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综述与进展
氧杂环丙烷环加成反应研究进展
冯涛, 杜佳, 闫文静, 李兴, 高文超, 常宏宏, 魏文珑
2019, 39(5): 1197-1213  doi: 10.6023/cjoc201811035
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摘要:
氧杂环丙烷是一类环内含有氧原子的三元环状化合物,由于其本身的特殊结构和独特性质,它们可与含有各种不饱和键的化合物发生多种环加成反应,以此来制备种类更加丰富的含氧杂环化合物,综述了近年来氧杂环丙烷与含有各种不饱和键的化合物发生的环加成反应的研究进展,主要包括[3+2]、[3+3]和[4+3]等环加成反应,并对其发展方向进行了展望.
环金属铱配合物在发光电化学池中的应用
周文静, 刘志谦, 王志平, 胡斯帆, 梁爱辉
2019, 39(5): 1214-1225  doi: 10.6023/cjoc201812010
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与有机电致发光二极管(OLED)相比,发光电化学池(LEC)的器件结构更加简单,可以采用高功涵金属作为电极,因此在照明领域和移动设备终端显示方面具有巨大的应用前景,与其相关的研究与开发越来越受到科学界的重视.基于离子型过渡金属配合物的发光电化学池,由于具有不需要额外添加离子型导电材料和可以充分利用单线态和三线态激子的优点,受到业界广泛关注.与其它离子型过渡金属配合物相比,离子型铱配合物具有发光效率高、光学稳定性好以及发光颜色容易调节等优点.综述了近10年环金属铱配合物在发光电化学池中的应用,重点对离子型铱配合物在发光电化学池中的应用进行了评述,并对环金属铱配合物在发光电化学池领域的发展进行了展望.
不同介质中氰根传感器的研究进展
曲文娟, 房虎, 黄青, 张有明, 林奇, 姚虹, 魏太保
2019, 39(5): 1226-1243  doi: 10.6023/cjoc201810018
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摘要:
氰根离子对于哺乳动物来说具有很强的毒性,因为它会影响人体许多正常的功能,比如血管、视觉、中枢神经、心脏、内分泌和代谢系统.此外,含氰的盐类化合物仍然在人类的生产生活中广泛使用,特别是在电镀和塑料制造业、黄金和白银开采、制革工业、冶金等方面,从而导致了环境的污染.因此,人工合成的氰根选择性受体或荧光传感器在阴离子识别领域引起了广泛的关注.由于化学传感器具有合成方法简单、廉价、响应速度快,以及与氰根反应前后比色和/或荧光变化等优点,因此在过去的数十年中,被广大科研工作者深入研究.根据在不同介质中的氰根离子响应,本文从四个方面总结了2010年以来氰根离子传感器的研究进展:(1)纯有机相中的氰根离子识别,(2)含水介质中的氰根离子识别,(3)纯水相中的氰根离子识别,(4)固相中的氰根离子识别.这些传感器针对在溶液中和固体材料中氰根离子的检测,以及对氰根离子裸眼检测的研究,从而实现了在环境以及食物样品中方便、快捷地实时检测氰根离子.
异呋咱含能化合物合成及性能研究进展
薛琪, 毕福强, 张家荣, 张俊林, 王伯周, 张生勇
2019, 39(5): 1244-1262  doi: 10.6023/cjoc201811029
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异呋咱涵盖1,3,4-噁二唑和1,2,4-噁二唑,是一类用于构成高能钝感含能材料的基本单元.此类化合物已成为含能材料领域的研究热点之一.概述了两大类异呋咱含能化合物及其含能衍生物的最新研究进展,着重探讨了异呋咱环化反应机理和构建方法,介绍了代表性异呋咱含能化合物的物化和爆轰性能,并对其发展前景进行了展望.
膦烯化合物的合成及应用研究进展
黄海洋, 丁海新, 徐双双, 柏江, 肖强
2019, 39(5): 1263-1276  doi: 10.6023/cjoc201811038
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含有P=C双键膦烯化合物在均相催化、有机光伏材料、有机光电材料和纳米功能材料等领域有着重要的潜在应用价值,但是由于合成难度大和结构稳定性差等原因,其研究进展一直较为缓慢.从膦烯化合物的性质、合成方法及应用等方面系统总结了近几十年来膦烯化合物的研究进展,为从事相关研究的科学家提供参考.
多取代呋喃合成最新研究进展
张文生, 许文静, 张斐, 李焱
2019, 39(5): 1277-1283  doi: 10.6023/cjoc201811023
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呋喃是一类重要的五元含氧杂环化合物,其不仅是许多天然产物、药物和生物活性分子的核心结构,而且还是重要的有机合成中间体,具有广泛的应用价值.因此,呋喃及其衍生物的合成一直是有机化学家关注的研究热点之一.对2013年以来多取代呋喃的合成新方法进行了综述,包括二取代、三取代、四取代呋喃和苯并呋喃等.
环糊精参与的过渡金属催化有机反应
陈雅琪, 桂鑫, 段尊斌, 朱丽君, 项玉芝, 夏道宏
2019, 39(5): 1284-1292  doi: 10.6023/cjoc201809012
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环糊精是一种通过α-1,4-糖苷键将D-吡喃葡萄糖单元连接在一起而形成的环状低聚糖,具有“内疏水、外亲水”的刚性锥形空腔结构.正是由于这个独特的“内疏水、外亲水”空间结构,使得环糊精从被发现以来,越来越受到科学工作者的关注.过渡金属催化剂作为重要的工业催化剂,与环糊精体系结合可同时发挥金属的催化性能和环糊精的分子识别和相转移等功能,极大地改善其催化性能.主要综述了环糊精参与的过渡金属催化的有机化学反应,以金属价态分类介绍了常见的0至4价过渡金属参与催化的有机反应,并对环糊精参与的金属共催化体系的未来发展前景进行了展望,预计今后该催化体系将会有更广阔的应用,不断开发出更加高效和更有选择性的催化系统.
过渡金属催化有机钛试剂的偶联反应研究进展
黄辉, 李娟华, 刘昆明, 刘晋彪
2019, 39(5): 1293-1303  doi: 10.6023/cjoc201810036
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有机钛试剂廉价低毒,形态多样,具有优异的化学、区域和立体选择性.通过调整中心钛原子的配体可对有机钛试剂的反应活性进行调控.近年来,有机钛试剂参与的偶联反应引起了化学家们的广泛关注.从有机钛试剂类型出发,就过渡金属催化有机钛试剂的偶联反应进行了简要综述.
咪唑并[1, 2-a]吡啶化合物绿色合成的研究进展
赵鑫雨, 丁扬扬, 吕英涛, 康从民
2019, 39(5): 1304-1315  doi: 10.6023/cjoc201809034
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咪唑并[1,2-a]吡啶化合物是由五元和六元稠和的氮杂环化合物,在多种天然产物中被发现,表现出广泛的药理学活性,具有重要的研究意义和广阔的医药应用前景,因此有关于此类化合物的多样性的合成策略被不断报道.近年来,绿色化学是当代化学的热门方向之一,科学家们对绿色合成越来越重视,不断开发出各种绿色合成方案,其中一锅“多组分”反应、微波反应和固相合成这几种绿色、高效的合成方法一直是研究热点,就从这三类绿色合成的方法对咪唑[1,2-a]吡啶类化合物近几年绿色合成的研究进展加以概括总结.
Article
Copper-Catalyzed Aerobic Oxidative Coupling of Aromatic Sulfonyl Hydrazides with Amines:A New Access to Aromatic Sulfonamides
Zhenlei Zhang, Peng Qian, Zhenggen Zha
2019, 39(5): 1316-1322  doi: 10.6023/cjoc201903009
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A copper(Ⅱ)-catalyzed aerobic oxidative coupling of aromatic sulfonyl hydrazides with amines for the synthesis of aromatic sulfonamides was described. In contrast to previously described methods, this reaction employs copper/O2 as the catalytic system, and generates N2 as the only byproduct, which provides an environmentally benign synthetic route for aromatic sulfonamides.
Synthesis, Fungicidal and Insecticidal Activity of Novel Tetronic Acid Hydrazinyl Derivatives
Yu Zhao, Aiying Guan, Wanzhen Li, Weiwei Wang, Xinlei Liu, Ming'an Wang
2019, 39(5): 1344-1353  doi: 10.6023/cjoc201811041
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A series of novel 3-acetyl-4-hydrazinyl-5, 5-disubstitutedtetronic acid and (E/Z)-3-(1-hydrazinylethyli-dene)-5, 5-disubstitutedfuran-2, 4-dione derivatives were designed and synthesized, and four methyl 5-methyl pyrazole-4-carboxylate were obtained unexpectedly. Their structures were confirmed by high-resolution mass spectrum (HR-ESI-MS), 1H NMR, 13C NMR spectral data and X-ray diffraction. The bioassay results of the hydrazinyl compounds along with the amino analogues indicated that some compounds exhibited moderate to excellent fungicidal activities against phytopathagens. For example, compounds 5G, 5H, 5I and 5i showed 100% in vivo control efficacy against Colletotrichum lagenarium, and compound 5G also exhibited 100% in vivo control efficacy against Erysiphe graminis, Puccinia polysora and Colletotrichum lagenarium at 400 μg/mL. Compounds 5b, 5E and 6F showed 100% mortality against Plutella xylostella, compounds 6A, 6g and 6H exhibited 100% mortality against Myzus persicae, and compound 6b showed 100% mortality against Tetranychus cinnabarinus at 600 μg/mL. The 5, 5-spiro cyclohexyl moiety significantly improved the fungicidal activity of the tetronic acid derivatives, and the introduction of the substituted hydrazino group to the furan-2, 4-dione skeleton led to higher insecticidal and acaricidal activities. 5G and 5i were found to have the most potential to be further modified for searching new fungicide as the lead compounds.
Synthesis of Dihydropyrano[3, 2-c]pyrazolone through 1, 3-Dipolar Cycloaddition of Nitrilimines with Methyl Coumalate
Bo Wang, Qijun Wang, Honglei Liu, Jianning Liao, Jiaxing Huang, Hongchao Guo
2019, 39(5): 1354-1361  doi: 10.6023/cjoc201810015
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The 1, 3-dipolar cycloaddition of nitrilimines with methyl coumalate or pyranone worked efficiently in the presence of iPr2NEt under room temperature to give functionalized dihydropyrano[3, 2-c]pyrazol-5(1H)-one derivatives in high to excellent yields with excellent diastereoselectivities.
Molecular Design of High Energy Density Materials with Bis(3, 4, 5-substituted-pyrazolyl)methane Derivatives
Wanjun Wang, Huan Li, Renming Pan, Weihua Zhu
2019, 39(5): 1362-1371  doi: 10.6023/cjoc201812001
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A series of bis(3, 4, 5-substituted pyrazolyl)methane derivatives were designed as candidates of high energy density materials (HEDMs). The heats of formation (HOFs), electronic structure, energetic properties and thermal stabilities were studied using density functional theory (DFT) method. The difluoroamino groups could increase energy gaps of electronic structure, density and detonation properties among the title compounds. Bis[3, 5-bis(difluoroamino)-4-nitropyrazolyl]methane (C2) had excellent properties of potential HEDM. Its crystal density (ρ, 2.11 g/cm3) and impact sensitivity (h50, 6.8 J) were even higher than those of hexanitrohexaazaisowurtzitane (CL-20), meanwhile its detonation velocity (D, 9.80 km/s) and detonation pressure (P, 46.62 GPa) were very close to CL-20.
Electrochemical Synthesis of Tetrasubstituted Hydrazines by Dehydrogenative N-N Bond Formation
Enqi Feng, Zhongwei Hou, Haichao Xu
2019, 39(5): 1424-1428  doi: 10.6023/cjoc201812007
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An electrochemical synthesis of tetrasubstituted hydrazines through dehydrogenative dimerization of secondary amines has been developed. The reactions are conducted in a simple undivided cell with constant current. The use of electricity to promote the reactions obviates the need for transition metal catalysts and oxidizing reagents, providing an efficient and sustainable access to tetrasubstituted hydrazines with diverse electronic properties.
Strong-Acid Cation Exchange Resin Catalyzed Synthesis of Bis(indolyl)methanes in Water
Ruize Zhang, Guodong Wang, Hongshuang Li, Guiyun Duan, Kai Wang, Chengcai Xia
2019, 39(5): 1429-1435  doi: 10.6023/cjoc201810011
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An efficient protocol for conversion of aldehyde and indole into bis(indolyl)methanes derivatives catalyzed by strong-acid cation exchange resin has been developed. The H2O was used as solution and recycle catalyst can be used six times. Various bis(indolyl)methanes derivatives were obtained in excellent yields.
Synthesis and Luminescent Properties of 6-Methoxy-quinazolinone-pyridine Difluoroboron Dyes
Jia Zhou, Lu Liu, Cheng Zhong, Yang Fu, Zhibin Song, Yiyuan Peng
2019, 39(5): 1444-1449  doi: 10.6023/cjoc201901003
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6-Methoxyquinazolinone-pyridine difluoroboron dyes (BODIQPys) have been synthesized in two simple steps with 2-amino-5-methoxybenzamide and 2-methylpyridines as starting materials. These quinazolinone-based difluoroboron (BF2) complexes exhibited highly efficient green luminescence and remarkable fluorescence in the solid-state with very large Stokes shift (Δλ up to 220 nm in MeCN). The introduction of methoxy group at 6-position of BODIQPy caused the red-shifted emission by the enhancement of charge transfer property. The introduction of halogen atom at pyridine moiety of BODIQPy can tune the LUMO levels in regularity while their HOMO levels remain intact.
研究论文
微波辐射下超细高岭土催化的肟类化合物的高效合成
梁玲, 牟佳玲, 陈悦, 王梦莎, 洪志
2019, 39(5): 1323-1332  doi: 10.6023/cjoc201811021
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以廉价易得的超细高岭土为催化剂,羰基类化合物和盐酸羟胺为原料,PEG-400为溶剂,在微波辐射的条件下高效地合成一系列肟类化合物,同时探究了催化剂、溶剂种类、反应时间、反应温度等条件对反应的影响,并对所得的产物进行了熔点、核磁、红外、质谱数据检测.该方法具有反应时间短(5~15 min)、产率高、操作简便和环境友好等优点.另外,也初步探索了超细高岭土催化的微波辐射下肟交换反应及肟醚类化合物合成反应,产率分别为42%~67%与59%~72%.
三苯基膦催化下联烯丁酸酯与橙酮的陆氏[3+2]环化反应研究:制备螺[1-苯并呋喃-3-酮-2, 5'-环戊烯]类化合物
苏瀛鹏, 冯亚威, 曹林丹, 薛文轩, 石娅, 常兵兵, 黄丹凤, 王克虎, 胡雨来
2019, 39(5): 1333-1343  doi: 10.6023/cjoc201812022
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在PPh3催化下,橙酮和联烯酸酯可通过陆氏[3+2]环化反应成功构建含有螺[1-苯并呋喃-3-酮-2,5'-环戊烯]的多环结构单元.该反应条件温和,操作简单,并且底物适用性好,产率高.该方法学的研究为applanatumin A等天然产物的合成奠定了基础.
诺蒎酮基噻唑腙类化合物的合成及对α-淀粉酶的抑制活性
张强健, 王芸芸, 赵雨珣, 马崇慧, 杨益琴, 徐徐, 谷文, 王石发
2019, 39(5): 1372-1382  doi: 10.6023/cjoc201812032
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以天然β-蒎烯衍生物诺蒎酮为原料,经缩合和环化等反应,合成了24个诺蒎酮基噻唑腙类化合物,采用1H NMR,13C NMR,HRMS等方法对其结构进行表征,研究了噻唑腙类化合物对α-淀粉酶的抑制活性.结果表明,与阳性对照阿卡波糖相比,有6种化合物对α-淀粉酶表现出优良的的抑制活性,其中4-(2-(2-(6,6-二甲基-3-(4-甲基苄亚基)双环[3.1.1]庚烷-2-亚基)肼基)噻唑-4-基)苯酚(SZ14)的IC50值可达到4.11 μmol/L.从化合物的结构与活性关系看,R2的结构对活性具有显著的影响.抑制动力学结果表明,这6种化合物是针对α-淀粉酶的非竞争性抑制剂.采用分子对接方法评价了噻唑腙类化合物与α-淀粉酶的结合亲和力,并分析探索了化合物SZ14α-淀粉酶的结合方式.
碳酸钠促进的羧酸对α, β-不饱和酮的Oxa-Michael加成合成酯
王兴予, 朱雪庆, 姜炜, 高亚茹
2019, 39(5): 1383-1395  doi: 10.6023/cjoc201812038
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酯键普遍存在于各类精细化学品、医药、农药和功能材料中,酯键的形成在复杂产物合成中往往是最具挑战性的步骤.oxa-Michael加成反应是一类重要的形成碳-氧键的反应,醇作为亲核试剂对αβ-不饱和酮的oxa-Michael加成已被广泛而深入地研究,但使用有机酸为亲核试剂对αβ-不饱和酮的oxa-Michael加成反应由于其内在的挑战性而研究得很少.迄今为止,还没有一例普遍适用的有机酸对αβ-不饱和酮的oxa-Michael加成反应报道.这里,报道了一个碳酸钠水溶液促进的有机酸对αβ-不饱和酮的oxa-Michael加成反应.本反应的底物范围非常广泛,具有很好普适性,反应条件温和,成本低廉,绿色环保,可以用于制备很多类型酯化物,是一类较普遍适用的酯类化合物的合成方法.
三氯异氰尿酸促进下腙的氯化反应研究
宗吴中, 胡雨来, 王小平, 刘佳欣, 黄丹凤, 王克虎
2019, 39(5): 1396-1403  doi: 10.6023/cjoc201811039
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以三氯异氰尿酸为氯源,探索了腙和三氟乙醛芳腙的氯化反应,高产率地得到了一系列氯代芳腙和三氟乙酰氯芳腙化合物.该方法具有反应条件温和,反应时间短,易于操作,氯源稳定、价格低廉等特点,提供了一种高效合成氯代芳腙及三氟乙酰氯芳腙的新方法.
氮杂环卡宾(NHC)催化下多取代环戊烯的串联合成
李莎, 杨雯涵, 罗鲜, 姚昌盛
2019, 39(5): 1404-1410  doi: 10.6023/cjoc201812035
[摘要]  (52) [HTML全文] (52) [PDF 556KB] (1)
摘要:
在氮杂环卡宾(N-heterocyclic carbene,NHC)催化下,αβ-不饱和羧酸经过原位活化后与2-(2-氧代-2-芳乙基)丙二腈发生Michael加成、羟醛缩合、脱羧等反应,一锅法合成了多取代环戊烯类化合物.该方法具有底物范围广、原料易得、反应条件温和、产率高、操作简便等优点,为多官能化环戊烯类化合物的高效合成提供了新思路.
苯基三氟硼酸钾催化的硅烷还原羰基化合物成醇反应
刘建辉, 王星旸
2019, 39(5): 1411-1416  doi: 10.6023/cjoc201810010
[摘要]  (55) [HTML全文] (55) [PDF 436KB] (1)
摘要:
研究了以有机硅烷为还原剂选择性还原羰基的反应,在2.5 mol% C6H5BF3K,2.2 epuiv.(EtO)3SiH作用下,甲醇为溶剂,室温下将羰基还原为醇.以中等至较高产率得到目标产物.该方法在羰基还原上表现出良好的选择性,为羰基还原提供了一种新的方法.
离子液体中钯催化O-甲氧基炔酮肟醚串联环化/溴化反应
李建晓, 林绍, 黄瑞康, 李灿, 杨少容
2019, 39(5): 1417-1423  doi: 10.6023/cjoc201812006
[摘要]  (52) [HTML全文] (52) [PDF 503KB] (2)
摘要:
在离子液体[Cpmim]Cl中,利用O-甲氧基炔酮肟醚为反应底物,以5 mol% Pd(TFA)2为催化剂,2 equiv.CuBr2为溴源,以中等至优良产率(68%~90%)合成了系列4-溴代异噁唑衍生物,其结构均经1H NMR,13C NMR及HRMS确证.该反应具有产率高、底物适用范围广、原子经济性高等优点.此外,生成的产物通过进一步的修饰与转化可以衍生为结构复杂的、具有潜在生物活性的异噁唑活性分子.
基于咔唑和三嗪单元的位点调控设计并合成高效蓝光热活化延迟荧光分子
王彤彤, 华晓晨, 郁友军, 袁熠, 冯敏强, 蒋佐权
2019, 39(5): 1436-1443  doi: 10.6023/cjoc201810016
[摘要]  (43) [HTML全文] (43) [PDF 1125KB] (1)
摘要:
利用咔唑作为给体基元、三嗪作为受体基元,通过有效组合和位点调控设计合成了两个发光机理-热活化延迟荧光(TADF)分子:m-CzTri和p-CzTri.这两个材料均发射明亮的蓝色荧光,且具有非常小的单线态-三线态激子分裂能.计算模拟表明,给体和受体基团分离了最高占据轨道(HOMO)和最低未占据轨道(LUMO),使它们之间交叠很小.此外,测试了它们的热学、电化学、光物理和器件性质,其中,m-CzTri作为发光分子的有机发光二极管(OLED)器件的色坐标为(0.15,0.25),得到了高达18%的外量子效率.
研究简报
丙二酸二甲酯均相催化加氢合成3-羟基丙酸甲酯的研究
方霄龙, 段宁, 章敏, 张春燕, 刘睿, 朱红平
2019, 39(5): 1450-1455  doi: 10.6023/cjoc201812014
[摘要]  (101) [HTML全文] (101) [PDF 496KB] (2)
摘要:
以乙酰丙酮钌和膦胺配体作为催化剂体系,用于催化丙二酸二甲酯加氢制3-羟基丙酸甲酯.围绕催化反应性能,系统探讨了配体结构和用量、温度、时间以及溶剂等对丙二酸二甲酯转化率和3-羟基丙酸甲酯产率的影响.研究发现,乙酰丙酮钌和o-二苯基膦苯胺构成的催化剂体系在合适反应条件下可以有效催化丙二酸二甲酯选择性加氢制3-羟基丙酸甲酯.在优化的反应条件下,这一催化体系也可以催化多种不同结构酯类分子加氢制醇.
手性联萘酚聚合物在不对称环氧化反应中的应用
蔡瀚, 欧阳昆冰, 阳年发
2019, 39(5): 1456-1459  doi: 10.6023/cjoc201810029
[摘要]  (47) [HTML全文] (47) [PDF 497KB] (1)
摘要:
小分子手性催化剂存在着不便于与产物分离且催化剂难以回收重复使用等问题,这使得聚合物负载型的可回收催化剂得到了广泛的关注和研究.本工作成功地将可重复使用的手性联萘酚聚合物负载的二乙基锌催化剂用于(E)-αβ-不饱和芳基酮的不对称环氧化反应中.在对反应条件进行了优化后研究了反应的底物普适性,进一步探索了回收后的催化剂在以上不对称反应中的催化效率.该反应中对映体过量值最高能达到94%.分别对聚合物进行了回收利用实验,结果表明经过多次重复使用的聚[(S)-3-丙烯酰胺基-2,2'-二羟基-1,1'-联二萘]的手性诱导能力并没有明显下降.
含尿嘧啶结构单元二肽衍生物的设计、合成及生物活性研究
唐雪梅, 范莉, 张泽朝, 杨大成
2019, 39(5): 1460-1468  doi: 10.6023/cjoc201811040
[摘要]  (49) [HTML全文] (49) [PDF 5080KB] (1)
摘要:
为探索新型抗糖尿病分子,设计了含有尿嘧啶结构单元的二肽衍生物.以尿嘧啶、多聚甲醛和半胱氨酸为原料,经过两步反应获得关键中间体S-胸腺嘧啶-L-半胱氨酸(IM-2),再经氨基保护、羧基酯化和氨基酸偶联,顺利合成了16个二肽衍生物.所得目标化合物均经1H NMR、13C NMR和HRMS进行结构确认,并开展了过氧化物酶体增殖物受体反应元件(PPRE)激动活性、α-葡萄糖苷酶-rat抑制活性、二肽基肽酶-4(DPP-4)抑制活性筛选.生物活性结果显示,这些二肽衍生物的PPRE相对激动活性、α-葡萄糖苷酶和DPP-4抑制活性都很弱;同时发现,该类分子的α-葡萄糖苷酶抑制活性变化趋势与PPRE激动活性、DPP-4抑制活性变化趋势相反,这为新型多肽多靶点药物的设计提供了新思路.
锌-脯氨酸复合物催化的水相Knoevenagel缩合
颜世强, 郭伟, 王文笙, 张伟
2019, 39(5): 1469-1474  doi: 10.6023/cjoc201812046
[摘要]  (41) [HTML全文] (41) [PDF 669KB] (1)
摘要:
报道了锌-脯氨酸复合物催化下的水相Knoevenagel缩合反应.17种芳香醛以及2种脂肪环酮与丙二腈在80℃下反应5~10 min,能够以84%~99%的收率得到相应的Knoevenagel缩合产物.催化剂回收重复使用10次,其催化活性不受影响.
基于荧光共振能量转移效应的比例计量型水合肼荧光探针的设计、合成及其应用研究
杨滋琦, 刘兴坤, 姜鲁南, 王美
2019, 39(5): 1483-1488  doi: 10.6023/cjoc201811034
[摘要]  (82) [HTML全文] (82) [PDF 559KB] (1)
摘要:
水合肼(N2H4)是一种高毒性水溶生化试剂,具有致癌、致畸、致突变的能力.为了准确检测环境及生命体内N2H4浓度,基于荧光共振能量转移(FRET)原理,设计合成了两个双发射比例计量型探针(FRET-1/2),探针结构均经核磁共振氢谱、碳谱和高分辨质谱确证.研究结果表明,两个探针对N2H4均表现出较高的选择性和良好的灵敏性,可用于检测水样中N2H4浓度.
新型N-取代苯基-2-吡唑基烟酰胺类化合物的合成及其生物活性
尚俊峰, 刘巧霞, 王宝雷, 李正名
2019, 39(5): 1489-1496  doi: 10.6023/cjoc201810025
[摘要]  (49) [HTML全文] (49) [PDF 516KB] (1)
摘要:
基于含吡啶基吡唑的邻甲酰氨基苯甲酰胺类农药分子结构,采用“酰基移位”的策略,以2-氯-3-氰基吡啶和4-溴吡唑或3,5-二甲基吡唑为起始原料,简便合成了14个结构新颖的N-取代苯基-2-吡唑基烟酰胺类目标化合物.通过1H NMR、13C NMR和HRMS对新化合物进行了结构表征.初步生物活性测试结果表明,目标化合物在200 mg/L浓度下大多具有明显的杀虫活性,其中N-[4-氯-2-(乙氨基甲酰基)-6-甲基苯基]-2-(3,5-二甲基-1H-吡唑-1-基)烟酰胺(Il)对东方粘虫(Mythimna separata Walker)具有70%的致死率;部分化合物在50 mg/L浓度下对苹果轮纹病菌(Physalospora piricola)和番茄早疫病菌(Alternaria solani Sorauer)表现出较好的杀菌活性,其中2-(4-溴-1H-吡唑-1-基)-N-[2-(环丙氨基甲酰基)-4-碘-6-甲基苯基]烟酰胺(If)和2-(4-溴-1H-吡唑-1-基)-N-[4-氯-2-(乙氨基甲酰基)-6-甲基苯基]烟酰胺(Ih)对苹果轮纹病菌的抑制率分别达到62.9%和54.3%,2-(4-溴-1H-吡唑-1-基)-N-[4-氯-2-(正丙氨基甲酰基)苯基]烟酰胺(Id)对番茄早疫病菌具有54.5%的抑制率.研究结果为今后新型2-吡唑基烟酰胺类衍生物的深入研究提供了重要参考信息.
二甲双胍硫化氢盐的合成、结构鉴定和稳定性研究
胡曰富, 崔桂玲, 黄文才, 杨黎, 齐庆蓉
2019, 39(5): 1503-1508  doi: 10.6023/cjoc201811031
[摘要]  (194) [HTML全文] (194) [PDF 883KB] (1)
摘要:
随着硫化氢作为人体内重要内源性气体信号分子研究的不断深入,有机小分子硫化氢供体的研究也取得了较大的进展,但目前尚无一种硫化氢供体药物上市.二甲双胍是临床上治疗糖尿病的一线药物,近年来被报道还具有减肥、抗癌、抗衰老等多种生理活性.鉴于硫化氢和二甲双胍在重大疾病治疗中的良好前景,设计了一种全新的硫化氢供体二甲双胍硫化氢盐,前人对该类有机碱硫化氢盐的系统研究几乎为空白,更无将其作为硫化氢供体的报道.首先将二甲双胍盐酸盐处理得到二甲双胍游离碱,再与硫化氢反应形成二甲双胍硫化氢盐.通过氢谱、碳谱、元素分析及X单晶衍射对其进行了结构确证.采用碘量法、醋酸铅法和荧光亚甲蓝法测定了二甲双胍硫化氢盐中硫化氢的含量,均大于96.00%;采用高效液相色谱(HPLC)测定了二甲双胍硫化氢盐中二甲双胍的含量大于98.50%,且二甲双胍硫化氢盐的溶液及固体均相对稳定.上述研究结果表明,二甲双胍硫化氢盐有望作为一种新结构类型的硫化氢供体进行深入的研究和开发.
Note
Cytotoxic Secondary Metabolites from an Endophytic Fungal Strain of Phomopsis phyllanthicola
Hongxin Liu, Haohua Li, Yuchan Chen, Haibo Tan, Weimin Zhang
2019, 39(5): 1475-1478  doi: 10.6023/cjoc201812009
[摘要]  (47) [HTML全文] (47) [PDF 383KB] (0)
摘要:
The chemical investigation of the broth extract of the endophytic fungus Phomopsis phyllanthicola A658, which was isolated from the medicinal plant Pogostemon cablin, resulted in the isolation of one new compound, named dothiorelone O (1) and one new natural product 2-(3, 5-dihydroxy-2-(7-hydroxyoctanoyl)phenyl)acetic acid (2), along with four known derivatives. Their structures were fully characterized by means of detailed spectroscopic analysis for new structures, and in comparison with published data for known compounds. Moreover, all of the compounds were evaluated for in vitro cytotoxic activities against SF-268, MCF-7, HepG-2, and A549 tumor cell lines.
Two New Isocoumarins Isolated from a Mangrove-Derived Fungus Penicillium citrinum HL-5126
Rongqing Mei, Guolei Huang, Bin Wang, Meng Bai, Youping Luo, Guangying Chen, Caijuan Zheng
2019, 39(5): 1479-1482  doi: 10.6023/cjoc201812008
[摘要]  (60) [HTML全文] (60) [PDF 433KB] (0)
摘要:
Two new isocoumarins derivatives, penicimarins J (1) and K (2), were isolated from the mangrove-derived fungus Penicillium citrinum HL-5126. Their structures were elucidated through extensive 1D NMR, 2D NMR and HR-ESI-MS spectroscopic analyses. The absolute configurations of 1 and 2 were determined by comparison of their circular dichroism (CD) spectra with the literature. Compounds 1 and 2 showed inhibitory activities against α-glucosidase with the IC50 values of 18.37 and 25.86 μg/mL, respectively.
Notes
Synthesis and Antimicrobial Activity Evaluation of Aminoguanidine Derivatives Containing a Biphenyl Moiety
Haihong Yu, Shengchao Zhou, Tingting Guo, Zhuo Liang, Huabin Chen, Weikai Dai, Mingxia Song
2019, 39(5): 1497-1502  doi: 10.6023/cjoc201811012
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摘要:
A series of aminoguanidine derivatives containing a biphenyl moiety were designed, synthesized, and characterized by spectra methods using chalcone-aminoguanidine derivative as the lead compound. The antibacterial activity of the target compounds was evaluated. The results indicated that most of the target compounds showed potent inhibitory activity with the minimum inhibitory concentration values (MICs) in range of 0.5~8 μg/mL. Among of which, 2-((4'-bromo-[1, 1'-biphenyl]-4-yl)methylene)hydrazine-1-carboximidamide (3j) exhibited broad-spectrum antibacterial activity, effective to all the chosen strains including two multidrug-resistant gram-positive strains, showed the most potent inhibitory against S. aureus CMCC(B) 26003, E. faecalis CMCC 29212 and multidrug-resistant S. aureus ATCC 33591 with a MIC value of 0.5 μg/mL. Moreover, low cytotoxicity of compound 3j (HEK 293T, IC50=60.90 µmol/L) was found. These results suggested that the Compound 3j, with high safety, was potential and valuable in the research of novel antibacterial drugs.
亮点介绍
亮点介绍(4)篇
2019, 39(5): 1509-1510
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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]  (169) [HTML全文] (169) [PDF 1793KB] (169)
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]  (220) [HTML全文] (220) [PDF 1971KB] (220)
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]  (144) [HTML全文] (144) [PDF 602KB] (144)
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]  (249) [HTML全文] (249) [PDF 1035KB] (249)
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]  (294) [HTML全文] (294) [PDF 811KB] (294)
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]  (159) [HTML全文] (159) [PDF 567KB] (159)
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]  (189) [HTML全文] (189) [PDF 882KB] (189)
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]  (138) [HTML全文] (138) [PDF 1560KB] (138)
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]  (121) [HTML全文] (121) [PDF 1248KB] (121)
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]  (125) [HTML全文] (125) [PDF 561KB] (125)
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]  (144) [HTML全文] (144) [PDF 2553KB] (144)
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
[摘要]  (100) [HTML全文] (100) [PDF 467KB] (100)
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]  (121) [HTML全文] (121) [PDF 814KB] (121)
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]  (121) [HTML全文] (121) [PDF 3978KB] (121)
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]  (106) [HTML全文] (106) [PDF 2437KB] (106)
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]  (105) [HTML全文] (105) [PDF 456KB] (105)
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]  (119) [HTML全文] (119) [PDF 401KB] (119)
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]  (93) [HTML全文] (93) [PDF 1491KB] (93)
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]  (108) [HTML全文] (108) [PDF 475KB] (108)
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]  (112) [HTML全文] (112) [PDF 1319KB] (112)
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
[摘要]  (97) [HTML全文] (97) [PDF 1706KB] (97)
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]  (90) [HTML全文] (90) [PDF 498KB] (90)
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]  (92) [HTML全文] (92) [PDF 4056KB] (92)
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]  (94) [HTML全文] (94) [PDF 1693KB] (94)
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]  (148) [HTML全文] (148) [PDF 502KB] (148)
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]  (121) [HTML全文] (121) [PDF 570KB] (121)
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]  (91) [HTML全文] (91) [PDF 1609KB] (91)
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]  (94) [HTML全文] (94) [PDF 719KB] (94)
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]  (87) [HTML全文] (87) [PDF 535KB] (87)
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]  (108) [HTML全文] (108) [PDF 528KB] (108)
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]  (86) [HTML全文] (86) [PDF 494KB] (86)
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]  (128) [HTML全文] (128) [PDF 414KB] (128)
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]  (98) [HTML全文] (98) [PDF 500KB] (98)
摘要: