Facile and Convenient Synthesis of Pyrazole,Pyridine, Pyridazine,Pyrazolo[3,4-b]pyridine,and Pyrazolo[5,1-c][1,2,4]triazine Derivatives

Abstract

A convenient synthesis of a series of pyrazole, pyridine, pyridinethione, pyridazine, pyrazolo[3,4-b]pyridine, imidazo[1,2-a]pyrimidine, and pyrazolo[5,1-c][1 Kumar , R. 5-(1-Substituted)alkyl pyrimidine nucleosides as antiviral (herpes) agents . Curr. Med. Chem. 2004 , 11 , 2749 – 2766 . [Google Scholar] 2 Holy , A. ; Günter , J. ; Dvoráková , H. ; Masojídková , M. ; Andrei , G. ; Snoeck , R. ; Balzarini , J. ; De Clercq , E. Structure–antiviral activity relationship in the series of pyrimidine and purine N-[2-(2-phosphonomethoxy)ethyl] nucleotide analogues, 1: Derivatives substituted at the carbon atoms of the base . J. Med. Chem. 1999 , 42 , 2064 – 2086 . [Google Scholar] 4 Brandes , W. ; Daum , W. ; Krauss , P. Fungicidal oxime ethers. Ger. Patent 2,623,847, 1977; Chem. Abstr . 1978 , 88 , 120822h . [Google Scholar]]triazine derivatives incorporating a pyrimidine moiety, via the reactions of the versatile, readily accessible 3-oxo-N-(pyrimid-2-yl)butanamide with the appropriate reagents, is described.     

Synthesis,Crystal Structure and Biological Activity of a Novel Complex： Co（L）2（CH3OH）2Cl2 （L = 3-（1,2,4-Triazole-yl）-6-chloro-pyridazine）

The title compound, Co（L）2（CH3OH）2Cl2 （L = 3-（1,2,4-triazole-yl）-6-chloro-pyridazine） 1, has been synthesized and its crystal structure has been determined by X-ray analysis. Complex 1 crystallizes in the triclinic system, space group P1 with a = 6.018（3）, b = 9.832（5）, c = 9.921（5）A, a = 78.270（8）, β = 74.550（8）, γ = 83.807（8）°, V = 553.1（5）A^3, Z = 1, C14H16Cl4CoN10O2, Mr = 557.10, Dc = 1.673 g/cm^3, F（000） = 281,μ（MoKα） = 1.293 mm^-1, the final R = 0.0453 and wR = 0.1181 for 1539 observed reflections with I 〉 2σ（I）. The Co（II） ion is in a distorted centrosymmetric six-coordinate octahedral environment with two Ntriazole, two Omethanol and two Cl atoms. Via hydrogen bonds the configuration of 1 has been extended into 1D chains which are developed to 2D layers via π-π sticking action, and these layers are further extended into a 3D network by hydrogen bonds. The antibacterial activity of the title compound has been detected, and the results show that the ligands and cobalt（II） complex exhibit certain fungicidal activity against several bacteria. Furthermore, the spectral properties of the title compound have been also studied and discussed.     

Click Chemistry Derived Pyridazines: Electron‐Deficient Building Blocks with Defined Conformation and Packing Structure

A series of 3,6‐bis(4‐triazolyl)pyridazines equipped with terminal phenyl substituents with varying degree of fluorination were synthesized by using the facile copper‐catalyzed azide–alkyne cycloaddition and their structures were thoroughly investigated in the gas phase, in solution, and in the solid state by employing DFT calculations, NMR spectroscopy, and single‐crystal X‐ray diffraction, respectively. On the molecular level, their structure is governed by the strong preference of the triazole‐pyridazine linkages for the anti ‐conformation. The supramolecular organization of the molecules in the crystalline solid is controlled by π‐stacking, C−H⋅⋅⋅π as well as C−F⋅⋅⋅H interactions. The latter can conveniently be tuned by the number and position of fluorine substituents in the terminal phenyl units, giving rise to either herringbone‐like, 1D or 2D lamellar packing. Electrochemistry and optical spectroscopy of all compounds suggest that they might find use as electron‐transporting/hole‐blocking materials in organic electronics.     

哒嗪—碘电荷转移复合物的导电性

本文制备了哒嗪-碘电荷转移复合物,导电率达1—10~2S/cm。使之与碘混合在碘含量达98％时,仍具有1S/cm的导电率。用电压端短路法测量导电率的温度依赖性,发现在室温—-30℃导电率升高20％,在-30—100℃间导电率下降为室温时的-10％或更小。还报道了元素分析、x射线光电子能谱及激光拉曼光谱的数据。     

Synthesis of Novel Polyfunctionally Substituted Thieno[2,3‐c]pyridazines

4‐Cyano‐5,6‐dimethylpyridazin‐3‐(2H)‐thione 3b was used as a key intermediate for the synthesis of novel polysubstituted thieno[2,3‐c]pyridazines.     

新型化学杂交剂哒嗪酮衍生物的合成及其对小麦去雄活性研究

从吡喃酮与不同的芳基重氮盐的偶联反应制备了1,4-二氢-3-羧基哒嗪-4-酮类化合物,并首次以它们为原料分别与氨基硫脲和肼或苯肼进行环合反应得到了两类去雄化学杂交剂杂环化合物--哒嗪酮氨基噻唑以及哒嗪吡唑酮化合物.初步去雄活性实验显示哒嗪酮氨基噻唑盐酸盐类化合物在较高剂量时具有去雄活性,在剂量为2100g/ha时去雄率达99%左右.     

Synthesis of new 1<Emphasis Type="Italic">H</Emphasis>-pyridazine derivatives <Emphasis Type="Italic">peri</Emphasis>-annelated with acenaphthene and acenaphthylene

The reaction of 6-acetyl-5-hydroxyacenaphthene with methylhydrazine afforded 1,3-dimethyl-1H-6,7-dihydroacenaphtho[5,6-de]pyridazine. Its dehydrogenation with chloranil gave 1,3-dimethyl-1H-acenaphtho[5,6-de]pyridazine, which is a heteroaromatic compound with an essentially new topology of the ρsystem. The reaction of 3-methyl-1H-6,7-dihydroacenaphtho[5,6-de]pyridazine with 3,5-di-tert-butyl-1,2-benzoquinone yielded a dimer containing the acenaphthene and acenaphthylene moieties of peri-annelated 1H-1,2-diazines connected in positions 1′ and 9.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 777–780, March, 2005.     

6-羟基富烯及环戊二烯并[d]哒嗪的合成

本文以6, 6-二烷基富烯与烯丙基格氏试剂反应所得的取代环戊二烯基负离子与芳酰氯反应, 合成了5个新的6-羟基富烯化合物(1-5)。用此化合物与肼反应, 合成了5个新的环戊二烯并[d]哒嗪化合物(6-10)。通过^1H NMR、IR及元素分析确定了它们的结构。