4-[重氮(吡啶-4-基)甲基]吡啶 | 177428-05-6

• 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
• 中文名称: 4-[重氮(吡啶-4-基)甲基]吡啶
• 英文名称: di(4-pyridyl)diazomethane
• 英文别名: Diazodi(4-pyridyl)methan；diazodi(4-pyridyl)methane；4,4'-(Diazomethylene)dipyridine；4-[diazo(pyridin-4-yl)methyl]pyridine
• CAS: 177428-05-6
• 化学式: C₁₁H₈N₄
• 分子量: 196.211
• InChiKey: IWUJKAWQHGINPP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  27.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-[重氮(吡啶-4-基)甲基]吡啶 以 various solvent(s) 为溶剂， 生成 C₁₁H₈N₂
  参考文献：
  名称：

  Preparation of Sterically Congested Di(4-pyridyl)diazomethanes and Characterization of Triplet Carbenes from Them

  摘要：

  Di(4-pyridyl)diazomethanes having two and four ortho chlorine groups were prepared, and the triplet carbenes generated from them were characterized by ESR and UV/vis at low temperature and time-resolved UV/vis at room temperature. An appreciable increase in the stability of triplet carbenes is achieved by introducing ortho chlorine groups.

  DOI：

  10.1021/ol047467p
• 作为产物：
  描述：

  二吡啶-4-甲酮 在 sodium hydroxide 、 一水合肼 、 mercury(II) oxide 作用下， 以 乙醇 、 正己烷 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 4-[重氮(吡啶-4-基)甲基]吡啶
  参考文献：
  名称：

  Koga, Noboru; Ishimaru, Yoichiro; Iwamura, Hiizu, Angewandte Chemie, 1996, vol. 108, # 7, p. 802 - 804

  摘要：

  DOI：

文献信息

• Molecule-Based Magnets in Heterospin Systems
  作者：Noboru Koga、Satoru Karasawa

  DOI：10.1246/bcsj.78.1384

  日期：2005.8

  Our approaches to the molecule-based magnets by using heterospin systems are reviewed. In our heterospin systems consisting of the organic 2p spins and the metal ion 3d spins, various pyridines carrying the organic spins were used as binding ligands for 3d metal ions. Carbenes generated by photolysis of diazo groups and persistent N-tert-butylaminoxyl radicals were employed as the organic spin sources. First, various model complexes were prepared and their magnetic couplings between the organic spin and the metal ion through the pyridine ligand were revealed. Based on the results of magnetic studies on model complexes, ferri- and ferromagnetic complexes having linear chain structures were designed and successfully prepared. When our heterospin systems were used under solution conditions, new fields were opened. Assemblies formed in frozen solution had magnetic behaviors exhibiting slow magnetic relaxations. Especially, when the anisotropic metal ion, high-spin cobalt(II) ion, was used as the metal ion in our heterospin system, the complex formed in frozen solution functioned as a single-molecule magnet (SMM). Such formation of a monometallic SMM was the first example reported.

  回顾了我们使用异自旋系统制备基于分子的磁体的方法。在我们的由有机 2p 自旋和金属离子 3d 自旋组成的异质自旋系统中，携带有机自旋的各种吡啶被用作 3d 金属离子的结合配体。通过重氮基团的光解产生的卡宾和持久的N-叔丁基氨氧基自由基被用作有机自旋源。首先，制备了各种模型配合物，并揭示了它们通过吡啶配体在有机自旋和金属离子之间的磁耦合。基于对模型配合物的磁性研究结果，设计并成功制备了具有线性链结构的铁磁和铁磁配合物。当我们的异质自旋系统在溶液条件下使用时，新的领域被打开。在冷冻溶液中形成的组件具有表现出缓慢磁弛豫的磁性行为。特别是，当各向异性金属离子、高自旋钴(II)离子用作我们的异质自旋系统中的金属离子时，在冷冻溶液中形成的复合物起到单分子磁体(SMM)的作用。这种单金属 SMM 的形成是第一个报道的例子。
• Formation of Ferromagnetic Chains by Photolysis of 1:1 Complexes of Bis(hexafluoroacetylacetonato)copper(II) with Diazodi-4-pyridylmethane
  作者：Yoko Sano、Masakazu Tanaka、Noboru Koga、Kenji Matsuda、Hiizu Iwamura、Pierre Rabu、Marc Drillon

  DOI：10.1021/ja970624d

  日期：1997.9.1

  Bis(hexafluoroacetylacetonato)copper(II) Cu(hfac)2} formed with diazodi-4-pyridylmethane yellow-green plates (a) and dark green bricks (b) in a 1:1 complex. X-ray crystal and molecular structure analysis of a single crystal of a revealed that the two pyridyl nitrogens of two different ligand molecules are coordinated with Cu(II) in a trans configuration to produce a one-dimensional chain. Complex

  双（六氟乙酰丙酮）铜（II）Cu（hfac）2}与重氮二-4-吡啶基甲烷黄绿色板（a）和深绿色砖（b）以1：1复合物形成。单晶的 X 射线晶体和分子结构分析表明，两个不同配体分子的两个吡啶基氮与 Cu(II) 以反式构型配位以产生一维链。复合物 b 包含溶剂分子。摩尔磁化率的温度依赖性表明，虽然复合物在辐照前是稀释的 Cu(II) 顺磁体，但由于 Cu(II) 的 3d 自旋和 di-4-pyridylcarbene 的 2p 自旋，它们成为铁磁链。重氮组。磁化强度的场依赖性表明铁磁链的表观自旋量子数等于 S = ca。33. 6 复杂 b. 一种理论方法表明，相邻的 Cu(II) 和沿链的卡宾中心之间的铁磁相互作用为 J/kB = ...
• Tacticity versus dimension of the extended structures in the crystals of heterospin magnets made of transition-metal complexes with the poly(aminoxyl) radical
  作者：Hiizu Iwamura、Katsuya Inoue、Noboru Koga

  DOI：10.1039/a707641j

  日期：——

  Bis- and tris(aminoxyl) radicals and di(4-pyridyl)diazomethane form crystalline complexes with extended structures upon reaction with [M(hfac)2] (M=MnII or CuII, and hfac=hexafluoroacetylacetonate). Organic 2p and metal 3d spins in these complexes order at 3.4–46 K depending on the dimensions of the extended structures and the magnitude of exchange coupling between the adjacent spins. In the crystals of one-dimensional systems, the polymeric chains are isotactic in that free radical or precursor ligands and/or metal centres have the same chirality along any given chain. The polymeric chains are syndiotactic and cross link to form two-dimensional honeycomb or three-dimensional crossed parallel networks.

  双（氨基氧）和三（氨基氧）自由基以及二（4-吡啶基）重氮甲烷与 [M(hfac)2]（M=锰Ⅱ或铜Ⅱ，hfac=六氟乙酰丙酮）反应后形成具有扩展结构的结晶络合物。这些复合物中的有机 2p 和金属 3d 自旋在 3.4-46 K 下有序，这取决于扩展结构的尺寸和相邻自旋之间交换耦合的大小。在一维系统的晶体中，聚合物链是同向的，即自由基或前体配体和/或金属中心在任何给定的链上都具有相同的手性。聚合链是双向的，交叉连接形成二维蜂巢或三维交叉平行网络。
• Photochemical Formation of Ferrimagnetic Chains from a Pair of Polymeric Complexes Made of Octahedral Bis(hexafluoroacetylacetonato)manganese(II) with Diazodi(4-pyridyl)methane in the Cis and Trans Configurations as Repeating Units
  作者：Satoru Karasawa、Yoko Sano、Takeyuki Akita、Noboru Koga、Tetsuji Itoh、Hiizu Iwamura、Pierre Rabu、Marc Drillon

  DOI：10.1021/ja981293n

  日期：1998.10.1

  and revealed χmolT vs T plots characteristic of ferrimagnetic chains after irradiation for 97 h; interaction between the manganese(II) ion and the photogenerated carbene is antiferromagnetic in both complexes. The antiferromagnetic exchange coupling parameters (J) in the photolyzate of complex a and b were estimated by a theoretical treatment through a procedure of extrapolation by using s...

  制备了与重氮二(4-吡啶基)甲烷(1)配位的二(六氟乙酰丙酮)锰(II)的两种1:1锰配合物a和b。配合物 a 和 b 分别在正交空间群 Pbca 和单斜晶系 C2/c 中结晶。来自两个不同分子 1 的两个吡啶基氮原子以顺式和反式构型与锰离子配位，分别在配合物 a 和 b 中形成八面体锰配合物的螺旋形和锯齿形无限链。在 SQUID 磁化计上测量辐照前后两种晶体的磁化率 (χmol)，并显示辐照 97 小时后亚铁磁链的 χmolT 与 T 曲线特征；锰 (II) 离子和光生卡宾之间的相互作用在两种配合物中都是反铁磁性的。
• Diazodi(4-pyridyl)methane and Diazophenyl-(4-pyridyl)methane as Photoresponsive Ligands for Metal–Carbene Hetero-Spin Systems
  作者：Noboru Koga、Yoichiro Ishimaru、Hiizu Iwamura

  DOI：10.1002/anie.199607551

  日期：1996.4.19