-jiao1, 3, TIAN Meng-hua4, YANG Zi-xian2, MA Yan-fen1, 3, TIAN Xian-jiao1, 3 (1.The Research Institute of Ethnic Minority Medicine, 2. Department of Science and Engineering, 3.Department of life sciences, Dehong Teachers’ College, Dehong 678400, China; 4.Zhaotong Tianma Research Institute, Zhaotong 657000, China), Huaxue Shiji, 2018, 40 (11),

Abstract: Compared the content of flavonoid, polyphenol in Hospitalitermes majusculus by establishing the simultaneous extraction method, which provides a scientific basis for resource exploration and comprehensive evaluation of Hospitalitermes majuscules in the study. Analyzing the factors like ethanol volume fraction through single factor investigation, solid/liquid ratio, temperature and extraction time how to affect the content of flavonoid, polyphenol in Hospitalitermes majusculus by using refluxing extraction. Then, the orthogonal experiment was carried out. The antioxidative activity of the extracts from the Hospitalitermes majusculus was tested by using the DPPH free radical and OH free radical activitymethod. The best extracting technology for flavonoid, polyphenol in Hospitalitermes majusculuas follows: ethanol volume fraction is 50%the liquid ratio is 1:40, extracting temperature is 80 , extraction time is 2 h. In this condition, the extracted process stability was good, the results were accurate and reliable, and the process was simple and operable. The research shows that the flavonoids and total phenol content was 11.27 mg/g, 11.19 mg/g, DPPH· IC50(half clearance rate) was 0.75 mg/mL, ·OH IC50 was 2.66 mg/mL. The results show that the water bath-reflux method can simultaneously extract the flavonoids, polyphenols in the Hospitalitermes majusculus. The extracts of Hospitalitermes majusculus has certain antioxidant activity.

Key words: Hospitalitermes majusculus; flavonoids; phenolic; antioxidan

 

硫酸铵存在下硫氰酸钾-CTMAB-丙醇双水相体系萃取分离银

左国强*1,张晓杰1,赵亚鹏2,李雅倩1

1. 济源职业技术学院 冶金化工系,河南 济源  454600

2. 济源市疾病预防控制中心,河南 新乡  453007

 

摘要:研究了在硫酸铵存在下硫氰酸钾-CTMAB-丙醇双水相体系萃取分离银的行为及最佳分相条件。考察了硫氰酸钾和CTMAB用量、体系pH对萃取率的影响,实验表明,在10.0 mL30%)的丙醇溶液中,控制溶液酸度在pH 1 5,加入1.5 g(NH4)2SO40.8 mL0.4 mol/LKSCN0.2 mL0.01 mol/LCTMABAg+SCN生成的配离子Ag(SCN)2能与CTMAB阳离子生成离子配合物,进而萃取到丙醇上层,方法通过火焰原子吸收光谱法(AAS)检测萃取后丙醇相中银的含量得到证实。Ag+质量浓度在0.4 2 μg/mL范围内呈线性关系,回归方程为A=0.0178c+0.0025r = 0.9964。干扰实验表明,Ag+能够从常见过渡元素Pb2+Cd2+Zn2+Co2+Ni2+Fe2+Mn2+的混合液中分离出来,加标回收率在91% 104%之间。

关键词:双水相;原子吸收;银

中国分类号:O657.7             文献标识码:A             文章编号:0258-32832018

 

Extraction of Silver by Potassium Thiocyanate-CTMAB – Propanol Extraction System in the Presence of Ammonium Sulfate Aqueous Two-Phase ZUO Guo-qiang*1, ZHANG Xiao-jie1, ZHAO Ya-peng2, LI Ya-qian1(1.Department of Metallurgy and Chemical Engineering, Jiyuan Vocational and Technical College, Jiyuan 454600,China; 2. Department of Chemistry, Henan Normal University, Xinxiang 453007,China), Huaxue Shiji, 2018, 40(1)

Abstract: In the presence of Ammonium sulphate, the extraction behavior of Ag+based onpotassium thiocyanate-CTMAB - propanol system was investigated and the optimal condition of phase separation was selected. The effects of reaction conditions, such as the amount of KSCN and CTMAB, pH, on the extraction rate were investigated. Results showed that, the charged complex compound Ag(SCN)2- can form a kind of ion-association complex with CTMAB in the pH 1 5 media ,when 0.8mL 0.4 mol/ LKSCN, 0.2mL0.01 mol/LCTMAB and 1.5 g (NH4)2SO4 were added, it is easily extracted into the propanol phase. The mass concentration of Ag+ was linear in the range of 0.4 2 μg/mL, the regression equation is A=0.0178C+0.0025the correlation coefficient is 0.9964. The interfering experiment shows that Ag+ can be completely separated from Pb2+Cd2+Zn2+Co2+Ni2+Fe2+Mn2+. The recovery of standard addition was between 91% 104%.

Key words: aqueous two-phase; atomic absorption spectrometry; Silver

 

2-甲基-4-氰基苯甲酸甲酯一步法制备2-甲基-4-甲醛肟基苯甲酸甲酯

刘明1,杨文豪1,张冕1,范伟伟1, 2,王勇*1, 2,李立威1, 2

 (1.荆楚理工学院,化工与药学院,湖北荆门 4480002.荆门医药工业技术研究院,湖北荆门  448000)

摘要:肟类化合物具有优异的杀菌、杀虫、杀螨、植物生长调节、抗肿瘤、抗病毒生物活性。对该类化合物的分子设计、合成与生物活性研究是药物化学和农药研究的热点之一。以2-甲基-4-氰基苯甲酸甲酯为原料与盐酸羟胺在碳酸钠碱性条件下一步反应直接制得目标产物2-甲基-4-甲醛肟基苯甲酸甲酯,接着对该目标产物进行IRMSUV1HNMR13CNMR表征和结构确定。该方法采用氰基化合物为前体一步反应即可得到肟类化合物,操作简单、方便,适应于大规模生产。

关键词:有机合成;肟;氰基; 结构表征

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

 

4-(hydroxyimino-methyl)-2-methyl Benzoic Acid Methyl Ester is Prepared from 4-cyano-2-methyl-benzoic Acid Methyl Ester by One-step Reaction LIU Ming1, YANG Wen-hao1, ZHANG Mian1, FAN Wei-wei1,2,WANG Yong*1,2, LI Li-wei1,2 (1.College of Chemical Engineering and Pharmacy, Jingchu University of Technology, Jingmen 444800, China; 2.Jingmen Institute of Pharmaceutical Industry Technology, Jingmen 444800, China), Huaxue Shiji, 2018, 40(11),

AbstractOxime-based compounds have been received considerable attention by pesticide and pharmaceutical chemists for their excellent bactericidal, insecticidal, acaricidal, plant growth regulating, antitumor, and antiviral bioactivities. At present, the research on molecular design, synthesis and biological activity of these compounds are still one of the hot topics in chemistry. In this work, 4-(hydroxyimino-methyl)-2-methyl benzoic acid methyl ester (2) was synthesized by reaction of 4-cyano-2-methyl-benzoic acid methyl ester (1) with hydroxylamine hydrochloride in the presence of Na2CO3. Compound 2 was fully characterized and confirmed by IR, MS, 1HNMR and 13CNMR. This method uses a cyano compound as a precursor to obtain oxime compound by one-step reaction, which is simple, convenient and suitable for mass production.

Key wordsSynthesize; Oxime; Cyano; Structure Characterized

 

镇痛药他喷他多中间体的合成及工艺优化

郑美娟1,吕育财1,戴秋红2,代齐敏3,龚大春*1

1.三峡大学生物催化重点实验室,湖北 宜昌  4430022.安琪酵母股份有限公司酶制剂事业部,湖北 宜昌 4430023.能特科技股份有限公司,湖北 荆州  434000

 

摘要:采用酮基还原酶和葡萄糖脱氢酶耦合催化方法制备了他喷他多手性中间体(S)-4-(3-甲氧基苯基)-3-甲基-4-氧代丁酸甲酯[(S)-TT5]。经过正交工艺优化,最佳反应条件:底物4-(3-甲氧基苯基)-3-甲基-4-氧代丁酸甲酯(TT2)浓度66.1 g/L,酮基还原酶用量为每克TT2 12U,辅酶NADH用量为8 g/L,反应温度为30 ℃,反应时间为10 h时,底物TT2转化为(3S,4S)-4-羟基-4-(3-甲氧基苯基)-3-甲基丁酸甲酯[(3S,4S)-TT3(主要产物)]的收率为92.5%,d.e.值为99.5%;再经次氯酸钠氧化得(S)-TT5,收率98%,e.e.99.6%。

关键词(S)-4-(3-甲氧基苯基)-3-甲基-4-氧代丁酸甲酯;他喷他多中间体;生物催化

中图分类号:R914.5     文献标志码:A     文章编号:0258-3283(2018)

 

Biocatalysis Process of the Key Intermediate of Tapentadol Methyl (S)-4-(3-Methoxyphenyl)-3-methyl-4-oxobutanoate ZHENG Mei-juan1, LV Yu-cai1, DAI Qiu-hong2, DAI Qi-min3, GONG Da-chun*1 (1.Biocatalysis Key Lab. of China Three Gorges University, Yichang 443002, China; 2.Angel Yeast Co., Ltd., Yichang 443002, China; 3.Neng Te Co., Ltd., Jingzhou 434000, China), Huaxue Shiji, 2018, 40 (11),

Abstract: The key intermediate of tapentadol, methyl (S)-4-(3-methoxyphenyl)-3-methyl-4-oxobutanoate [(S)-TT5] was prepared by the coupling biocatalysis through ketoreductase and glucose dehydrogenase. The optimum reaction conditions were obtained through the orthogonal test. The result showed that, methyl (3S,4S)-4-hydroxy-4-(3-methoxyphenyl)-3-methylbutanoate [(3S,4S)-TT3, main product] can be transformed from methyl 4-(3-methoxyphenyl)-3-methyl-4-oxobutanoate (TT2) with a yield of 92.5 and 99.5 d.e. value under the conditions as follows: TT2 concentration 66.1 g/L, ketoreductase usage to 1 g TT2 12U, coenzyme NADH usage 8 g/L, reaction temprature 30 and reaction time 10 h. Then TT3 was subjected to oxidization by sodium hypochlorite to prepare (S)-TT5 with a yield of 98and 99.6 e.e. value. This biocatalysis method has not yet been reported in literature.

Key words: methyl (S)-4-(3-methoxyphenyl)-3-methyl-4-oxobutanoate; intermediate of tapentadol; biocatalysis