Synthesis and Biological Activity of 3‐Methyl‐1H‐pyrazole‐4‐carboxylic Ester Derivatives

In search of novel pyrazole derivatives with bioactivity, a series of 3‐methyl‐1H‐pyrazole‐4‐caboxylic: ester derivatives were synthesized via α‐oxoketene dithioacetals as starting material. The structures of all compounds prepared were confirmed by ^lH NMR, IR, MS and elemental analyses. Preliminary bioassays indicated that some compounds showed fungicidal activity against wheat rust, phoma asparagi and antiviral activity against TMV.     

Design,Synthesis, Antifungal Activities and SARs of (R)‐2‐Aryl‐4,5‐dihydrothiazole‐4‐carboxylic Acid Derivatives

Based on the structure of natural product 2‐aryl‐4,5‐dihydrothiazole‐4‐carboxylic acid, a series of novel (R)‐2‐aryl‐4,5‐dihydrothiazole‐4‐carboxylic acid derivatives were designed and synthesized. Their structures were characterized by ¹H NMR, ¹³C NMR and HRMS. The single crystal structure of compound 9b was determined by X‐ray diffraction analysis. The antifungal activities were evaluated for the first time. The bioassay results indicated that most compounds exhibited moderate to good antifungal activities. The antifungal activities of compound 13a (against Cercospora arachidicola Hori), 13d (against Alternaria solani), and 16e (against Cercospora arachidicola Hori) were 61.9%, 67.3% and 61.9%, respectively, which are higher than those of the commercial fungicides chlorothalonil and carbendazim. Moreover, compound 13d exhibited excellent antifungal activities against 7 kinds of the fungi tested (66.7%, 77.3%, 63.0%, 87.9%, 70.0%, 70.0% and 80.0% at 50 µg?mL). Therefore, 13d can be used as a new lead structure for the development of antifungal agents.     

新型藤黄酸衍生物的合成及其抗肿瘤活性

以藤黄酸(1)为原料,分别与HBr和有机胺反应,合成了9个新型的藤黄酸衍生物(2~6),其结构经1HNMR,MS和HR-MS表征。采用MTT法测定了2~6对人结肠腺癌细胞(RKO)、人肝癌细胞(HepG-2)和人卵巢腺癌细胞(OVCAR-3)的体外抗肿瘤活性。结果表明,藤黄酸(N-丙基对甲苯磺酰胺)酯3,藤黄酸(N-丙基苯丙酰胺)酯4和N-色胺藤黄酰胺6b的抗肿瘤活性显著高于1;33-羟基转位藤黄酸2的抗肿瘤活性则大大降低。     

Synthesis and Characterization of 2,7‐Linked Carbazole Oligomers

A set of monodisperse 2,7‐linked carbazole oligomers (3‐mer, 5‐mer, 7‐mer, and 9‐mer) was synthesized, and their photophysical, electrochemical, and thermal properties were investigated. In solutions, these oligomers exhibited bright blue emission with almost quantitative fluorescence quantum yield. The emission spectra of these oligomers in films are quite different. 3‐Mer and 5‐mer exhibited featureless emission spectra, whereas 7‐mer and 9‐mer showed well‐resolved emission spectra.     

Synthesis of Some Novel 1,4‐Phenylene‐bis‐thiazolyl Derivatives and Their Anti‐hypertensive α‐blocking Activity Screening

A series of novel 1,4‐phenylene‐bis‐thiazolyl derivatives were synthesized and evaluated for their anti‐hypertensive activities as α‐blocking agents and some of them showed promising activities.     

新型芳基修饰的藤黄酸衍生物的合成及其抗肿瘤活性

以取代酚或羟基吡啶为原料,在无水碳酸钾存在下,与溴代醇发生威廉姆森醚合反应制得中间体--芳（杂环）氧基醇(2a~2k); 2a~2k分别与藤黄酸通过光延反应合成了藤黄酸衍生物（3a~3k）。以DDC/HOSu为偶联剂,芳酸与3-氨基-1-丙醇经偶联反应制得中间体--芳酰氨基醇（5a~5h）; 5a~5h分别与藤黄酸通过光延反应合成了藤黄酸衍生物（6a~6h）。 2, 3, 5和6为新化合物,其结构经¹H NMR, ESI-MS和HR-MS表征。采用MTT法测定了3和6对肺腺癌细胞(A549)、肝癌细胞(HepG-2)和乳腺癌细胞(SK-BR-3)的体外抗肿瘤活性。结果表明：部分化合物对肿瘤细胞的抑制活性明显高于藤黄酸。     

Synthesis and Anti‐tumor Evaluation of Novel C‐37 Modified Derivatives of Gambogic Acid

Gambogic acid (GA, 1 ), the most prominent representative of Garcinia natural products, has been reported to be a promising anti‐tumor agent. In order to further explore the structure‐activity relationship of GA and discover novel GA derivatives as anti‐tumor agents, 17 novel C‐37 modified derivatives of GA were synthesized and evaluated for their in vitro anti‐tumor activities against A549, HCT‐116, BGC‐823, HepG2 and MCF‐7 cancer cell lines. Among them, 11 compounds were found to be more potent than GA against some cancer cell lines. Notably, compound 8 was almost 5–10 folds more active than GA against A549 and BGC‐823 cell lines with the IC₅₀ values of 0.12 µmol·L^?1 and 0.57 µmol·L^?1, respectively. Chemical modification at C‐37 position of GA by introducing of hydrophilic amines could lead to increased activity and improved drug‐like properties. These findings will enhance our understanding of the structure‐activity relationship (SAR) of GA and lead to the discovery of novel GA derivatives as potential anti‐tumor agents.     

新型川芎嗪阿魏酸衍生物的合成及其抗血小板聚集活性

以阿魏酸及其类似物为原料,设计并合成了6个新型的川芎嗪阿魏酸衍生物,其结构经1H NMR,13C NMR,IR及MS表征.初步药理活性测试结果显示,部分化合物的血小板抑制率较高.     

Rapid Synthesis of Novel and Known Coumarin‐3‐carboxylic Acids Using Stannous Chloride Dihydrate under Solvent‐Free Conditions

Various coumarin‐3‐carboxylic acid (=2‐oxo‐2H‐1‐benzopyran‐3‐carboxylic acid; CcaH) derivatives have been synthesized in good yields using catalytic amounts of SnCl₂?2 H₂O under solvent‐free conditions. This inexpensive, nontoxic, and readily available catalytic system (10 mol‐%) efficiently catalyzes the Knoevenagel condensation and intramolecular cyclization of various 2‐hydroxybenzaldehydes or acetophenones with Meldrum's acid. High product yields, use of inexpensive and safe catalyst, and solvent‐free conditions display both economic and environmental advantages.     

Chemical Synthesis and In Vitro Antitumor Activity of Quinizarin Glycoside Analogs

A series of new glycoside derivatives of quinizarin were synthesized and characterized by NMR and IR spectrometry, and in vitro antitumor activity of some of these derivatives was evaluated against the mouse leukaemia P388 and the human leukaemia HL-60 cell lines by the standard MTT assay. They were proven to possess moderate antitumor activity.     

1H, 13C and 15N NMR spectroscopic characterization of unexpected degradation products of the nifedipine analogue bis(2‐cyanoethyl) 2,6‐dimethyl‐4‐(2‐nitrophenyl)‐1,4‐dihydro‐3,5‐pyridinedicarboxylate

In the course of saponification experiments with bis(2‐cyanoethyl) 2,6‐dimethyl‐4‐(2‐nitrophenyl)‐1,4‐dihydro‐3,5‐pyridinedicarboxylate ( 1 ), an analogue of the calcium channel blocker nifedipine, three unexpected degradation products were isolated. The compounds were identified as 3‐(2‐acetamido‐1‐carboxy‐1‐propenyl)‐1‐hydroxy‐2‐indolecarboxylic acid ( 3 ), 9‐hydroxy‐1,3‐dimethyl‐β‐carboline‐4‐carboxylic acid ( 4 ) and 6‐hydroxy‐2,4‐dimethyl‐5‐oxo‐5,6‐dihydrobenzo[c][2,7]naphthyridine‐1‐carboxylic acid ( 6 ). The structures of these compounds were deduced from one‐ and two‐dimensional ¹H, ¹³C and natural abundance ¹⁵N NMR experiments (¹H,¹H‐COSY, gs‐HSQC, gs‐HMBC, ¹⁵N gs‐HMBC), and corroborated by comparison of their NMR data with the respective data for structurally similar compounds. Copyright © 2002 John Wiley & Sons, Ltd.     

金诺芬衍生物的合成及抗肿瘤活性

设计合成了一类新型金诺芬衍生物, 采用核磁共振波谱(NMR)和高分辨质谱(HRMS)确认了其结构. 以目标化合物处理肿瘤细胞后, 采用四氮唑蓝盐(MTS)法检测细胞增殖情况, 用流式细胞仪检测细胞凋亡情况, 采用蛋白质免疫印迹(Western blot)法检测总的泛素化蛋白(Ub-Prs)、 K48 位链接多聚泛素化蛋白以及蛋白酶体外源性特异性底物(GFPu)的表达情况. 结果表明, 金诺芬衍生物可通过抑制蛋白酶体功能来发挥抗肿瘤效果.     

Synthesis of a Regioisomer of β‐Lapachone and Analogs as Potent Antitumor Agents

A regioisomer of β‐lapachone and two analogs were synthesized and evaluated for their antitumor activities. All three compounds tested were found to exhibit promising activities against PC‐3, HepG2, and Raji cancer cell lines in μM range.     

甘草次酸衍生物的合成及其抗癌活性

设计合成了6种甘草次酸衍生物,用元素分析、波谱分析鉴定了它们的结构,并比较了它们的体内、体外抗癌活性,均表现出较好的活性,尤其是化合物Ⅰa,Ⅰb口服效果比盐酸氮芥还好,表现出甘草次酸对氮芥有明显的增效应用。     

Synthesis,Structure, and Fluorescent Properties of Lanthanide Complexes Based on 8‐Hydroxyquinoline‐7‐carboxylic Acid

The lanthanide complex [Eu₃(8‐HQCA)₃(COOH)(OH)₂(H₂O)₃]_n · nH₂O (8‐HQCA = 8‐hydroxyquinoline‐7‐carboxylic acid) was synthesized and characterized. Single‐crystal X‐ray diffraction shows that the trinuclear structures are linked by ligands to form 2D layers. The results of DFT calculation shows that energy can be transferred effectively from the ligand to Eu^III ions. A series of heteronuclear complexes {[(Eu_1–xY_x)₃(8‐HQCA)₃(COOH) (OH)₂(H₂O)₃]_n · nH₂O (x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8)} were synthesized and their luminescent properties were studied. The results showed that the doping of Y^III ions could change the fluorescent intensity of the Eu^III complex, but could not change their positions.     

1,2,3-三唑取代的1,4-二氢-4-氧代-1,5-二氮杂萘-3-羧酸衍生物的设计、合成与HIV整合酶抑制活性评价

一价铜催化端炔与叠氮化物的1, 3-环加成反应是一种快速构建小分子库并筛选其可能性质的的主要方法。本文报道了1,2,3-三唑取代的1,4-二氢-4-氧代-1,5-二氮杂萘-3-羧酸衍生物的设计与合成。在该类化合物中,疏水性与亲水性片段通过Click反应有效地连接。所设计化合物8和12的结构通过光谱手段进行了表征;其可能的HIV整合酶抑制活性也进行了筛选。     

Synthesis, Characterization and Crystal Structure of [Na2(APZC)2(μ-H2O)2(μ3-H2O)]n

The synthesis and spectroscopic properties of a Na^＋ complex with ligand 3-aminopyrazine-2-carboxylic acid were described. The resulting complex was characterized by elemental analysis, IR, UV-Vis, NMR spectroscopy and single crystal X-ray diffraction method. The title compound crystallizes in the triclinic system with space group . The crystalline structure of this compound consists of supramolecular architectures involving strong intramolecular N—H…O in pyrazine molecules and intermolecular O—H…N, O—H…O, and N—H…N hydrogen bonds between substituted pyrazine and water molecules.