N,N’-bis(pyridine-4-yl)formamidine | 1240106-59-5

• 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: N,N’-bis(pyridine-4-yl)formamidine
• 英文别名: N,N'-bis(pyridin-4-yl)formamidine；N,N'-di(pyridin-4-yl)formamidine；N,N'-dipyridin-4-ylmethanimidamide
• CAS: 1240106-59-5；387831-58-5
• 化学式: C₁₁H₁₀N₄
• 分子量: 198.227
• InChiKey: UQRQDPRDRYGJBO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  50.2
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N,N’-bis(pyridine-4-yl)formamidine 、 silver(I) acetate 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以64%的产率得到
  参考文献：
  名称：

  Au(I) and Ag(I) formamidinate tetranuclear complexes and coordination polymers: Synthesis, structures and luminescent properties

  摘要：

  Reactions of AuCIS(CH3)(2) and Ag(I) salts (AgSCN, AgOAc and AgSbF6) with the lithiated formamidines afforded the tetranuclear complexes [Au-4(4-pyf)(4)]center dot 4CH(3)OH [4-Hpyf = N,N'-bis(pyridine-4-yl)formamidine], 1, [Au-4(pmf)(4)] [Hpmf = N,N'-bis(pyrimidine-2-yl)formamidine], 2, and [Ag-4(pmf)(4)], 3, and the coordination polymers [Ag-2(OAc)(4-pyf)](n), 4, and {[Ag-2(4-pyf)(2)]center dot THF}(n), 5, which have been structurally characterized by X-ray crystallography. The intramolecular Au center dot center dot center dot Au separations in 1 and 2 are in the range 2.8832(2)-3.3338(10) angstrom and the Ag center dot center dot center dot Ag separations in 3-5 are 2.7927(3)-2.9819(19) angstrom, indicating the existence of aurophilicity and argentophilicity, respectively. Complex 3 is a unique tetranuclear complex of the type Ag-4(form)(4) in which "form" represents the formamidinate ligands. The short lifetimes of 1.06-49.15 ns for 1-5 indicate that the emissions belong to fluorescence. Moreover, complex 4 emits white luminescence in the solid-state and the CIE coordinate appears at (0.30, 0.38), which represents the first single-emitting component white phosphor in the class of formamidinate coordination polymers.

  DOI：

  10.1016/j.ica.2018.07.024
• 作为产物：
  描述：

  4-氨基吡啶 、 原甲酸三甲酯 在 choline chloride*2SnCl2 作用下， 反应 4.0h， 以66%的产率得到N,N’-bis(pyridine-4-yl)formamidine
  参考文献：
  名称：

  Deep eutectic solvent promoted highly efficient synthesis of N, N’-diarylamidines and formamides

  摘要：

  摘要 采用深共晶溶剂作为双重催化剂和反应介质，在不使用有害有机溶剂和催化剂的情况下高效地对芳香胺进行 N-甲酰化反应。芳香胺与原甲酸三甲酯和甲酸在 70 ℃ 的深共晶溶剂中进行处理，可以得到相应的 N-甲酰基衍生物，收率良好甚至极佳。这种简单的铵深共晶溶剂，很容易从氯化胆碱和氯化锡中合成，具有 100% 的原子经济性，适用于工业和实验室。此外，在深共晶溶剂中加热原甲酸三甲酯和芳香族伯胺，可以高产率生成相应的 N,N'-二芳基酰胺。

  DOI：

  10.1016/j.crci.2012.06.011

文献信息

• Insight into the mechanism of three component condensation leading to aminomethylenebisphosphonates
  作者：Ewa Dąbrowska、Agnieszka Burzyńska、Artur Mucha、Ewa Matczak-Jon、Wanda Sawka-Dobrowolska、Łukasz Berlicki、Paweł Kafarski

  DOI：10.1016/j.jorganchem.2009.07.025

  日期：2009.11

  mechanism of the reaction remains unknown. p-Nitroaniline has been found an interesting tool to shed light on this matter. Its use allowed to separate and identify four intermediates, both non-phosphorus and phosphorus containing, and subsequently suggest the mechanism of the whole process. The acquired knowledge was helpful in explanation the route and the final product structure obtained for more

  伯胺，亚磷酸二乙酯和原甲酸三乙酯的三组分反应，然后加合物的酸水解，以良好的收率提供了N-取代的氨基亚甲基双膦酸。它用途广泛，通常用于制备具有潜在抗骨质疏松，抗菌，抗癌，抗寄生虫或除草活性的化合物。但是，反应机理仍然未知。p-硝基苯胺已被发现是阐明这一问题的有趣工具。它的使用可以分离和鉴定出四种不含磷和含磷的中间体，随后提示了整个过程的机理。获得的知识有助于解释使用4-氨基吡啶进行更复杂反应的路线和最终产物结构。毫无疑问地证明了吡啶氮原子的另外的烷基化，导致意外的N-（1-烷基吡啶-4-氨基）亚甲基双膦酸。
• Amine Exchange in Formamidines: An Experimental and Theoretical Study
  作者：Marinha dF. Capela、Nicholas J. Mosey、Liyan Xing、Ruiyao Wang、Anne Petitjean

  DOI：10.1002/chem.201002389

  日期：2011.4.11

  simultaneous proton‐induced electrophilicity enhancement that allows for the exchange of their amine portion. The NC(H)NH fragment, therefore, undergoes “imine‐like” exchange with N‐containing nucleophiles. Because of the prototropic equilibrium, the NC(H)NH fragment may behave as a “bisimine” centred on the same carbon, in which both N‐containing fragments can be exchanged. Considering the proton‐induced

  Ñ  -含有H甲脒结合相当强关联为羧酸，以形成良好限定的几何形状的络合物以同时质子诱导的亲电性的增强，其允许它们的胺部分的交换。所述NC（H） NH片段，因此，经过“亚胺样”与含N亲核试剂交换。由于质子的平衡，所述NC（H） NH片段可以表现为“双亚胺”为中心在相同的碳，其中两个含N片段可以被交换。同时考虑C的质子诱导致敏N单元和明确定义的甲am-羧酸配合物几何形状，应该可以使用羧酸作为模板，通过甲form内的动态胺交换来合成确定的结构。这项研究重点介绍了基于进料胺（脂肪族胺，芳香族胺和烷氧基胺）性质的三种交换方式，以及基于胺离去基团的交换规则。经过该分析，提供了通过动态交换形成羧酸模板化大环化合物的概念证明。
• Luminescence properties and optimized structural conformations of the S₀, S₁ and T₁ states of a tetranuclear formamidinate complex based on Au^I and Ag^I metal ions
  作者：Wayne Hsu

  DOI：10.1107/s2053229619008581

  日期：2019.7.1

  N,N′-Bis(pyridin-4-yl)formamidine (4-pyfH) was reacted with Au^I and Ag^I metal salts to form a novel tetranuclear complex, tetrakis[μ-N,N′-bis(pyridin-4-yl)formamidinato]digold(I)disilver(I), [Ag₂Au₂(C₁₁H₉N₄)₂] or [Au _x Ag_4–x (4-pyf)₄] (x = 0–4), 1, which is supported by its metallophilicity. Due to the potential permutation of the coordinated metal ions, six different canonical structures of 1 can be obtained. Complex 1 shows an emission at 501 nm upon excitation at 375 nm in the solid state and an emission at 438 nm upon excitation at 304 nm when dispersed in methanol. Time-dependent density functional theory (TD-DFT) calculations confirmed that these emissions can be ascribed to metal-to-ligand charge transfer (MLCT) processes. Moreover, the calculations of the optimized structural conformations of the S₀ ground state, and the S₁ and T₁ excited states are discussed and suggest a distorted planar conformation for the tetranuclear Au₂Ag₂ complex.

  N,N′-双(吡啶-4-基)甲脒(4-pyfH)与 AuI 和 AgI 金属盐反应生成一种新型四核配合物，即四[μ-N,N′-双(吡啶-4-基)甲脒]二金(I)二银(I)，[Ag2Au2(C11H9N4)2] 或 [Au x Ag4-x (4-pyf)4］(x = 0-4)，1，其亲金属性证明了这一点。由于配位金属离子的潜在排列方式，可以得到 1 的六种不同的典型结构。络合物 1 在固态下于 375 纳米波长激发时会发出 501 纳米波长的光，而分散在甲醇中时，于 304 纳米波长激发时会发出 438 纳米波长的光。与时间相关的密度泛函理论（TD-DFT）计算证实，这些发射可归因于金属-配体电荷转移（MLCT）过程。此外，还讨论了 S0 基态、S1 和 T1 激发态的优化结构构象，并提出了四核 Au2Ag2 复合物的扭曲平面构象。
• Stepwise formation of heteronuclear coordination networks based on quadruple-bonded dimolybdenum units containing formamidinate ligands
  作者：Wayne Hsu、Yu-Sian Li、Hsiu-Yi He、Kuan-Ting Chen、Hong-Sheng Wu、Davide M. Proserpio、Jhy-Der Chen、Ju-Chun Wang

  DOI：10.1039/c4ce00474d

  日期：——

  The first 2D and 3D heteronuclear coordination networks based on quadruple-bonded dimolybdenum units containing formamidinate ligands are reported.

  首次报道了基于含有甲脒配体的四键二钼单元的二维和三维异核配位网络。