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综述与进展
甘氨酸衍生物α-C(sp3)-H键官能团化反应的研究进展
祝志强, 肖利金, 谢宗波, 乐长高
2019, 39(9): 2345-2364  doi: 10.6023/cjoc201903006
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摘要:
α-氨基酸是构成蛋白质的基本结构单元,不仅广泛存在于许多具有重要生物活性的有机分子和天然产物中,而且还可作为有机催化剂或配体用于不对称合成.其中,甘氨酸类化合物在有机合成中是一类非常有用的模块,通过甘氨酸衍生物的α-C(sp3)-H键官能团化高效构建种类丰富的α-取代的α-氨基酸是一种极吸引人的合成策略.介绍了近年来甘氨酸衍生物α-C(sp3)-H活化后与不同有机试剂偶联构建碳-碳键和碳-杂键以及甘氨酸衍生物参与的氧化串联/环化反应的研究进展.
基于Huisgen内盐的环化反应研究进展
刘奕奕, 周荣
2019, 39(9): 2365-2378  doi: 10.6023/cjoc201903041
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摘要:
发展高效、高选择性的有机合成方法是有机化学的一项重要研究内容.近年来,叔膦与偶氮二甲酸酯加成形成的Huisgen内盐在氮杂环化合物的合成上显示出独特的优越性和高效性,吸引了众多有机化学家的研究兴趣,基于Huisgen内盐的环化反应得以大量报道.根据亲电试剂的种类不同,综述了Husigen内盐与羰基化合物、缺电子烯烃、亚胺以及其他亲电试剂的环化反应.
点击反应在糖聚肽及其类似物合成中的应用
王昭, 郝凌云, 张小娟, 盛瑞隆
2019, 39(9): 2379-2391  doi: 10.6023/cjoc201903038
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摘要:
糖聚肽是一类由聚肽/聚氨基酸与糖类化合物共价相连构成的高分子化合物,因其良好的生物相容性及独特的生物学性能,在自组装、组织工程、药物输送等领域均显示出广泛的应用前景,成为近年来蓬勃发展的热点领域.高效合成结构规整可控的糖聚肽是该领域的热点和难点.点击化学的快速发展为糖聚肽的合成提供了高效便捷的途径.系统综述了点击反应在糖聚肽两种合成策略中的应用——通过聚合后修饰法将糖分子引入到聚氨基酸前体侧链上以及对糖苷化的α-氨基酸-N-羧酸酐(glyco-NCA)"可点击"化学单体的开环聚合反应,同时也总结了通过点击反应将含糖功能基元化学偶联到聚氨基酸链末端合成糖聚肽类似物的策略,并对其优缺点和发展方向进行了简要讨论.
2, 3-二氢喹唑啉-4(1H)-酮类化合物的合成研究进展
张晓鹏, 朱妍洁, 朱奕崧, 李政伟, 张贵生
2019, 39(9): 2392-2402  doi: 10.6023/cjoc201903025
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摘要:
2,3-二氢喹唑啉-4(1H)-酮是一类重要的含氮稠杂环化合物,具有广泛的药理及生物活性,在药物合成与研发领域有着重要应用价值,因而其合成方法也倍受人们关注.归纳总结了2,3-二氢喹唑啉-4(1H)-酮类化合物的合成研究进展,主要介绍了以邻氨基苯甲酰胺、靛红酸酐、邻硝基苯甲酰胺、邻叠氮基苯甲酰胺、邻溴苯甲酰胺、邻溴苯甲腈、邻氨基苯甲酸、邻氨基苯甲腈、邻氨基N-甲基-N-丙二烯基苯甲酰胺、N-烷基苯胺等为起始原料的2,3-二氢喹唑啉-4(1H)-酮类化合物的合成研究进展概况及其反应机理.最后对该类化合物的合成研究进展进行了总结,并对其发展前景进行了展望.
β-羰基膦氧化合物的合成研究进展
阮利衡, 刘畅, 孙京, 周明东
2019, 39(9): 2403-2411  doi: 10.6023/cjoc201901027
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β-羰基膦氧化合物是一类非常重要的有机膦化合物在有机合成化学中具有广泛的用途,科研工作者一直致力于开发更加简单、绿色、高效的合成方法.总结归纳了近年来β-羰基膦氧化物合成策略的研究进展,主要概述了通过磷中心自由基加成反应及水合反应高效制备β-羰基膦氧化合物的合成路线.
马来酰亚胺双键参与的官能化反应研究进展
杨振华, 祝家楠, 文彩月, 葛迎香, 赵圣印
2019, 39(9): 2412-2427  doi: 10.6023/cjoc201902012
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马来酰亚胺是一类海洋天然生物碱、生物活性分子和功能材料的重要结构母核,并能转化为琥珀酰亚胺、四氢吡咯及2-吡咯酮等化合物,具有广泛的应用价值.以马来酰亚胺为合成子构建含有马来酰亚胺和琥珀酰亚胺结构单元的化合物已成为有机合成研究热点之一.对马来酰亚胺双键参与的官能化反应进行了综述,重点在马来酰亚胺的Michael加成、氧化偶联和环加成反应.
N-苄基脱除研究进展
周光伟, 张莉珠, 薛亚涵, 李加荣
2019, 39(9): 2428-2442  doi: 10.6023/cjoc201901031
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N-苄基是有机胺的常用保护基团,因其脱除具有便捷、高效的特点,在有机合成特别是药物和天然产物研究中具有重要地位.近年来,大量科研工作者对N-苄基脱保护进行广泛的研究,但相关工作分散,缺乏系统性综述.因此,从还原脱苄、氧化脱苄、酸碱脱苄等几个方面,系统全面地概述了N-苄基脱除研究的进展.
亚砜脱氧还原方法研究进展
李伟林, 陈炫颖, 郑天骄, 邹祺, 陈文博
2019, 39(9): 2443-2457  doi: 10.6023/cjoc201901028
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亚砜还原为硫醚作为有机合成中一类重要的转化,其应用一直受到人们的广泛关注.随着金属有机的发展,研究人员发展了许多条件温和、实用有效的亚砜还原方法.从还原剂的种类出发,详细介绍了近二十年里亚砜脱氧还原反应的研究进展,分析了这些还原体系所具有的优势及其潜在不足,并探讨了部分反应机理,最后对亚砜还原领域的发展进行了展望.
甲醇低温脱氢均相过渡金属催化剂研究进展
张翔, 郭彩红, 武海顺
2019, 39(9): 2458-2466  doi: 10.6023/cjoc201902032
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能源紧缺和环境污染已成为世界所面临的重大难题,开发绿色能源、寻找化石燃料的替代品迫在眉睫.甲醇由于其含氢密度高、结构简单、环境友好等优点成为未来储氢的理想载体.降低甲醇脱氢反应温度,提高反应选择性,研发均相甲醇脱氢催化剂一直受到国内外的广泛关注.本文围绕甲醇热脱氢和甲醇水相重整,总结了近年来报道的过渡金属均相催化剂反应体系,重点介绍了钌、铑、铱、铁、锰基络合物的结构特点、催化甲醇脱氢条件、反应产率以及催化机理,分析比较了催化剂在使用过程中的活性差异,并对进一步提高水相重整催化剂性能做了展望.
生物小分子成像用双光子荧光探针
黄池宝, 陈会, 李福琴, 安思雅
2019, 39(9): 2467-2484  doi: 10.6023/cjoc201901024
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生物体内活性小分子(生物小分子),不仅数量多,涉及到无机小分子,如SO2,H2S,NO与CO等,而更多的是有机小分子,如单煻、低聚糖、激素、辅酶、甘油、刺激因子、调节因子和维他命等;而且在病理、生理等方面有着至关重要的功能,发挥着举足轻重的作用,直接影响身体健康与疾病的发生.因此,对生物体内小分子的实时观测和监控是十分必要的,而双光子荧光探针正是实现这一目标的必选锐器.双光子荧光探针的定点激发、高横向与纵向分辨率、无光漂白性、无光致毒性和组织深度成像等诸多优点而彰显其无与伦比的优越性,可以很好地对细胞或组织内的生物小分子进行实时动态三维观测和监控.综述了近5年来相继开发的CO、单糖(葡萄糖、β-半乳糖苷酶)、SO2、硫化氢、NO、过氧(硫)化物、硫醇/硫酚、1O2、甲醛、HNO、HClO、O2·-和ONOO-等双光子荧光探针,系统全面地剖析了这些双光子荧光探针的传感机制,并展望了生物小分子显微用双光子荧光探针的发展与愿景.
研究论文
一种新型连续检测镉离子和焦磷酸阴离子的逻辑门荧光传感器及其细胞成像研究
常永新, 李白, 郭淼, 蔡永红, 徐括喜
2019, 39(9): 2485-2491  doi: 10.6023/cjoc201903010
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设计并合成了一种基于8-羟基喹啉(8-HQ)的连续检测Cd2+和焦磷酸阴离子(PPi)的荧光传感器L.在传感器L的DMSO/H2O(V/V=1/1,0.01 mol/L,Hepes-HCl buffer,pH=7.20)溶液中加入Cd2+后导致荧光发射峰(Em=537 nm)猝灭,检测限低至5.87×10-8 mol/L.通过Job's曲线图和质谱验证传感器L和Cd2+离子之间以1:1化学计量比结合,结合常数为4.38×104 L/mol.复合传感器L-Cd2+体系具有通过配体置换法对PPi高度选择性检测性能.L可以作为一种逻辑门荧光传感器检测Cd2+和PPi.传感器L可以用于对活细胞中的Cd2+和PPi的荧光成像.
芳腈化合物的成对电化学合成
曹志成, 刘建超, 褚有群, 赵峰鸣, 朱英红, 佘远斌
2019, 39(9): 2499-2506  doi: 10.6023/cjoc201903052
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采用循环伏安法(CV)和恒电流电解法(CCE)研究了对甲氧基苯甲醇(p-MeOC6H4CH2OH)电化学氧化氰化合成相应芳腈化合物.考察了水的体积分数、硫酸浓度、电解温度、电极材料、电流密度和溶剂等因素对该电化学氧化氰化行为的影响.结果显示,以四丁基高氯酸铵(Bu4NClO4)为电解质,羟胺(HAM)为氮源,在含0.15 mol·L-1 H2SO4及30%水的DMSO体系中,电流密度为10 mA/cm2条件下恒温60℃电解8 h,对甲氧基苯腈(p-MeOBN)的收率为90%.通过对反应底物普适性研究,发现含不同对位和邻位取代基的芳香伯醇均可通过电氧化氰化反应有效转化为相应的腈(61%~92%),并提出了该电氧化氰化反应的可能机理.本工作提出了一种在一室型无隔膜电解槽中,以原位生成醛的方式,无需加入额外的催化剂,通过阴阳两极协同反应的成对电化学合成腈类化合物的方法.
由氨茴内酐合成12H-色烯[2, 3-b]喹啉-12-酮和6H-色烯[4, 3-b]喹啉-6-酮
孙婉婉, 毛玉健, 蒋静, 余靓, 陈凌云, 胡延维, 张士磊
2019, 39(9): 2525-2533  doi: 10.6023/cjoc201903034
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高温下氨茴内酐可以和4-羟基香豆素反应得到两种位置异构的杂环化合物12H-色烯[2,3-b]喹啉-12-酮和6H-色烯[4,3-b]喹啉-6-酮.该反应是一种热促下的转化,不需要催化剂或者添加物的协助,也没有毒害的废弃物产生.反应路线简短,优于已有的制备此类杂环的其它方法.
咔唑并噻唑类蓝色荧光材料的合成及电致发光性质
张婷, 邱子夜, 程肖杰, 张雨露, 汪徐春
2019, 39(9): 2534-2540  doi: 10.6023/cjoc201902035
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以钯为催化剂,通过C-C和C-N偶联反应分别合成了两种咔唑并噻唑类蓝色荧光材料:TCz-PCz和TCz-TPA,并采用质谱、1H NMR、13C NMR和元素分析等对其结构进行了鉴定.系统地研究了这些材料的热稳定性、光物理性质和电化学行为,结果表明这些化合物具有良好的热稳定性和形态稳定性,热分解温度高达400℃,玻璃化转变温度为119℃.在溶液中,这两种材料均发射出强的蓝光,荧光量子效率分别为71%和73%;这些分子的HOMO能级分别为-5.41和-5.21 eV,较高的HOMO能级有利于器件中空穴从空穴传输层向发光层的注入和传输.以TCz-PCz为发光材料,通过真空蒸镀技术制备了非掺杂型有机电致发光器件,研究了其电致发光性能.结果显示该器件具有稳定的蓝光发射,启亮电压仅为3.1 V,最大发光亮度和电流效率分别为2190 cd·m-2和2.88 cd·A-1.
噻唑烯酮与稳定硫叶立德[2+1]环加成反应
万洪维, 于健, 杨寿山, 杜广芬, 何林
2019, 39(9): 2549-2559  doi: 10.6023/cjoc201902003
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噻唑酮衍生的烯烃可以与稳定的硫叶立德发生形式的[2+1]环加成反应,以30%~99%的产率和1:1~10:1的非对映选择性得到螺环丙烷噻唑酮衍生物.
超分子有机框架对喜树碱类开环羧酸盐的负载及其内酯化动力学
闫萌, 彭文昶, 王辉, 张丹维, 黎占亭
2019, 39(9): 2567-2573  doi: 10.6023/cjoc201903071
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喜树碱在弱碱性生理介质中主要以无生物活性的开环羧酸盐形式存在,肿瘤微环境具有弱酸性,而超分子有机框架可以富集和输送负离子药物至肿瘤微环境和肿瘤细胞内.为评估通过超分子有机框架富集和输送喜树碱类开环羧酸盐到肿瘤微环境及肿瘤细胞内,利用肿瘤弱酸性微环境驱动其内酯化,从而发展羧酸盐为前药的可能性,利用透析实验研究了两个超分子有机框架对喜树碱,SN-38和10-羟基喜树碱开环羧酸盐负离子的吸收和保留效应,利用吸收光谱研究了三个羧酸盐在弱酸性生理盐水介质中内酯化形成活性喜树碱分子的动力学.结果表明超分子有机框架对三个羧酸盐均具有显著的保留效应,在pH为6.5的弱酸性介质中,羧酸盐转化为相应内酯的(表观)半衰期分别为120,22和31 h,远短于临床应用的喜树碱类药物伊立替康和拓扑替康重复用药间隔时间(14和21 d),为后续研究提供了依据.
白杨素衍生物的合成及体外抗弓形虫活性研究
尚凡凡, 金澜, 张海滨, 朴莲荀, 全哲山
2019, 39(9): 2574-2580  doi: 10.6023/cjoc201901016
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设计并合成了18个未见报道的白杨素类衍生物,采用噻唑蓝(MTT)比色法对所有化合物进行体外抗弓形虫活性测定,其化学结构均经过1H NMR,13C NMR以及HRMS的联合确证.结果显示,7-甲氧基-8-(NN-双(二乙羟基)-磺酰胺基)-白杨素(D2)的选择性指数为1.76,其抗弓形虫活性明显强于先导化合物白杨素及阳性对照药磺胺嘧啶,具有深入的研究价值.
含树枝状和3D三苯胺衍生物有机染料的合成与光伏性能研究
周鑫云, 谢凌超, 吴凯乐, 谭松庭
2019, 39(9): 2589-2598  doi: 10.6023/cjoc201902023
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设计合成了三种以树枝状和3D三苯胺衍生物为给体单元,苯甲酸为受体单元,苯并噻二唑(BT)或双氟苯并噻二唑(DFBT)作为第二受体单元的有机染料,系统研究了不同给体和第二受体单元对染料敏化剂的光物理性能、电化学性能和光伏性能的影响.以树枝状三苯胺衍生物为给体单元的有机染料具有较高的摩尔吸收系数,以3D三苯胺衍生物(IDTTPA)为给体单元的有机染料具有较宽的吸收光谱.基于三种有机染料的染料敏化太阳能电池分别获得了5.27%,4.22%和5.50%的能量转换效率.采用1 mmol·L-1鹅去氧胆酸(CDCA)共吸附剂对电池进行优化后,三种染料的能量转换效率分别提升到5.46%,4.98%和6.26%.
含咔唑/苯并咪唑环的2, 5-二取代-1, 3, 4-噻二唑酰胺衍生物的合成及对PTP1B/TCPTP抑制活性的评价
李英俊, 赵月, 靳焜, 高立信, 盛丽, 刘雪洁, 杨鸿境, 林乐弟, 李佳
2019, 39(9): 2599-2608  doi: 10.6023/cjoc201901013
[摘要]  (7) [HTML全文] (7) [PDF 2180KB] (0)
摘要:
合成了一系列新型含咔唑/苯并咪唑环的2,5-二取代-1,3,4-噻二唑酰胺衍生物.利用IR,1H NMR,13C NMR和元素分析对其进行了结构表征.评价了目标化合物对蛋白酪氨酸磷酸酶1B(PTP1B)和T细胞蛋白酪氨酸磷酸酶(TCPTP)的抑制活性,讨论了结构与活性的关系.实验结果显示,绝大多数化合物对PTP1B的抑制活性超过高度同源的TCPTP的抑制活性,其中2-(9-咔唑基亚甲基)-5-(3-氯苯甲酰氨基)-1,3,4-噻二唑(5c)对PTP1B的抑制活性最高[IC50=(2.43±0.43)μg/mL],2-(9-咔唑基亚甲基)-5-(4-甲基苯甲酰氨基)-1,3,4-噻二唑(5b)和化合物5c对PTP1B的抑制活性均高于阳性对照药物齐墩果酸.对目标化合物5c进行分子对接研究和密度泛函理论(DFT)计算.分子对接结果表明,5c与PTP1B酶通过形成氢键、疏水和π-π等相互作用形成稳定的复合物.
L-鸟嘌呤异核苷的全合成研究
唐杰, 董祥有, 欧阳文良, 朱云龙, 丁海新, 肖强
2019, 39(9): 2609-2615  doi: 10.6023/cjoc201901045
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摘要:
发展了一条改进的L-鸟嘌呤异核苷全合成路线.以L-核糖为起始原料,合成了3,5-O-二苄基-1-脱氧-L-核糖,再与碱基N2N2-二叔丁氧羰基-6-氯鸟嘌呤发生关键的Mitsunobu反应来合成异核苷6.经过9步反应,以37.3%的总收率合成了L-鸟嘌呤异核苷,其中Mitsunobu反应构建异核苷键具有立体专一性、高产率、条件温和、区域选择性高等优点.该方法可以作为鸟嘌呤异核苷的通用合成路线.
樟脑磺酸噻唑腙类化合物的设计、合成及抗氧化应用
张强健, 王芸芸, 赵雨珣, 马崇慧, 徐徐, 谷文, 杨益琴, 王石发
2019, 39(9): 2616-2624  doi: 10.6023/cjoc201901053
[摘要]  (7) [HTML全文] (7) [PDF 1076KB] (0)
摘要:
以樟脑衍生物樟脑磺酸为原料,经缩合、环化等反应,合成了22个樟脑磺酸噻唑腙类化合物,采用1H NMR、13C NMR、HR-MS等方法对产物的结构进行表征,并研究了它们的抗氧化活性.结果表明,不同取代基的樟脑磺酸噻唑腙类化合物表现出不同的抗氧化活性,其中(2-(2-(4-(4-氰基苯基)噻唑-2-基)亚肼基)-7,7-二甲基双环[2.2.1]庚-1-基)甲磺酸(Q19)消除1,1-二苯基-2-三硝基苯肼(DPPH)自由基的IC50值可达到176 μmol/L,(2-(2-(4-(4-氟苯基)噻唑-2-基)亚肼基)-7,7-二甲基双环[2.2.1]庚-1-基)甲磺酸(Q3)消除2,2-联氮-二(3-乙基-苯并噻唑-6-磺酸)二铵盐(ABTS)自由基的IC50值可达到20.6 μmol/L,(E)-(7,7-二甲基-2-(2-(4-(3-甲苯基)噻唑-2-基)亚肼基)双环[2.2.1]庚-1-基)甲磺酸(Q8)对羟基自由基的消除率可达到66.2%,(2-(2-(4-(4-联苯基)噻唑-2-基)亚肼基)-7,7-二甲基双环[2.2.1]庚-1-基)甲磺酸(Q20)消除过氧自由基的IC50值可达到20.7 μmol/L,均远超过阳性对照trolox的抗氧化活性.(2-(2-(4-(2-羟基苯基)噻唑-2-基)亚肼基)-7,7-二甲基双环[2.2.1]庚-1-基)甲磺酸(Q16)抑制酪氨酸酶的IC50值可达154.9 μmol/L,也优于阳性对照曲酸.对樟脑磺酸基噻唑腙类化合物的抗氧化机理进行了探索.
2-去氢表雄酮苯亚甲基衍生物的合成及抗炎活性研究
朱丽, 杨艳秋, 高佩佩, 安雪, 孙莹莹, 孙晓雯, 侯悦, 单丽红
2019, 39(9): 2625-2631  doi: 10.6023/cjoc201901039
[摘要]  (79) [HTML全文] (79) [PDF 501KB] (0)
摘要:
阿尔茨海默症作为21世纪全球主要健康危机之一,由于其发病机制的复杂性,目前还未找到很好的解决办法.为了找到更加经济有效的治疗神经退行性疾病的药物,合成了一系列新型2-去氢表雄酮苯亚甲基衍生物,并研究了其对脂多糖(LPS)激活小胶质细胞株BV-2 NO释放及细胞存活率的影响.结果表明所合成化合物作用24 h后,对LPS活化的小鼠小胶质细胞株BV2的NO释放均有不同程度的抑制作用,且具有一定的浓度依赖性.活性最好的化合物15β,16β-亚甲基雄甾-2-(3-氯)-苯亚甲基-4,6-二烯-3,17-二酮(5a)和15β,16β-亚甲基雄甾-2-(3,4,5-三甲氧基)-苯亚甲基-4,6-二烯-3,17-二酮(5j)的IC50值分别为2.69和3.28 μmol·L-1,优于阳性对照米诺环素.此类化合物在涉及活化小胶质细胞的神经退行性疾病方面的作用值得进一步研究.
含全氟环丁基芳基醚结构的疏水性聚碳酸酯的合成及性能研究
胡丹, 赵昆峰, 童琴, 何丹农
2019, 39(9): 2639-2644  doi: 10.6023/cjoc201812048
[摘要]  (7) [HTML全文] (7) [PDF 1149KB] (0)
摘要:
以商业化的对羟基苯甲醚为原料,合成了一种新型的含有全氟环丁基芳基醚结构的疏水性聚碳酸酯.该聚合物在不降低材料透明性的前提下,表现出了优异的热稳定性和疏水性,其热分解温度为351℃,涂膜与水的接触角为110°.为了进一步探究全氟环丁基芳基醚结构对聚碳酸酯的性能影响,以含有全氟环丁基芳基醚结构的单体和双酚A单体为原料,合成了一系列具有不同全氟环丁基芳基醚基团含量的聚碳酸酯.通过性能比较可知,将全氟环丁基芳基醚结构引入聚碳酸酯,能够降低聚碳酸酯的分散度,提高其热稳定性和疏水性.
N-溴代丁二酰亚胺促进的环丙烯羧酸酯的区域选择性开环反应
许露露, 叶倩雯, 程冬萍, 李小年, 许孝良
2019, 39(9): 2645-2649  doi: 10.6023/cjoc201812029
[摘要]  (8) [HTML全文] (8) [PDF 439KB] (1)
摘要:
环丙烯类化合物含有环内碳碳双键,巨大的环张力导致其具有活泼的化学反应特性.主要研究了N-溴代丁二酰亚胺促进的环丙烯二羧酸酯类化合物的区域选择性开环,得到官能化的αβ-不饱和羧酸酯类化合物.该反应条件温和,操作简单.
Articles
A New Dicyano-vinyl Modified Difurylperhydrocyclopentene Photoswitch: Fluorescent Properties, Sensing Ability and in vivo Application
Tianjiao Zheng, Xuanying Chen, Liangliang Zhu, Daolei Wang, Qi Zou, Tao Zeng, Wenbo Chen
2019, 39(9): 2492-2498  doi: 10.6023/cjoc201903033
[摘要]  (6) [HTML全文] (6) [PDF 4327KB] (0)
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Recently, fluorescent labeling techniques have been greatly developed with the aid of highly optimized small-molecule fluorescent dyes, fluorescent proteins and advanced tagging techniques. Many reasonable strategies have been used to design fluorescent diarylethene, mainly focusing on the introduction of luminophores by conjugated junction and the modification of aryl cores in the diarylethene. Compared to thiophene, furan has superior properties such as solubility, biodegradable ability and rigidity fluorescence. Therefore, difurylethene is a better candidate for fluorescent labeling techniques. Herein, a new fluorescent photoswitch based on dicyano-vinyl modified difurylethenes was designed and prepared. This compound demonstrates typical reversible photochromism in solution and outstanding performance for the fluorescent detection of cyanide ions with excellent selectivity, sensitivity and high contrast. Furthermore, the mechanism of sensing toward cyanide ions was explained by 1H NMR titrations experiments. Owing to the strong fluorescence from a superior derivation with furan instead of thiophene, it is successfully applied as the fluorescent dyes and probe for detecting cyanide ions in vivo application.
Synthesis and Biological Activity Research of 4-Substitued-1-(2-methyl-6-(pyridin-3-yl)-nicotinoyl) Semicarbazides
Hongyu Hu, Jun Wu, Jianfeng Yuan, Zhenni Wang, Chenfan Li, Xiaoyan Yan, Meijuan Fang, Shengxian Zhao
2019, 39(9): 2507-2514  doi: 10.6023/cjoc201902033
[摘要]  (14) [HTML全文] (14) [PDF 1072KB] (0)
摘要:
A series of 4-substitued-1-(2-methyl-6-(pyridin-3-yl)-nicotinoyl) semicarbazides were synthesized via molecular hybridization strategy. The synthesized compounds were screened for their anticancer potential against different cancer cells viz human hepatocelular carcinoma (QGY-7703), non-small cell lung (NCl-H460) and human breast (MCF-7) cancer cell lines by methyl thiazolyl tetrazolium (MTT) assay. 1-(2-Methyl-6-(pyridin-3-yl)nicotinoyl)-4-(2, 4, 6-trichlorophenyl)semicarbazide (4n) showed significant anticancer activity in these cancer cell lines with a range of IC50 values from 8.89 μmol/L to 11.45 μmol/L. Further biology studies showed that 4n treatment obviously increased the level of cleaved PARP and induced the apoptosis in QGY-7703 cells.
Synthesis of Benzyl Phenol from Benzyl Aryl Ether by Polyphosphoric Acid-Catalyzed Benzyl Rearrangement
Zhuyun Liu, Juanjuan Xu, Bin Ling, Yanxiang Li, Guangcong Liu, Lizhong Wang, Guochun Zhou
2019, 39(9): 2515-2524  doi: 10.6023/cjoc201901042
[摘要]  (10) [HTML全文] (10) [PDF 516KB] (0)
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The rearrangement activity of benzyl aryl ether catalyzed by polyphosphoric acid (PPA) was systematically investigated. Optimal structural tuning of substitutions of electron withdrawing group (EWG) and electron donating group (EDG) at phenolic moiety or benzyl moiety benefits the rearrangement and the regio-selectivity of the rearrangement obeyed the substitution directing rule at the aromatic ring. This readily available rearrangement method is of practical interest for the benzylation of diverse aromatic phenols.
Synthesis and Antitumor Activity Evaluation of 2, 4-Substituted Py-rimidine Derivatives Containing Trifluoromethyl
Yaqi Meng, Erdong Li, Yang Zhang, Shuan Liu, Chongnan Bao, Peng Yang, Luye Zhang, Danqing Zhang, Jikuan Wang, Yaxin Chen, Na Li, Jingchao Xin, Peirong Zhao, Yu Ke, Qiurong Zhang, Hongmin Liu
2019, 39(9): 2541-2548  doi: 10.6023/cjoc201903022
[摘要]  (8) [HTML全文] (8) [PDF 608KB] (0)
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In order to find more effective antitumor drugs, a series of novel 2, 4-substituted pyrimidine derivatives containing trifluoromethyl were designed, synthesized, and evaluated for antitumor activity aganist EC-109 (human esophageal cancer cell), MGC-803 (human gastric cancer cell), PC-3 (human prostate cancer cell) and HepG-2 (human liver cancer cell). The results showed that some compounds displayed moderate to potent antitumor activity against PC-3. Among them, 2-(((4-((1-methyl-1H-tetrazol-5-yl)thio)-6-(trifluoromethyl)pyrimidin-2-yl)thio)methyl)benzo[d]thiazole (13w) possesses strong antitu-mor activity against PC-3 with IC50 value of 1.76 μmol·L-1, and the antitumor activity is significantly better than the positive control drug of 5-fluorouracil.
Synthesis of Bicyclic ortho-Aminocarbonitrile Derivatives Catalyzed by 1, 4-Diazabicyclo[2.2.2]octane
Shiqiang Yan, Daoqing Dong, Chunwen Xie, Wensheng Wang, Zuli Wang
2019, 39(9): 2560-2566  doi: 10.6023/cjoc201901023
[摘要]  (7) [HTML全文] (7) [PDF 477KB] (0)
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One-pot three-component reactions catalyzed by 1, 4-diazabicyclo[2.2.2]octane (DABCO) for the synthesis of bicyclic ortho-aminocarbonitrile derivatives (21 examples, 68%~96%) have been developed. The reactions proceeded smoothly at room temperature and generated the corresponding products in short reaction time with high to excellent yields. Importantly, the desired products could be easily collected through simple filtration and washing with ethanol.
Design, Synthesis and Biological Activity Screening of Novel Amide Derivatives Containing Aromatic Thioether Group
Xuewen Hua, Nannan Liu, Zhijin Fan, Guangning Zong, Yi Ma, Kang Lei, Hao Yin, Guiqing Wang
2019, 39(9): 2581-2588  doi: 10.6023/cjoc201903004
[摘要]  (8) [HTML全文] (8) [PDF 1872KB] (0)
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A series of amide derivatives containing aromatic sulfide and sulfone groups synthesized in our previous work displayed excellent nematocidal activity at 200 μg/mL. In order to explore the effect of structural modification of the amide bridge on biological activity in a more delicate way, two series of novel target compounds were designed and synthesized by adopting amide group flipping and introducing N-sulfonyl substituted amide bonds. The bioassays indicated that the structural modification of the amide bridge had important effects on their nematocidal and fungicidal activities, which the introduction of the N-sulfonyl substituent on the amide group was favorable to improving the nematocidal activity in comparison with compounds . The molecular docking revealed that directly attaching the carbonyl or sulfonyl groups in the amide bridge to the aromatic rings was advantageous to the nematocidal activity.
Synthesis of Quinazolinone Derivatives Catalyzed by Alkaline Protease
Zongbo Xie, Hongxia Li, Liansheng Liu, Jin Lan, Zhiyu Hu, Zhanggao Le
2019, 39(9): 2632-2638  doi: 10.6023/cjoc201901037
[摘要]  (10) [HTML全文] (10) [PDF 458KB] (0)
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Alkaline protease-catalyzed synthesis of quinazolinone derivatives was developed between β-keotester and o-aminobenzamide. Because ethanol is one kind of eco-friendly solvents, this method can reduce the impact of solvents on the environment. Alkaline protease as a biocatalyst has many advantages, e.g. high catalytic activity, environmentally friendly, wide variety of sources and simple operation. In addition, a variety of quinazolinone derivatives was obtained with good to excellent yields just using 2000 U alkaline protease as catalyst.
研究简报
8-羟基异香豆素的合成方法研究
郭冬冬, 张武霞, 王永强
2019, 39(9): 2650-2654  doi: 10.6023/cjoc201906001
[摘要]  (9) [HTML全文] (9) [PDF 458KB] (0)
摘要:
对8-羟基异香豆素的合成方法进行研究.以麦氏酸为原料,通过傅克酰基化,羰基保护,酯基还原,脱保护,得到关键中间体3-乙炔基-2-(羟甲基)环己-2-烯-1-酮,再经酸性环化加成,环己烯酮环的芳构化,2,3-二氯-5,6-二氰对苯醌(DDQ)氧化等步骤,合成得到8-羟基异香豆素.合成的化合物结构经过1H NMR,13C NMR,IR,HRMS表征.
3-芳基异噁唑啉-吡唑-5-甲酰胺类化合物的合成及杀虫活性研究
钟良坤, 江涛, 张帆, 付庆, 刘幸海, 许天明, 丁成荣, 陈杰, 袁静, 谭成侠
2019, 39(9): 2655-2662  doi: 10.6023/cjoc201903056
[摘要]  (20) [HTML全文] (20) [PDF 566KB] (0)
摘要:
以5,5-二甲氧基-2,4-二氧代戊酸乙酯为原料,设计合成了一系列含芳基异噁唑啉结构的吡唑-5-甲酰胺类化合物,产物结构经1H NMR,13C NMR和HRMS确认.初步杀虫活性测试表明,多数化合物在500 mg/L浓度下对粘虫(Mythimna separate)有着较高的活性(致死率≥ 80%),在100 mg/L的浓度下,有三种化合物对粘虫仍有中等程度的活性(致死率≥ 60%).在500 mg/L时,有四种化合物对苜蓿蚜(Aphis craccivora)也有较好的活性(致死率≥ 80%).因此,对该类化合物的结构优化可作为寻求新型杀虫剂而进行深入研究.
C(3)-1, 2, 4-三氮唑取代的1, 5-苯并硫氮杂䓬的合成及抑菌活性
王岩, 孔令满, 王冉冉, 田克情, 张萍
2019, 39(9): 2663-2670  doi: 10.6023/cjoc201901041
[摘要]  (6) [HTML全文] (6) [PDF 503KB] (0)
摘要:
设计合成了3类C(3)-1,2,4-三氮唑取代的1,5-苯并硫氮杂䓬化合物,2,3-二氢/2,5-二氢/2,3,4,5-四氢-3-(1,2,4-三氮唑)-4-芳基-1,5-苯并硫氮杂䓬.研究了中间体及目标产物的合成条件,确定了其中2个副产物的结构.目标产物的抑菌活性测试表明,2,3-二氢/2,5-二氢-3-(1,2,4-三氮唑)-4-芳基-1,5-苯并硫氮杂䓬对新生隐球菌和白色念珠菌表现出很高的抑制作用,在200 μg/disc的浓度下,有4个化合物对新生隐球菌的抑制作用高于对照药物氟康唑,有3个化合物对白色念珠菌的抑制活性高于对照药物氟康唑.初步抑真菌构效关系研究表明,1,2,4-三氮唑环和C=N双键是2,3-二氢-3-(1,2,4-三氮唑)-4-芳基-1,5-苯并硫氮杂䓬抑真菌活性的关键药效团.
磷脂酰基醇3-激酶抑制剂甲磺酸普喹替尼的合成
沈大冬, 朱金林, 吴国锋, 盛力, 高浩凌, 王普
2019, 39(9): 2676-2680  doi: 10.6023/cjoc201902020
[摘要]  (11) [HTML全文] (11) [PDF 469KB] (0)
摘要:
甲磺酸普喹替尼是一种新颖的磷脂酰基醇3-激酶(PI3K)抑制剂,临床实验结果显示对肿瘤治疗有较好的效果.报道了公斤级合成该抑制剂的方法,以2,6-二氯嘌呤为起始原料,通过氨基上保护、区域选择性SN2亲核取代反应、Buchwald-Hartwig偶联反应,氨基脱保护成盐合成了甲磺酸普喹替尼,该法操作简单,总收率达到48%,为其放大生产提供了有效途径.
Notes
Synthesis of 3-Dehydroxyphomonol
Qingqing Ye, Mengfan Zhang, Yaozong Liu, Zhen Yang
2019, 39(9): 2671-2675  doi: 10.6023/cjoc201903014
[摘要]  (6) [HTML全文] (6) [PDF 401KB] (0)
摘要:
A concise synthesis of 3-dehydroxyphomonol has been accomplished in six steps from commercially available (R)-4-chloro-3-hydroxy-butyric acid ethyl ester or (S)-2-propyl-oxirane. The key steps involved Grignard reaction, Prins cyclization and palladium-catalyzed intramolecular alkoxycarbonylation to install the tetrahydropyran ring. The synthesis demonstrated an application of protecting-group-free strategy.
亮点介绍
亮点介绍(4)篇
2019, 39(9): 2681-2684
[摘要]  (8) [HTML全文] (8) [PDF 905KB] (0)
摘要:
ACCOUNT
Transition-Metal-Catalyzed Carbonylative Synthesis and Functionalization of Heterocycles
Zhiping Yin, Zechao Wang, Xiao-Feng Wu
2019, 39(3): 573-590  doi: 10.6023/cjoc201809004
[摘要]  (354) [HTML全文] (354) [PDF 1793KB] (354)
摘要:
Heterocycles are ubiquitous in natural products, pharmaceuticals, organic materials, and numerous functional molecules. These structural units probably constitute the largest and most varied family of organic compounds. Hence the development of new procedures for heterocycles synthesis has been a hot research topic for over centuries. Among all the new synthetic methods, transition-metal-catalyzed reactions are attractive. Those reactions can formulate complicated heterocycles efficiently from available starting materials under mild conditions and atom economical routes. Among them, transition-metal-catalyzed carbonylation reaction has become an efficient and useful tool in organic synthesis since the first hydroformylation reaction developed by W. Reppe at BASF in the 1930s. Since then impressive progress has been achieved in this area. In nowadays, various types of carbonylation reactions were established. Substrates including aryl halides, olefins, alkynes or simply C-H bond can be activated and produce the corresponding carbonyl-containing compounds smoothly. On the other hand, carbon monoxide was discovered and identified in the 18th century. Since the first applications in industry around 80 years ago, academic and industrial laboratories have explored uses of CO in chemical reactions broadly. However, because of the special physical properties of CO, organic chemists were often reluctant to apply carbonylations frequently in laboratories. Hence, different kinds of CO surrogates were developed and applied in carbonylation reactions, such as metal carbonyl compounds M(CO)x, formates, alcohols, formic acid, aldehyde, biomass and carbon dioxide. Those CO surrogates offer interesting opportunities for carbonylation reactions. This account mainly outlines our progress in the development of transition-metal-catalyzed carbonylative synthesis and functionalization of heterocycles from 2012 to 2018. With copper, palladium, rhodium, ruthenium and iridium as the catalysts and relying on the activation of carbon-halogen and carbon-hydrogen bonds, we are able to synthesis various of heterocycles by using CO gas or CO surrogates as the C1 building blocks.
综述与进展
检测活性氮/活性氧的分子荧光探针
矫春鹏, 刘媛媛, 路文娟, 张平平, 王延风
2019, 39(3): 591-616  doi: 10.6023/cjoc201810013
[摘要]  (502) [HTML全文] (502) [PDF 1971KB] (502)
摘要:
活性氮和活性氧是具有强生物活性的化学物质.在人体细胞中,由于酶促或非酶促过程均可生成过氧化物,该物种的异常水平会引起氧化损伤与衰老和各种疾病,如心血管疾病、神经性疾病、阿尔茨海默病、帕金森病甚至癌症.因此,发展选择性识别和高灵敏度的分子荧光探针,实现活性氮或活性氧的有效检测具有重要意义.分子荧光探针检测法与成像技术具有灵敏度高、选择性强、损伤性小和细胞相容性好等优点,并在阐述活性氮和活性氧的病理生理过程中起到重要作用,在生物和医学等领域应用广泛.然而,由于活性氮和活性氧自身的特殊性而存在许多难题,例如反应活性高、存在周期短等一直困扰研究人员.着重综述了近年来发展的分子荧光探针用于活性氮和活性氧的检测及细胞成像工作的研究进展,提出进一步构建新型分子荧光探针用于活性氮和活性氧检测面临的挑战、未来发展方向及展望.
亚磺酸钠参与合成含硫化合物研究进展
黄国保, 李秀英, 罗金荣, 罗志辉, 谭明雄
2019, 39(3): 617-624  doi: 10.6023/cjoc201809030
[摘要]  (282) [HTML全文] (282) [PDF 602KB] (282)
摘要:
亚磺酸钠(RSO2Na)性质稳定、合成简单、价格低廉,在有机合成化学领域被广泛应用.综述了最近五年来亚磺酸钠在合成含硫化合物反应中的最新研究进展.分别叙述了其在有机反应中构建S-C键、S-杂键(S-S键、S-N键以及S-P键)的底物适应范围和反应机理,为今后亚磺酸钠的在有机合成中的应用提供参考.
烯烃的双官能团化反应研究进展
付晓飞, 赵文献
2019, 39(3): 625-647  doi: 10.6023/cjoc201808031
[摘要]  (560) [HTML全文] (560) [PDF 1035KB] (560)
摘要:
作为一类重要的有机化学反应,烯烃的双官能团化反应不仅可以经济有效地一步合成多位点反应产物,而且可以将起始原料转化为多种含有生物活性或药物活性的化合物,同时还为构建化学结构的多样性提供了更多的方法,所以发展烯烃的双官能团化反应十分重要.对近十二年来各类烯烃的双官能团化反应进行了综述.主要分为:铜催化的烯烃的双官能团化反应、其它过渡金属催化的烯烃的双官能团化反应以及非金属催化的烯烃的双官能团化反应.同时对该类反应的发展前景进行了展望.
聚乙二醇:绿色有机合成的新媒介
肖立伟, 戴富才, 李政, 景学敏, 孔洁, 刘光仙
2019, 39(3): 648-660  doi: 10.6023/cjoc201807056
[摘要]  (555) [HTML全文] (555) [PDF 811KB] (555)
摘要:
聚乙二醇(PEG)可以溶解多种有机物和金属配合物,具有良好的热稳定性、难挥发、无毒、能生物降解、廉价易得,易于回收和循环使用.PEG作为绿色介质已经成功地应用到许多有机反应中,如碳-碳偶联反应、碳-杂偶联反应、多组分反应、缩合反应、加成反应、取代反应、氧化反应、还原反应等.总结了近年来PEG作为反应介质在不同有机反应中的应用情况.
铜催化下含氮化合物的Chan-Lam偶联反应的研究进展
段希焱, 刘宁, 王佳, 马军营
2019, 39(3): 661-667  doi: 10.6023/cjoc201808015
[摘要]  (371) [HTML全文] (371) [PDF 567KB] (371)
摘要:
构筑碳-氮键在有机合成和药物化学领域有着重要的意义.近年来关于碳氮键合成反应的研究取得了长足的进展.其中铜催化的Chan-Lam偶联反应是构筑碳氮键最有效和直接的方式之一.系统综述了近十多年Chan-Lam偶联反应直接构筑C-N键的催化机理、反应体系、底物范围及结构特点等.
化学-酶多步串联反应及其在高附加值手性化合物高效、绿色合成中的应用
廖旭, 蒋岩, 赖石林, 刘源岗, 王士斌, 熊兴泉
2019, 39(3): 668-678  doi: 10.6023/cjoc201807038
[摘要]  (389) [HTML全文] (389) [PDF 882KB] (389)
摘要:
与化学催化或酶催化合成相比,化学-酶相结合的多步串联反应是一种更简单、高效、经济的方法,兼具酶催化剂的高效、高选择性等优点,且合成原料价廉易得,合成工艺简捷高效,生产环境绿色友好,所得产品光学纯度高,使其在高附加值手性化合物的开发和合成方面得到了广泛的应用.近年来,化学家们通过改变催化剂和设计更为合理的反应方式,致力于将化学-酶催化反应条件变得更为容易,从而将其应用于更多反应领域.综述了近年来国内外化学-酶多步串联反应,如酶与金属催化、酶与有机催化、酶与新型反应技术等相结合多步串联合成手性醇类、环氧类、杂环类以及其他手性化合物的研究进展,并对该领域的发展趋势进行了展望.
菲并咪唑类衍生物蓝光材料的研究进展
邱志鹏, 谭继华, 蔡宁, 王凯, 籍少敏, 霍延平
2019, 39(3): 679-696  doi: 10.6023/cjoc201807007
[摘要]  (299) [HTML全文] (299) [PDF 1560KB] (299)
摘要:
即将出现的全球能源危机和低效的能源利用推动了节能设备在显示和照明领域中的应用.节能的有机发光二极管被认为是新一代智能显示器,成为未来节能照明光源最具竞争力的候选产品之一.而高效深蓝色材料的分子设计由于其固有的宽带隙,载流子电荷传输不平衡以及其在固态下的低效率,发展受到很大限制.菲并咪唑基团作为一种新型蓝光材料的构筑单元,具吸引力的双极特性和优异的荧光效率,引起了科研工作者的强烈兴趣.对于菲并咪唑基团深蓝光材料的分子设计及其光物理性能研究具有重要的意义.综述了近几年来含有菲并咪唑类基团蓝光材料的发展状况,对菲并咪唑基团衍生物电致发光器件的发光机理、设计思路与最新进展进行了综述,并对其在未来全彩显示和固态照明领域上的前景进行了展望.
研究论文
一种黄酮荧光探针对肼的识别及细胞成像
鞠志宇, 舒朋华, 谢智宇, 蒋雨晴, 陶伟杰, 许志红
2019, 39(3): 697-702  doi: 10.6023/cjoc201808035
[摘要]  (256) [HTML全文] (256) [PDF 1248KB] (256)
摘要:
以邻羟基苯乙酮和对甲基苯甲醛为原料,合成了合成了一种3-羟基黄酮酯化物HFBA.通过探针HFBA对N2H4的识别性质研究,结果表明,探针HFBA在二甲亚砜-水溶液[V(DMSO):V(H2O)=7:3,PBS 20 mmol/L,pH=7.4]中对N2H4具有良好的选择性和灵敏度,且响应快速,抗干扰能力强,其检测限为0.11 μmol/L.细胞成像实验表明,探针HFBA可用于细胞内N2H4的检测.
Sc(Ⅲ)催化胺对邻亚甲基苯醌氮杂迈克尔加成反应合成贝蒂碱衍生物
张硕, 赵宁, 李庆刚, 张嘉祺, 侯梓桐, 刘一帆, 于一涛, 彭丹, 王峰, 李冰, 李金辉
2019, 39(3): 709-719  doi: 10.6023/cjoc201808045
[摘要]  (271) [HTML全文] (271) [PDF 561KB] (271)
摘要:
邻亚甲基苯醌化合物是一类非常活泼和重要的中间体,被广泛应用于天然产物和药物化学中.以2-[羟基(苯基)甲基]苯酚类化合物和胺为原料,1,2-二氯乙烷为溶剂,在Sc(Ⅲ)促进下原位生成邻亚甲基苯醌,并发生氮杂迈克尔加成反应合成贝蒂碱衍生物.反应在封管条件下90℃搅拌4 h完成,以76%~96%的产率得到目标产物.
基于新型帆船型络合物的超分子组装
张世龙, 蒋腊生
2019, 39(3): 720-726  doi: 10.6023/cjoc201810001
[摘要]  (271) [HTML全文] (271) [PDF 2553KB] (271)
摘要:
由于二芳基冠醚独特的大环型空腔结构及其对于客体分子的良好络合能力,利用分子内氢键成功设计了一类新型的、可通过酸碱控制其构型的帆船型自身络合物,对其进行了超分子组装,进而合成了一种新型索烃.通过利用分子间的电荷转移相互作用,以主体:客体=1:1的模板法,合成了一类新颖的索烃,利用了1H NMR、13C NMR、HRMS和1H-1H NOESY表征了其结构,希望通过改变酸碱环境控制其驱动.
铑/锌共催化苯酚对氧杂苯并降冰片烯的不对称开环反应研究
和振秀, 周永云, 孙蔚青, 樊瑞峰, 沈国礼, 樊保敏
2019, 39(3): 754-760  doi: 10.6023/cjoc201808027
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摘要:
通过研究发现[Rh(COD)Cl]2/ZnI2/(2R,4R)-(+)-2,4-bis(diphenylphosphino)pentane作为共催化体系,能有效地催化酚类亲核试剂对氧杂苯并降冰片烯的不对称亲核开环反应,获得较好的收率和良好的对映选择性.在优化后的反应条件下,该共催化体系具有良好的催化活性和底物适应能力,能够实现各种取代的酚类亲核试剂对氧杂苯并降冰片烯的不对称开环,高效而又经济地合成不同取代的含手性四氢萘结构单元的化合物.
稠合四环噻嗪烷-4-酮衍生物的合成及其抗肿瘤活性
牛丽萍, 邢顺凯, 李小六, 陈华
2019, 39(3): 771-777  doi: 10.6023/cjoc201807043
[摘要]  (250) [HTML全文] (250) [PDF 814KB] (250)
摘要:
以叔丁氧羰基(Boc)保护的脯氨醛1、氨基酸酯盐酸盐2a~2d和巯基水杨酸3a~3b为原料,三组分一锅法得到苯并噻嗪烷-4-酮中间体.酸性条件下脱除Boc,分子内酰胺缩合制备稠合四环噻嗪烷-4-酮衍生物6~11.新生成手性碳(1-C)的构型通过H-1和H-2的偶合常数及X-ray单晶衍射确定.测试了化合物抗Hela和A549的肿瘤细胞增殖活性.结果表明,部分化合物具有中等的抗Hela细胞活性,其中(13aR,13bR)-1,2,3,13b-四氢苯并[e]吡咯并[2',1':3,4]吡嗪并[2,1-b][1, 3]噻嗪-5,8(6H,13aH)-二酮(6b)的IC50值为9.50 μmol/L.所有化合物对A549的细胞没有抑制活性.
寨卡病毒抑制剂的虚拟筛选、设计、合成及生物活性研究
李彦忠, 齐思佳, 徐彦浩, 夏成才, 段桂运
2019, 39(3): 786-792  doi: 10.6023/cjoc201807053
[摘要]  (264) [HTML全文] (264) [PDF 3978KB] (264)
摘要:
由甲基转移酶和RNA聚合酶组成的多功能蛋白(NS5)是寨卡病毒复制过程中起主要作用的蛋白组分,其甲基转移酶(5M5B)部分是病毒复制和宿主固有免疫应答的中心参与者,因此被作为潜在抗寨卡病毒药物开发的首选靶标蛋白.将5M5B作为受体,利用其已知的结合位点与200多万个化合物小分子进行虚拟筛选,得到抗寨卡病毒的先导化合物2a,并对该先导化合物进行结构优化、改造、活性预测、化学合成、药理活性研究.使用1H NMR和13C NMR对所有合成的化合物进行了表征,并进行了体外活性测试.结果表明化合物3a[IC50=(7.69±0.36)μmol·L-1]的体外活性优于广谱抗病毒药利巴韦林活性[IC50=(8.15±0.42)μmol·L-1],本研究的方法与结果对寨卡病毒抑制剂的结构设计研究具有重要的指导作用.
系列红色染料的合成、光学性质及在蛋白标记中的应用
李慧芳, 冷鑫, 闫立润, 杨秉勤, 白银娟
2019, 39(3): 793-799  doi: 10.6023/cjoc201807036
[摘要]  (245) [HTML全文] (245) [PDF 2437KB] (245)
摘要:
以3-NN-二乙基氨基酚为原料合成了一系列荧光染料,用1H NMR,13C NMR,IR,HRMS对结构进行了表征,检测了新型染料的光学性质,标记了牛血清白蛋白,比较了新染料与菁染料(Cy3)在凝集素微阵列芯片上的荧光信号值.结果显示,新型染料的最大发射波长均在600 nm以上,斯托克斯位移约70 nm左右,染料/蛋白质(D/P)标记效率高达1.5~1.8,在凝集素微阵列中新染料和Cy3的荧光信号值相当.表明新染料可以作为荧光标记物用于凝集素微阵列中检测糖链的变化.
ARTICLES
Synthesis and Evaluation of Chalcone Derivatives as Novel Anticancer Agents
Qiwei Sheng, Wanqiu Zhao, Ming Zeng, Zhongpao Xie, Yaping Xia, Dongmei Cui
2019, 39(3): 703-708  doi: 10.6023/cjoc201808037
[摘要]  (220) [HTML全文] (220) [PDF 456KB] (220)
摘要:
Three series of chalcones bearing a piperidino, morpholino, and 1-methylpiperazino moiety were synthesized in two steps with the key step being Claisen-Schmidt condensation and tested for the activity against five cell lines, MCF-7 (human breast adenocarcinoma cell line), A549 (human lung adenocarcinoma epithelial cell line), HL-60 (human leukemia cell line), Hela (human cervical cancer cell line), and Bewo (human chorionic tumor cell line) by thiazolyl blue tetrazolium bromide (MTT) assay. Some chalcones exhibited good anticancer activity, and among them 4a, 4e, 4f, 4j, 4m, and 4o displayed the best anticancer activity for MCF-7 breast cancer cells, A549 lung cancer cells, and HL-60 leukemia cancer cells with IC50 values below 10 μmol/L, respectively.
Research on Reduction of α, α, α-Tribromomethyl Ketones via Thiophenol
Ying Yang, Hasimujiang Balati, Abudu Rexit Abulikemu
2019, 39(3): 727-733  doi: 10.6023/cjoc201810003
[摘要]  (233) [HTML全文] (233) [PDF 401KB] (233)
摘要:
α, α-Dibromomethyl ketones were synthesized with high yields through a thiophenol-promoted reduction of α, α, α-tribromomethyl ketones under mild conditions within one hour. A further mechanistic study showed that the reaction proceeded via a radical process. This is an example that uses thiophenol as the radical stimulator in the reduction of multi-halogenated compounds.
Nano-Gold Catalyzed Transesterification of (Hetero) aryl Esters with Alkyl Halides via C-O Activation
Hongpeng Ma, Chaolumen Bai, Yongsheng Bao
2019, 39(3): 734-746  doi: 10.6023/cjoc201809027
[摘要]  (199) [HTML全文] (199) [PDF 1491KB] (199)
摘要:
Nano-gold catalyzed transesterification of the (hetero) aryl ester with alkyl halides via C-O activation has been developed. In a series of supported AuNPs and PdNPs, the Au/γ-Al2O3 catalyst with an AuNP mean diameter of 3.63 nm and 3 wt% Au loading exhibited the best catalytic performance. The catalyst can be reused and shows high activity after five cycles. The X-ray photoelectron spectroscopy (XPS) analysis of the catalyst before and after the reaction suggested that the reaction might be performed via a catalytic cycle that began with Au0.
Synthesis, Biological Evaluation, and Structure-Activity Relationship Study of Unsaturated Spiroacetals as Potential Sex Attractants to Oriental Fruit Flies (Bactrocera dorsalis)
Jiuyi Li, Li Chen, Biaolin Yin
2019, 39(3): 747-753  doi: 10.6023/cjoc201808022
[摘要]  (209) [HTML全文] (209) [PDF 475KB] (209)
摘要:
Spiroacetal motif is widely distributed in many bioactive natural products of different origins and essentially contributes to various bioactivities. In this paper, two series of spiroacetals were synthesized and biologically evaluated as insect sex attractant towards oriental fruit flies (Bactrocera dorsalis) using methyleugenol as the standard. Biological evaluation demonstrated that a large part of the tested compounds triggered apparent electrophysiological responses from both male and female fruit flies. The stereochemistry of the spiroacetals and the substitution on their phenyl rings influenced the responses to some degree.
Synthesis and Applications of Excimer Host Materials Based on 2, 4, 6-Triphenyl-1, 3, 5-triazine and Fluorene Moieties
Xu He, Yuping Xiao, Xinlei Yuan, Shanghui Ye, Hongji Jiang
2019, 39(3): 761-770  doi: 10.6023/cjoc201806017
[摘要]  (220) [HTML全文] (220) [PDF 1319KB] (220)
摘要:
Three new bipolar derivatives based on 2, 4, 6-triphenyl-1, 3, 5-triazine and fluorene moieties, namely FTRZ, pTFTRZ and mTFTRZ were designed and synthesized by using 9-(4-(hexyloxy) phenyl) -9H-fluorene, 2-bromo-4, 6-diphenyl-1, 3, 5-triazine, 2, 4, 6-tris(4-bromophenyl) -1, 3, 5-triazine, and 2, 4, 6-tris(3-bromophenyl) -1, 3, 5-triazine through palladium-cata-lyzed cross-coupling reaction, which were reported as hosts for thermally activated delayed fluorescence organic light-emitting diodes (OLEDs). The 1H NMR, 13C NMR and MALDI-TOF-MS spectra were used to characterize the chemical structure of compounds FTRZ, pTFTRZ and mTFTRZ. Their thermal, photophysical and electrochemical properties as well as electroluminescent device performance were thoroughly investigated to correlate the optoelectronic properties with the topology-varied molecular structure. The thermal decomposition temperatures of compounds FTRZ, pTFTRZ and mTFTRZ are 427, 446 and 424℃ and their glass transition temperatures of compounds pFTRZ and mTFTRZ are 120 and 103℃, respectively. The optical band gaps of compounds FTRZ, pTFTRZ and mTFTRZ in toluene solution are 3.24, 3.29 and 3.24 eV, and their triplet energy levels are 3.04, 3.11 and 3.05 eV, respectively. Due to the π-π interaction between 2, 4, 6-triphenyl-1, 3, 5-triazine planes, compounds FTRZ, pTFTRZ and mTFTRZ form excimer in the thin film state. The electroluminescent properties of OLEDs using compounds FTRZ, pTFTRZ and mTFTRZ as the hosts and 2, 4, 5, 6-tetrakis(carbazol-9-yl) -1, 3-dicyanobenzene as the guest emitter were investigated. The green OLED of compound FTRZ as host material shows a peak emission at 510 nm with a maximum current efficiency of 6.7 cd/A, a maximum external quantum efficiency of 2.07% and a maximum brightness of 35718 cd/m2. The efficiency roll-offs of the OLEDs hosted by compounds FTRZ and pTFTRZ at 20000 cd/m2 are 3% and 2%, which are much better than the same device hosted by compound mTFTRZ.
Design, Synthesis and Evaluation of Novel Gd-Based 1, 4, 7, 10-Tetraazacyclododecan-N, N', N, N'-tetraacetic Acid-Hydrazide Derived Contrast Agents for Magnetic Resonance Imaging
Hongshun Sun, Jin Zhou, Yulong Li, Hong Jiang, Yan Zhang, Jianqiang Wang, Cheng Guo, Linjiang Shen
2019, 39(3): 778-785  doi: 10.6023/cjoc201808005
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摘要:
Magnetic resonance imaging (MRI) is widely used in diagnostic medicine and soft tissue imaging. Contrast agents (CAs) can improve the specificity of MRI enhancement. Herein, the design, synthesis and characterization of twelve novel Gd-based 1, 4, 7, 10-tetraazacyclododecan-N, N', N, N'-tetraacetic acid (DOTA) -hydrazide derived contrast agents for MRI were reported. Among of them, 5d, 5h and 5l exhibit higher longitudinal relaxivities than the clinical Gd-DOTA at 0.5 T. The relaxivities r1 of 5d, 5h and 5l are 4.67, 4.85 and 5.33 L·mmol-1·s-1 respectively. In vivo liver-target MRI shows that the potential of complex 5d was used as a novel liver-target contrast agent for MRI.
ARTICLE
Chemoselective Synthesis of Substituted Benzoxazines and Imidazolidines by Reactions of Hydroxyl Substituted Ethylenediamine Derivatives with Aldehydes
Zilong Tang, Ming Wang, Yuan Yao, Jingzhao Tan, Ningning Dai, Xinxing Li, Lifen Peng, Yinchun Jiao
2019, 39(3): 800-810  doi: 10.6023/cjoc201808003
[摘要]  (190) [HTML全文] (190) [PDF 498KB] (190)
摘要:
Lewis acid La(OTf) 3-catalyzed chemoselective cyclization of hydroxyl substituted ethylenediamine derivatives with aldehydes has been described for the first time, which provides efficient access to diversely functionalized 1, 3-imidazoli-dines and 3, 1-benzoxazines in generally good yields only by adjusting the position of the methylene group within hydroxyl substituted ethylenediamines. The reaction is suitable to aromatic aldehydes and aliphatic ones. Plausible mechanisms are also proposed to explain the observed reaction modes, wherein the nucleophilicity of nitrogen and oxygen atoms plays an important role in controlling the chemoselectivity.
α-Oxygenation of Benzylic Ethers to Esters Using MnOx-N@C Catalyst
Jing Liu, Cong Wan, Aili Zheng, Lianyue Wang, Kaiyue Yin, Dandan Liu, Shengde Wang, Lanhui Ren, Shuang Gao
2019, 39(3): 811-820  doi: 10.6023/cjoc201807011
[摘要]  (183) [HTML全文] (183) [PDF 4056KB] (183)
摘要:
A catalytic system for the oxidation of benzylic ethers to esters has been developed utilizing reusable MnOx-N@C as catalyst and tert-butyl hydroperoxide (TBHP) as benign oxidant under neat condition. The catalytic oxidation system has good functional groups tolerance and excellent chemoselectivity, and this catalytic procedure can also be scaled up.
Synthesis and Antitumor Activity of Novel Isolongifolic-Alkyl Dihydropyrimidinethione Derivatives
Chonghui Ma, Chenliang Wu, Yunyun Wang, Zhenzhen Huang, Qiangjian Zhang, Fuhao Dong, Wen Gu, Yu Shan, Shifa Wang
2019, 39(3): 821-829  doi: 10.6023/cjoc201807022
[摘要]  (186) [HTML全文] (186) [PDF 1693KB] (186)
摘要:
In this work, twelve dihydropyrimidinethione derivatives have been synthesized from isolongifolanone by aldol and cyclization reactions. The chemical structures were characterized by 1H NMR, 13C NMR and high resolution mass spectrometry (HRMS), and the structure of compound 3e was determined by X-ray single crystal diffraction. Their in vitro cytotoxicity against three cancer cell lines breast (MDA-MB-231), cervix (HeLa), liver (HepG-2) and one normal cell line mouse macrophages (Raw-264.7) were investigated. It was shown that these 12 compounds had good antitumor activity with IC50 values of 3.12~44.28 μmol/L. Among them, compounds 3j, 3g, and 3k had the best antitumor activity against MDA-MB-231 cells (IC50=3.12 μmol/L), HeLa cells (IC50=4.04 μmol/L) and HepG-2 cells (IC50=5.43 μmol/L), respectively. In addition, compound 3j arrested the cells in the G0/G1 phase of the MDA-MB-231 cell cycle and induced the early apoptosis of MDA-MB-231 cells in a dose-dependent manner.
研究简报
钯催化下稳定磷叶立德与烯丙基醇的脱水偶联反应
马献涛, 于静, 马瑞甜, 燕然, 张振雷
2019, 39(3): 830-835  doi: 10.6023/cjoc201812051
[摘要]  (299) [HTML全文] (299) [PDF 502KB] (299)
摘要:
报道了钯催化下酮基稳定的磷叶立德与烯丙基醇一锅法的烯丙化-Wittig反应.研究表明,在5 mol%四(三苯基膦)钯和20 mol%硼酸的共催化下,以52%~95%的收率得到官能化1,4-二烯化合物.该方法还可以进一步拓展到酯基以及氰基稳定的磷叶立德来合成对应的1,4-二烯化合物.
新型哌啶噻唑类化合物的合成及杀虫活性
丁成荣, 潘亚运, 殷许, 谭成侠, 张国富
2019, 39(3): 836-841  doi: 10.6023/cjoc201809009
[摘要]  (226) [HTML全文] (226) [PDF 570KB] (226)
摘要:
为了探寻新型的生物活性化合物,设计并合成了12个未见文献报道的新型哌啶噻唑类衍生物.生物活性测试研究发现,在500 μg/mL浓度下,目标化合物对粘虫表现出良好的抑制活性,而且在100 μg/mL下,(4-(5-(3-氯苯基)-4-甲基噻唑-2-基)哌啶-1-基)(4-甲基哌嗪-1-基)甲酮(1f)、(5-(3-氯苯基)-4-甲基噻唑-2-基)哌啶-1-基)(4-硝基-1H-吡唑-3-基)甲酮(1g)对粘虫的抑制率均达80%以上,另外在20 μg/mL下(5-(3-氯苯基)-4-甲基噻唑-2-基)哌啶-1-基)(4-硝基-1H-吡唑-3-基)甲酮(1g)仍具有50%的杀虫活性.
砂贝母中异甾体生物碱类成分的研究
黄金昌, 雷春, 阿吉艾克拜尔·艾萨, 俞媚华, 阿布力米提·伊力, 侯爱君
2019, 39(3): 842-847  doi: 10.6023/cjoc201809019
[摘要]  (195) [HTML全文] (195) [PDF 1609KB] (195)
摘要:
利用各种柱色谱和高效液相色谱等分离纯化方法,从砂贝母鳞茎中分离得到6个异甾体生物碱类化合物.根据质谱、一维/二维核磁共振谱和X射线单晶衍射等技术鉴定了它们的结构,分别为karelinine(1),5-epikarelinine(2),27-epiebeienine(3),ebeienine(4),persicanidine B(5)和heilonine(6),其中化合物1~3为新化合物.化合物1是贝母属中罕见的5β-jervine型异甾体生物碱,具有A/B环顺式稠合方式.化合物12也是贝母属中首次发现的具有15α-OH取代的jervine型生物碱.
纤枝金丝桃中3个新多环多异戊烯基间苯三酚类成分
王扣, 王赟, 王子明, 丁林芬, 胡建林, 陈佳
2019, 39(3): 848-851  doi: 10.6023/cjoc201807059
[摘要]  (186) [HTML全文] (186) [PDF 719KB] (186)
摘要:
利用多种色谱分离方法对纤枝金丝桃的化学成分进行研究,从其甲醇提取物的石油醚萃取部位分离得到3个新化合物,其结构经HRMS,1D和2D NMR等多种现代波谱鉴定为hyperlagarin A(1)、hyperlagarin B(2)和hyperlagarin C(3).
新型4-芳氨基嘧啶类衍生物的合成及其杀虫活性
吴宁捷, 程龙, 王剑, 郁季平, 邢家华, 许天明, 魏优昌
2019, 39(3): 852-860  doi: 10.6023/cjoc201807044
[摘要]  (190) [HTML全文] (190) [PDF 535KB] (190)
摘要:
以取代苯胺为起始原料,经重氮化、Meerwein芳基化、异硫氰化、加成、甲基化、环化等多步反应合成一系列结构新颖的4-芳氨基嘧啶类衍生物,并测试了目标化合物的杀虫活性.初步杀虫活性结果表明,在质量浓度500 mg/L时,大部分化合物对粘虫的致死率为100%;当质量浓度降至20 mg/L时,2-甲基-4-[N-(2-氯-4-氟苯基)氨基]-5-[2-三氟甲基-4-(苯氧基)苯基]-6-甲基嘧啶(6h)对粘虫和小菜蛾的致死率分别为80%和60%.
3-(((3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)亚甲基)氨基)取代苯并[d][1, 2, 3]三嗪-4(3H)-酮类化合物的合成及生物活性
张燕, 朱洪伟, 尚俊峰, 王宝雷, 李正名
2019, 39(3): 861-866  doi: 10.6023/cjoc201808033
[摘要]  (206) [HTML全文] (206) [PDF 528KB] (206)
摘要:
N-吡啶基吡唑甲酸乙酯、取代邻氨基苯甲酸为原料,经由还原、氧化、亲核加成、缩合、重氮化等多步反应,合成了一系列3-(((3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)亚甲基)氨基)取代苯并[d][1,2,3]三嗪-4(3H)-酮类目标化合物.初步生物活性测试结果表明,该系列化合物大多具有一定的杀虫活性,其中一个化合物在200 mg·L-1浓度下对东方粘虫(Mythimna separata Walker)具有70%的致死率;部分化合物表现出显著的抑菌活性,有两个化合物在50 mg·L-1浓度下对苹果轮纹病菌(Physalospora piricola)具有92.3%的抑制率,可作为新型抑菌先导结构,为后续的深入研究提供重要参考.
N-烷氧基取代酰胺类化合物的合成及杀菌活性
黄朋勉, 周智慧, 杜永磊, 庞怀林, 吕亮
2019, 39(3): 867-872  doi: 10.6023/cjoc201806029
[摘要]  (189) [HTML全文] (189) [PDF 494KB] (189)
摘要:
为寻找具有高杀菌活性的农药先导化合物,采用活性亚结构拼接的方法,将吡唑醚菌酯结构中羟基吡唑结构片段引入氟唑菌酰羟胺的结构中,合成了12个结构新颖的N-烷氧基酰胺类化合物.目标化合物的结构经过1H NMR,13C NMR和HRMS确证.杀菌活性测试表明,在测试浓度下,一些目标化合物对亚洲大豆锈病、黄瓜霜霉病或黄瓜白粉病表现出了一定的防效,其中化合物3a在100 mg/L测试浓度下对黄瓜白粉病的防效为95%.
Note
Efficient, Solvent-Free Aminolysis of Monoesters Catalyzed by Sodium
Tao Shen, Bo Ouyang, Shaodong Zhou, Chao Qian, Xinzhi Chen
2019, 39(3): 873-877  doi: 10.6023/cjoc201808006
[摘要]  (249) [HTML全文] (249) [PDF 414KB] (249)
摘要:
An efficient, solvent-free procedure using sodium as catalyst for the aminolysis of monoesters is reported. A detailed comparison of catalysts between sodium and sodium amide was made. It was found that the fresh sodium amide by in-situ synthesis of sodium with ammonia was more active than the indirectly adding sodium amide. As compared to the previously reported approaches, the procedure given in this work is much faster and performed under mild conditions. Furthermore, this procedure is applied successfully for the aminolysis of other monoesters.
亮点介绍
亮点介绍(8)篇
2019, 39(3): 878-881
[摘要]  (239) [HTML全文] (239) [PDF 500KB] (239)
摘要: