吡唑类化合物的合成研究进展

吡唑类化合物是一类重要的药物合成中间体,在抗肿瘤、抗病毒、抗抑郁等领域发挥着重要作用。本文综述了吡唑类衍生物的合成方法,包括1,3-亲电化合物与肼类的环化、1,3-偶极体系的环加成等。     

二吡唑基甲酮类化合物的合成和表征

以5-氨基-3-甲硫基-1H-吡唑-4-羧酸乙酯(1)为原料, 依次经肼解、与取代的乙烯酮二硫缩醛缩合和烷基化合成了一系列二吡唑基甲酮类化合物, 经¹H NMR, ¹³C NMR和元素分析确证了它们的结构, 部分化合物进一步经过了质谱表征.     

芳基吡唑腙及其双杂环化合物的合成与抗菌活性

通过1-苯基-3-(4-甲基苯基)-4-甲酰基吡唑与芳氧乙酰肼的加成反应,合成了5个新型的吡唑腙类化合物(3a～3e);3在酸性条件下环合,合成了5个新型的吡唑双杂环化合物(4a～4e). 3和4的结构经1H NMR,IR,MS和元素分析表征.对3和4分别进行了棉花枯萎病菌(A),棉花黄萎病菌(B),棉花立枯病菌(C),瓜果腐霉病菌(D),番茄早疫病菌(E)及向日葵菌核病菌(F)等初步的抑菌活性测试.结果表明,4的抑菌效果明显高于3;其中4d和4e对A,C和D的抑制率大于90%,对E和F的抑制率大于80%.     

吡唑肟醚类化合物的合成

以1-取代苯基-3-甲基-5-吡唑酮为起始原料,合成了6个具有肟醚结构的新吡唑化合物,其结构经^1H NMR,IR和元素分析确认。     

多取代吡唑合成最新研究进展

吡唑是一类重要的五元含氮杂环化合物,广泛存在于许多天然产物、生物活性分子和药物分子中,而且是一类重要的有机合成中间体.因此,近年来吡唑及其衍生物的合成引起了科学家们的极大兴趣,并得以迅速发展.对近年来多取代吡唑的合成新方法进行了综述,以期对相关领域的研究起到一定的辅助与推动作用.     

含氯羧酸吡唑醛肟酯化合物的合成及生物活性

含氯羧酸吡唑醛肟酯化合物的合成及生物活性;羧酸吡唑醛肟酯;合成;生物活性     

方酸类药物合成研究概况

本文对近年来方酸类药物的合成及用途等进行了比较详细的评述，开展了一些可望具有疗效的方酸衍生物的合成研究，并就方酸类药物的制备提出了新解。     

三（取代吡唑）硼氢化钾的合成

三（取代吡唑）硼氢化钾的合成郭胜利李贤均（四川大学化学系成都６１００６４）殷元骐（中国科学院兰州化学物理研究所兰州７３００００）关键词取代吡唑硼氢化合成中图分类号Ｏ６１４自１９６７年ＴｒｏｆｉｍｅｎｋｏＳ．［１］首次报道了多聚吡唑硼氢化钾ＫＨｎＢｐｚ...     

吡唑腙及其双杂环化合物的设计、合成及生物活性

利用Vilsmeier-Haak反应得到活性中间体,取代-4-甲酰基吡唑;将其与芳氧乙酰肼反应,合成5个吡唑腙类化合物3,再经关环反应,制得5个吡唑类双杂环化合物4。所有新化合物的结构均经IR,1H NMR,MS和元素分析确证了结构。对新化合物3,4分别进行了棉花枯萎病菌、棉花黄萎病菌、棉花立枯病菌、瓜果腐霉病菌、番茄早疫病菌、向日葵菌核病菌等初步的抑菌活性测试,结果表明,吡唑类双杂环化合物4的抑菌效果明显高于吡唑腙化合物3。在质量浓度为50mg/L时,3d、3e对番茄早疫病菌、向日葵菌核病菌有较好的抑制效果(﹥80%);双杂环化合物4对6种病菌均有明显的抑制效果(﹥70%),其中4d、4e对棉花立枯病菌的抑制率大于95%。     

新型吡唑腙类化合物的合成

吡唑肼作为合成含氮杂环的中间体为人们广泛关注, 为了寻找可能具有生物活性的杂环化合物, 设计并合成了两类新型含有吡唑基的腙类化合物, 其结构经¹H NMR, IR, MS和元素分析确证. 初步的除草与杀菌活性测定表明它们具有一定的活性.     

3,5-二(2-吡啶基)吡唑的合成方法改进

以2-吡啶甲酸为原料,经酯化、缩合、加成合成了平面四齿双核配体3,5-二(2-吡啶基)吡唑。改进合成方法使加成反应的产率由原来的66%提高到98%。     

Glucose‐coated superparamagnetic nanoparticle‐catalysed pyrazole synthesis in water

A green, benign, heterogeneous, superparamagnetic catalyst (Glu.@Fe₃O₄) was synthesized and characterized using Fourier transform infrared spectroscopy, X‐ray diffraction, thermogravimetric analysis, scanning electron microscopy and vibrating sample magnetometry. The prepared catalyst was used to achieve a high‐efficiency, low‐cost, eco‐friendly and easy‐to‐handle protocol for synthesizing substituted pyrazole derivatives from aldehydes, malononitrile and phenylhydrazine. The catalyst was also used in chromene synthesis. Glucose coated on magnetic nanoparticles provided excellent catalytic activity. The catalyst could be recycled for up to four runs without significant loss in catalytic activity.     

含吡唑基的苯骈咪唑的合成与光谱性能(英文)

在乙醇溶剂中,于温和条件下以邻苯二胺和1-苯基吡唑-4-醛为原料合成了一种结构新颖的含吡唑取代基的苯骈咪唑杂环化合物,通过元素分析,MS,1H NMR对所合成的苯骈咪唑化合物的组成与结构进行了表征,同时对该化合物的紫外-可见光谱和荧光光谱进行了研究.     

异色满并吡唑衍生物的合成及其抗炎作用

异色满（isochroman）属于异革并毗哺类杂环化合物，近年来，已经合成出许多具有镇痛、降压、抗组胶和抗肿瘤等药理活性的异色满类化合物，但大都为异色满环上的1，2，4位取代衍生物或者螺环化合物［”’j，关于并杂坏的异色满报道甚少，鉴于许多有生理活性的天然产物中带有咄哩环以及异色满衍生物所表现的药理性质，本文选择异色满酮一4的足二酮衍生物为原料，完成了异色满并毗峻衍生物的合成，并对其抗炎活性进行了研究．合成路线如下：所用仪器有BRUCKER七0型核磁共振仪，TMS为内标；Perkin－Elmer1730型红外分光光度计，KBr压片；…     

Mechanistic study on the Knorr pyrazole synthesis-thioester generation reaction

A novel Fmoc-SPPS compatible peptide thioester generation method leveraging Knorr pyrazole synthesis was reported recently. C-terminal peptide hydrazides, pentane-2,4-dione and excess arylthiol were added in one-pot to efficiently produce peptide thioesters in acidic aqueous solution at room temperature. To elucidate the detailed mechanism of this reaction and the origin of the effect of solution acidity, a theoretical investigation on the Knorr pyrazole synthesis-thioester generation reaction was carried out. Our computational results suggest that the reaction generally proceeds through three stages: hydrazone formation, pyrazole formation and thioester formation. The rate-determining step is the CO bond cleavage step in the pyrazole formation stage. The formed pyrazole is readily converted to thioester in the presence of excess thiophenol. The effect of solution acidity originates from the need for protonation of oxygen atoms to increase the electrophilicity of carbonyl group or the leaving ability of hydroxyl group.     

Convenient DABCO-catalyzed one-pot synthesis of multi-substituted pyrano[2,3-c]pyrazole dicarboxylates

We developed an efficient and simple one-pot synthesis of functionalized multi-substituted 2,4-dihydro-pyrano[2,3-c]pyrazole dicarboxylates from β-ketoesters, hydrazine, dimethyl acetylenedicarboxylate and malononitrile in EtOH. This four-component one-pot reaction carried out in the presence of DABCO catalyst showed advantages over a one-pot three-component method in its simple procedure, high yield and low toxicity.     

Polyethylene glycol-promoted synthesis of pyrimido[1,2-a]benzimidazole and pyrano[2,3-c]pyrazole derivatives in water

Synthesis of pyrimido[1,2-a]benzimidazole and pyrano[2,3-c]pyrazole derivatives were achieved using polyethylene glycol (PEG-400) as promoting reaction medium in water under catalyst-free conditions at reflux and room temperature, respectively. The structure of pyrimido[1,2-a]benzimidazole was confirmed using ¹H NMR, ¹³C NMR, DEPT, and HMBC experiments. The promising points for the present methodology are efficiency, generality, high yield, short reaction time, cleaner reaction profile, ease of product isolation, simplicity, potential of recycling reaction medium, and finally agreement with green chemistry protocols.     

Ketene dithioacetal mediated synthesis of 1,3,4,5-tetrasubstituted pyrazole derivatives and their biological evaluation

Abstract

Ketene dithioacetal mediated chemo- and regioselective synthesis of a series of novel 1,3,4,5-tetrasubstituted pyrazole derivatives (4a-l) integrated with a bioactive indole nucleus was achieved by reacting substituted 2-(1-methyl-1H-indole-3-carbonyl)-3,3-bis-(methylthio)-acrylonitrile (2) and substituted phenyl hydrazine hydrochloride (3) in the presence of a catalytic amount of anhydrous K₂CO₃ under reflux conditions. The structures were ascertained by ¹H NMR, NOESY, ¹³C NMR, FT-IR, and HRMS data. In vitro cytotoxicity evaluation of the synthesized compounds against MCF 7 (breast carcinoma) and normal Vero (monkey kidney) cell lines revealed that the compound 5-(5-Bromo-1-methyl-1H-indol-3-yl)-1-(4-cyano-phenyl)-3-methylsulfanyl-1H-pyrazole-4-carbonitrile (4k) showed significant cytotoxicity against MCF 7 (GI₅₀ = 15.6 µM) with low cytotoxicity against normal Vero cell line. Most of the synthesized compounds were also found to possess excellent anti-inflammatory and antioxidant (DPPH, NO, H₂O₂ and SOR) potential.     

Design,synthesis and insecticidal activities of novel anthranilic diamides containing polyfluoroalkyl pyrazole moiety

In order to discover new molecules with good insecticidal activities, a series of anthranilic diamides containing polyfluoroalkyl pyrazole were designed and synthesized, and their structures were characterized by ¹H NMR and HRMS. Bioassays demonstrated that some of the title compound exhibited excellent insecticidal activities. The larvicidal activities of compound 8a, 8c, 8g, 8k and 8l against Mythimna separata Walker were 100% at 0.8 mg/L. The insecticidal activities of compound 8a, 8c, 8e, 8g, 8k and 8l against Plutella xylostella Linnaeus were 100% at 0.4 mg/L. Surprisingly compounds 8a and 8c still showed 100% larvicidal activities against Plutella xylostella Linnaeus at 0.08 mg/L comparable to the commercialized Chlorantraniliprole. The LC₅₀ of compound 8a and 8c against M. separata is 0.048 and 0.043 mg/L respectively.     

Synthesis,crystal structure,and insecticidal evaluation of novel aryl pyrazole compounds containing aminophosphonate moiety

A series of novel aryl pyrazole derivatives containing aminophosphonate were designed and synthesized on the basis of the commercial insecticide Fipronil. Their structures were confirmed by ¹H NMR, FT-IR, elemental analysis, and compound 4 m was characterized by a single crystal X-ray diffraction analysis. The results of the preliminary bioassays showed that title compounds exhibited satisfactory insecticidal activities against Culex pipiens and Musca domestica. The introduction of an electron-withdrawing group to the para-position of the benzene ring was essential for high bioactivity.