DDQ氧化法合成3-溴-1-（3-氯-2-吡啶基）二1H-吡唑-5-甲酸酯类化合物

以DDQ为氧化剂,对3-溴-1-（3-氯-2-吡啶基）-4,5-二氢-1H-吡唑-5-甲酸酯类化合物进行氧化研究,合成了一系列3-溴-1-（3-氯-2-吡啶基）-1H-吡唑-5-甲酸酯类化合物,其结构经氢谱、碳谱和高分辨质谱分析确证,该方法具有操作简便、产率高、适用范围广等优点．     

Synthesis and biological assessment of novel cyanopyridine derivatives

New pyridine derivatives bearing p-dimethyl amino phenyl and p-bromophenyl moieties at position-4 and 6 have been prepared. The behavior of pyridone derivative 2 toward ethyl chloroacetate followed by hydrazine hydrate gave pyridinyl acetohydrazide derivative 7, and its behavior toward carbon electrophiles has been investigated by its reaction with aromatic aldehydes, ethyl acetoacetate, acetyl acetone, cyclohexanone, phthalic anhydride, maleic anhydride, and isatin affording the pyridine derivatives 8a–e to 16, respectively. Treatment of compound 2 with acrylonitrile in Et₃N, yielded the N- alkylated derivative 17. Some pyrazole derivatives have been synthesized by interaction of the chalcone 1 with hydrazine hydrate afforded pyrazole derivative 18. Treatment of compound 18 with benzoyl chloride and or acetic anhydride resulted in the formation of the acylated compounds 19 and 20. Elemental and spectroscopic pieces of evidence characterized all the newly synthesized compounds. Some of the synthesized compounds were tested for their antibacterial activities against Gram-positive and Gram-negative bacteria.     

新型含吡啶环取代的吡唑肟醚类化合物的合成及生物活性研究

为了寻找新型高效低毒的农药先导化合物,通过N-吡啶基吡唑肟与2-氯-5-氯甲基吡啶的缩合反应,合成了一系列含吡啶环取代的吡唑肟醚类化合物.目标化合物的结构均经1H NMR,13C NMR和元素分析确证.初步生物活性试验结果表明,部分化合物具有一定的杀菌、杀虫和植物生长调节活性.如化合物5e在浓度为50 μtg/mL时对番茄早疫的抑制率为61.4％;化合物5j在浓度为50 μg/mL时对花生褐斑的抑制率为60.2％;化合物5i在浓度为500 μg/mL时对蚜虫表现出50.3％的杀死率;化合物5f在浓度为10 μg/mL时对黄瓜子叶生根表现出71.0％的促进生长作用.     

N-[3-(4-喹唑啉基)氨基-1H-吡唑-4-甲酰基]醛腙类衍生物的合成及抗菌活性研究

以4-氯喹唑啉、3-氨基-4-吡唑甲酸乙酯和芳醛为原料,合成了13个新型的N-[3-(4-喹唑啉基)氨基-1H-吡唑-4-甲酰基]醛腙类化合物,通过IR,1H NMR,13C NMR和元素分析对其结构进行了确认.初步生物活性测试结果表明,在50 μg/mL浓度下,化合物5d对小麦赤霉菌和苹果腐烂菌的抑制率与对照药剂嗯霉灵相当;化合物5k对小麦赤霉菌的抑制率则高于噁霉灵.     

A One-dimensional Metallic Oxide Constructed from Molybdenum Clusters and Mn（Ⅱ）-[3-（2-pyridyl） pyrazole] Cationic Coordination Components

A new polyoxomolybdate compound [Mn II (L) 2 (Mo 8 O 26) 0.5 ] 2n (1,L=3-(2-pyridyl)pyrazole) has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analyses,TG and IR spectroscopy.The compound crystallizes in the triclinic system,space group P1 with a=10.063(4),b=11.554(5),c=11.554(5),α=88.89,β=74.839(4),γ=74.839(4)o,V=1249.8(9) 3,C 16 H 14 MnMo 4 N 6 O 13,M r=937.03,D c=2.490 g/cm 3,μ(MoKα)=2.521 mm 1,F(000)=898,Z=2,the final R=0.0390 and wR=0.0970 for 4000 observed reflections (I > 2σ(Ⅰ)).Single-crystal X-ray diffraction analysis results reveal that compound 1 owns a chain structure based on β-[Mo 8 O 26 ] 4anions,which are linked by Mn II (L) 2 units via the terminal oxygen atoms.     

四组分一锅法合成多取代吡喃[2,3-c]吡唑-5-腈

在三乙胺催化下,以乙酰乙酸甲酯、苯肼、芳醛和丙二腈等4组分为原料,经一锅法合成了一系列多取代的吡喃并[2,3-c]吡唑衍生物(5a～5j),反应在10～15 min内即可完成.所有产物由IR、1HNMR和MS确证.该方法具有产率高、操作简单等优点.     

Siamese‐Twin Porphyrin: A Pyrazole‐Based Expanded Porphyrin of Persistent Helical Conformation

The 3+3‐type synthesis of a pyrazole‐based expanded porphyrin 22 H₄ , a hexaphyrin analogue named Siamese‐twin porphyrin, and its homobimetallic diamagnetic nickel(II) and paramagnetic copper(II) complexes, 22 Ni₂ and 22 Cu₂ , are described. The structure of the macrocycle composed of four pyrroles and two pyrazoles all linked by single carbon atoms, can be interpreted as two conjoined porphyrin‐like subunits, with the two opposing pyrazoles acting as the fusion points. Variable‐temperature 1D and 2D NMR spectroscopic analyses suggested a conformationally flexible structure for 22 H₄ . NMR and UV/Vis spectroscopic evidence as well as structural parameters proved the macrocycle to be non‐aromatic, though each half of the molecule is fully conjugated. UV/Vis and NMR spectroscopic titrations of the free base macrocycle with acid showed it to be dibasic. In the complexes, each metal ion is coordinated in a square‐planar fashion by a dianionic, porphyrin‐like {N₄} binding pocket. The solid‐state structures of the dication and both metal complexes were elucidated by single‐crystal diffractometry. The conformations of the three structures are all similar to each other and strongly twisted, rendering the molecules chiral. The persistent helical twist in the protonated form of the free base and in both metal complexes permitted resolution of these enantiomeric helimers by HPLC on a chiral phase. The absolute stereostructures of 22 H₆ ²⁺, 22 Ni₂ , and 22 Cu₂ were assigned by a combination of experimental electronic circular dichroism (ECD) investigations and quantum‐chemical ECD calculations. The synthesis of the first member of this long‐sought class of expanded porphyrin‐like macrocycles lays the foundation for the study of the interactions of the metal centers within their bimetallic complexes.     

Efficient,One-Pot Synthesis of Triazolothiadiazinyl-pyrazolone and Pyrazolyl-triazolothiadiazine Derivatives via Multicomponent Reaction

A one-pot, multicomponent reaction of 3-(2-bromo acetyl)coumarins, 4-amino-5-hydrazino-4H-[1,2,4]triazole-3-thiol, and different derivatives of ethyl 2-(2-(aryl)hydrazono)-3-oxobutanoates provide an efficient and direct method for the synthesis of 4-(arylydrazono)-3-methyl-1-(6-(coumarin-3-yl)-7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazin-3-yl)-1H-pyrazol-5(4H)-ones (4a–h). A similar methodology was also developed for the synthesis of pyrazolyl-triazolothiadiazines (9a–f) using acetyl acetone, 4-amino-5-hydrazino-4H-[1,2,4]triazole-3-thiol, and different derivatives of phenacylbromide. The resulting products were characterized by analytical and spectral data.