4,4'-methylenebis(1-(2-pyridyl)-3,5-dimethylpyrazole) | 1429329-55-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 4,4'-methylenebis(1-(2-pyridyl)-3,5-dimethylpyrazole)
• 英文别名: 2-[4-[(3,5-Dimethyl-1-pyridin-2-ylpyrazol-4-yl)methyl]-3,5-dimethylpyrazol-1-yl]pyridine；2-[4-[(3,5-dimethyl-1-pyridin-2-ylpyrazol-4-yl)methyl]-3,5-dimethylpyrazol-1-yl]pyridine
• CAS: 1429329-55-4
• 化学式: C₂₁H₂₂N₆
• 分子量: 358.446
• InChiKey: LQYIVTKBTSUHNU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  27
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  61.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  copper(II) choride dihydrate 、 4,4'-methylenebis(1-(2-pyridyl)-3,5-dimethylpyrazole) 以 乙腈 为溶剂， 以75%的产率得到
  参考文献：
  名称：

  Synthesis and characterisation of dinuclear Co(II), Ni(II) and Cu(II) unsaturated helical complexes from a novel dipyridyl-bispyrazole ligand

  摘要：

  Reported here is the synthesis of a novel bis-bidentate ligand 4,4'-methylenebis(1-(2-pyridyI)-3,5-dimethylpyrazole), L, along with the synthesis and structural characterisation of three unsaturated dinuclear helical complexes that it forms with Co(II), 1, Ni(II), 2, and Cu(II), 3. The structure of 1, [LCoCl(H2O)](2) [CoCl4]center dot 2MeCN, is comprised of two Co(II) ions with octahedral geometry around which two ligand molecules wrap to generate a compact unsaturated double helicate, with coordination about each Co(II) completed by a water molecule and chloride ion. Packing of the complex is such that helicate species align head-to-tail, with the metal bound water molecule and chloride ligand on adjacent helicates hydrogen-bonding to each other in a reciprocal fashion to form a 1D polymer. Complex 2, [LNiCl](2)center dot xH(2)O, possesses a similar molecular structure to that found in 1, however in this instance the coordination about each octahedral Ni(II) ion is comprised from two ligand molecules and two chloride ions to yield a charge neutral unsaturated double helical species. Packing of adjacent helical species in 2 creates large void spaces throughout the crystal lattice within which disordered solvent molecules reside. The structure of 3, [LCu2Cl4], is a single stranded dinuclear helical species whereby one ligand molecule wraps about two highly distorted square planar Cu(II) centres, with two chloride ions completing the coordination sphere to yield a neutral species. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2012.09.035
• 作为产物：
  描述：

  2-肼吡啶 在 Oxone 、 二甲基亚砜 作用下， 反应 2.08h， 生成 4,4'-methylenebis(1-(2-pyridyl)-3,5-dimethylpyrazole)
  参考文献：
  名称：

  Oxone-DMSO触发亚甲基插入和C（sp 2）-C（sp 3）-HC（sp 2）键形成，以访问功能性双杂环。

  摘要：

  为了制备新型的双杂环支架，实现了新的C（sp 2）–C（sp 3）-H–C（sp 2）键的构建，实现了无金属亚甲基的插入。完整的机理研究包括实验研究和DFT计算，并且以中等到高产率制备了各种对称和不对称的双吡唑以及其他基于吡唑的双杂环分子。不对称吡唑中桥连亚甲基的进一步修饰产生了手性中心，从而扩展了该方法的范围。

  DOI：

  10.1021/acs.joc.9b03477

文献信息

• Discrete and Polymeric Cu(II) Coordination Complexes with a Flexible bis-(pyridylpyrazole) Ligand: Structural Diversity and Unexpected Solvothermal Reactivity
  作者：Chris S. Hawes、Paul E. Kruger

  DOI：10.1071/ch12443

  日期：——

  acetonitrile, and each contains a co-ligand formed by either decomposition of the solvent or ligand. Complex 3, [Cu4(NO3)4(µ-CH3COO)2(µ-OH)2L2], forms an unusual discrete cyclic tetrameric species containing acetate co-ligands derived through acetonitrile hydrolysis; whereas complex 4, [CuL(C2O4)(NO3)], forms a one-dimensional coordination polymer containing bridging oxalate co-ligands, formed through hydrolysis

  这里报道的是从双双齿配体4,4'-亚甲基双（1-（2-吡啶基）-3,5-二甲基吡唑）L衍生的五个铜配合物的合成和结构表征。络合物1 [Cu 2 L（CH 3 COO）4（OH 2）2 ]·6H 2 O是单链不饱和螺旋物质，形成高度连接的三维氢键网络，而[Cu 2 L（ NO 3）4 ]，2是衍生自[Cu 2 L]片段通过桥接硝酸根阴离子连接在一起，产生具有（6,3）拓扑结构的起伏二维薄片。配合物3，4，和5当单个批次内共结晶大号是溶剂热的条件下与铜（NO反应3）2 ·2.5H 2 Ó在乙腈中，并且每个含有的共配位体通过溶剂的任一分解而形成或配体。络合物3，[Cu 4（NO 3）4（µ-CH 3 COO）2（µ-OH）2 L 2]，形成不寻常的不连续的环状四聚体物质，其中包含通过乙腈水解得到的乙酸酯共配体；而配合物4 [Cu L（C 2 O 4）（NO 3）]形成一维配位聚合物，其中包含桥接
• Oxone-DMSO Triggered Methylene Insertion and C(sp²)−C(sp³)-H−C(sp²) Bond Formation to Access Functional Bis-Heterocycles
  作者：Jaspreet Kour、Vunnam Venkateswarlu、Praveen K. Verma、Yaseen Hussain、Gurudutt Dubey、Prasad V. Bharatam、Subash C. Sahoo、Sanghapal D. Sawant

  DOI：10.1021/acs.joc.9b03477

  日期：2020.4.3

  Metal-free insertion of a methylene group was achieved for the construction of a new C(sp2)–C(sp3)-H–C(sp2) bond in order to prepare novel bis-heterocyclic scaffolds. The complete mechanistic investigations included experimental study and DFT calculations, and various symmetric and unsymmetric bis-pyrazoles as well as other pyrazole-based bis-heterocyclic molecules were prepared in moderate to high

  为了制备新型的双杂环支架，实现了新的C（sp 2）–C（sp 3）-H–C（sp 2）键的构建，实现了无金属亚甲基的插入。完整的机理研究包括实验研究和DFT计算，并且以中等到高产率制备了各种对称和不对称的双吡唑以及其他基于吡唑的双杂环分子。不对称吡唑中桥连亚甲基的进一步修饰产生了手性中心，从而扩展了该方法的范围。
• Synthesis and characterisation of dinuclear Co(II), Ni(II) and Cu(II) unsaturated helical complexes from a novel dipyridyl-bispyrazole ligand
  作者：Chris S. Hawes、Paul E. Kruger

  DOI：10.1016/j.poly.2012.09.035

  日期：2013.3

  Reported here is the synthesis of a novel bis-bidentate ligand 4,4'-methylenebis(1-(2-pyridyI)-3,5-dimethylpyrazole), L, along with the synthesis and structural characterisation of three unsaturated dinuclear helical complexes that it forms with Co(II), 1, Ni(II), 2, and Cu(II), 3. The structure of 1, [LCoCl(H2O)](2) [CoCl4]center dot 2MeCN, is comprised of two Co(II) ions with octahedral geometry around which two ligand molecules wrap to generate a compact unsaturated double helicate, with coordination about each Co(II) completed by a water molecule and chloride ion. Packing of the complex is such that helicate species align head-to-tail, with the metal bound water molecule and chloride ligand on adjacent helicates hydrogen-bonding to each other in a reciprocal fashion to form a 1D polymer. Complex 2, [LNiCl](2)center dot xH(2)O, possesses a similar molecular structure to that found in 1, however in this instance the coordination about each octahedral Ni(II) ion is comprised from two ligand molecules and two chloride ions to yield a charge neutral unsaturated double helical species. Packing of adjacent helical species in 2 creates large void spaces throughout the crystal lattice within which disordered solvent molecules reside. The structure of 3, [LCu2Cl4], is a single stranded dinuclear helical species whereby one ligand molecule wraps about two highly distorted square planar Cu(II) centres, with two chloride ions completing the coordination sphere to yield a neutral species. (C) 2012 Elsevier Ltd. All rights reserved.