benzophenoneimine of 1,4-diaminobenzene | 62327-31-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: benzophenoneimine of 1,4-diaminobenzene
• 英文别名: DAB-benzophenone；DPAG1；N,N'-dibenzhydrylidene-p-phenylenediamine；N,N'-Dibenzhydryliden-p-phenylendiamin；N.N'-Bis-diphenylmethylen-p-phenylendiamin；N1,N4-Bis(diphenylmethylene)benzene-1,4-diamine；N-[4-(benzhydrylideneamino)phenyl]-1,1-diphenylmethanimine
• CAS: 62327-31-5
• 化学式: C₃₂H₂₄N₂
• 分子量: 436.556
• InChiKey: NCVWCKLTOBSUCC-UHFFFAOYSA-N

物化性质

• 熔点：
  180 °C(Solv: ethanol (64-17-5))
• 沸点：
  568.8±46.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.3
• 重原子数：
  34
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  benzophenoneimine of 1,4-diaminobenzene 在 sodium tetrahydroborate 、 tin(ll) chloride 作用下， 以 氯仿 、 乙腈 为溶剂， 反应 0.17h， 以89%的产率得到N~1~,N~4~-Bis(diphenylmethyl)benzene-1,4-diamine
  参考文献：
  名称：

  Control of Stepwise Radial Complexation in Dendritic Polyphenylazomethines

  摘要：

  The fourth generation of a dendritic polyphenylazomethine (DPA 134) has 2, 4, 8, and 16 imine groups in the first, second, third, and fourth shells, respectively (total, 30 imine groups). DPA G4 can trap 30 equiv of SnCl2 molecules, because the imine group is complexed with SnCl2 at a ratio of 1:1. During addition of 30 equiv of SnCl2 to DPA G4, four shifts in the isosbestic point were observed in the UV-vis spectra, and the amount of SnCl2 added in each step is in agreement with the number of imine groups in each shell of DPA G4. This result shows that the complexation of the imine groups in DPA G4 with SnCl2 occurs stepwise in the order of the first, second, third, and fourth shells. The unique stepwise complexation was also observed in DPA G2 and G3 as two and three shifts of the isosbestic point, respectively. The stepwise complexation was supported by TEM, NMR, and a novel shell-selective reduction (SSR) method for imines. An expansion in the molecular size of DPA G4 by the complexation was revealed by molecular modeling and TEM measurements. The stepwise complexation is caused by the different basicity of the imine groups between the shells, which was supported by the chemical shifts of the peaks attributed to the imine carbons in the C-13 NMR spectra. The gradients in the basicity were controlled by the introduction of electron-withdrawing or -releasing groups to the core of the dendrimers; the core imines were complexed last in DPAs having a 2,3,5,6-tetrafluoro or 2,5-dichlorophenyl core due to the low basicity of the core imines. The different complexation pattern was also clearly confirmed by the SSR method.

  DOI：

  10.1021/ja035608x
• 作为产物：
  描述：

  二苯甲酮 、 对苯二胺 在 三乙烯二胺 、 四氯化钛 作用下， 以 氯苯 为溶剂， 反应 12.58h， 以44%的产率得到benzophenoneimine of 1,4-diaminobenzene
  参考文献：
  名称：

  通过形式的氨基转移反应合成二维亚胺键合的共价有机骨架

  摘要：

  共价有机骨架（COF）是具有可调拓扑和功能的结晶，永久多孔，二维或三维聚合物。与亚胺或β-酮胺相比，与亚胺或β-酮胺连接的COF在化学上更稳定，从而使其在包括储能装置，质子传导膜和催化剂载体在内的广泛应用中更具前景。我们报告了基于N的正式转氨合成亚胺和β-酮胺连接的COF的通用且可扩展的方法芳基二苯甲酮亚胺。这些底物通常是传统多官能芳基胺单体的合成前体，并且更稳定，可溶且易于处理和纯化。通过X射线衍射和表面积分析表征，从该方法获得的与亚胺和β-酮胺连接的COF显示出优异的材料质量。最优化的COF的Brunauer-Emmett-Teller表面积（> 2600 m 2 / g）非常接近其理论值（2830 m 2/G）。该方法适用于常规的溶剂热条件和微波加热，以较短的反应时间提供相似或什至更高的材料质量。高材料质量，可扩展性和二苯甲酮亚胺单体的可用性都是该方法的吸引人的特征。

  DOI：

  10.1021/jacs.7b06913

文献信息

• Novel Phenylazomethine Dendrimers:  Synthesis and Structural Properties
  作者：Masayoshi Higuchi、Satoshi Shiki、Kimihisa Yamamoto

  DOI：10.1021/ol006241t

  日期：2000.10.1

  dendrimers consisting of a pi-conjugated backbone, the dendritic polyphenylazomethines (DPAs), were synthesized by the convergent method via the dehydration of aromatic ketones with aromatic amines in the presence of titanium(IV) tetrachloride. The obtained DPAs have a high solubility unlike the conventional linear polyphenylazomethines. NMR studies revealed the conformational rigidity of DPA G4. DPAs

  在四氯化钛（IV）存在下，通过芳族酮与芳族胺的脱水反应，通过收敛方法合成了由π-共轭骨架组成的新型树状聚合物，即树状聚苯基偶氮甲亚胺（DPA）。不同于常规的线性聚苯基偶氮甲亚胺，所获得的DPA具有高溶解度。NMR研究表明DPA G4的构象刚性。具有许多偶氮甲碱基团作为金属离子配位点的DPA有望成为新型配体。
• One-Step Synthesis of a Platinum Nanoparticle with Carbon Materials Using a Phenylazomethine Dendrimer as a Template
  作者：Osamu Enoki、Takane Imaoka、Kimihisa Yamamoto

  DOI：10.1246/bcsj.79.621

  日期：2006.4

  A phenylazomethine dendrimer was developed for the one-step preparation of a platinum nanoparticle–carbon nanocomposite. The dendrimer formed a complex with platinum tetrachloride (PtCl4) in a chloroform–acetonitrile mixed solvent. The coordination behavior between the dendrimer and the platinum salts was confirmed by UV–vis and 1H NMR titration experiments. The obtained dendrimer–PtCl4 complexes were pyrolyzed under a nitrogen atmosphere at 1000 °C, and converted to spherical and dispersed platinum nanoparticles on a pyrolytic graphite identified by transmission electron microscopy (TEM). A high resolution TEM (HR-TEM) image of the products showed some lattice fringes attributed to the presence of Pt(111) in the particles, and X-ray photoelectron spectra (XPS) of the products corresponded to those of Pt(0). These results indicated that PtCl4 was perfectly converted to metallic platinum through this pyrolysis condition. Raman spectra showed that the dendrimer remained as an amorphous carbon after pyrolysis. The electrode modified with the product showed a catalytic activity for dioxygen reduction, which electrochemically confirmed that part of the carbon was porous enough to let the substrate go through and to reach the platinum surface.

  为一步制备铂纳米粒子-碳纳米复合材料开发了一种苯基偶氮甲基树枝状聚合物。在氯仿-乙腈混合溶剂中，树枝状聚合物与四氯化铂（PtCl4）形成了复合物。树枝状聚合物与铂盐之间的配位行为通过紫外可见光和 1H NMR 滴定实验得到了证实。得到的树枝状聚合物-PtCl4 复合物在 1000 °C 的氮气环境下进行热解，并在热解石墨上转化为球形分散的铂纳米颗粒，经透射电子显微镜（TEM）鉴定。产物的高分辨率 TEM（HR-TEM）图像显示出一些晶格边缘，这是因为颗粒中存在 Pt(111)，而产物的 X 射线光电子能谱（XPS）与 Pt(0)相对应。这些结果表明，通过这种热解条件，PtCl4 完美地转化成了金属铂。拉曼光谱显示，热解后树枝状聚合物仍为无定形碳。经该产品修饰的电极显示出对二氧还原的催化活性，这在电化学上证实了部分碳的多孔性足以让基质穿过并到达铂表面。
• Controlled Storage of Ferrocene Derivatives as Redox-Active Molecules in Dendrimers
  作者：Yousuke Ochi、Mana Suzuki、Takane Imaoka、Masaki Murata、Hiroshi Nishihara、Yasuaki Einaga、Kimihisa Yamamoto

  DOI：10.1021/ja9064377

  日期：2010.4.14

  polyphenylazomethines (DPA) could encapsulate ferroceniums by complexation of the electron-donating skeleton of the DPA imines. Upon addition of ferroceniums to a series of dendritic polyphenylazomethines (DPAGX, where X is the generation number, X = 1-4), the UV-vis spectra showed changes in a manner similar to that observed for the complexation of metal ions with DPAGX. Stepwise shifts in the isosbestic

  树枝状聚苯偶氮甲碱 (DPA) 可以通过 DPA 亚胺的给电子骨架的络合来封装二茂铁。将二茂铁添加到一系列树枝状聚苯偶氮甲碱 (DPAGX，其中 X 是代数，X = 1-4) 后，UV-vis 光谱显示的变化类似于金属离子与 DPAGX 络合时观察到的变化。随着第 4 代树枝状聚合物 (DPAG4) 的第一层和第二层中亚胺基团的数量的变化，一致地观察到等吸收点的逐步变化。还发现 DPAG2 和 DPAG3 可捕获 6 当量的二茂铁。为了研究络合，进行了紫外-可见光谱、(57)Fe Mossbauer 光谱、电喷雾电离质谱 (ESI-MS)、循环伏安法 (CV) 和荧光光谱。我们证实中性二茂铁不能与亚胺基团络合，而二茂铁可以。利用二茂铁的氧化还原特性，我们能够以类似于氧化还原响应蛋白（如铁蛋白）的方式，以电化学方式控制二茂铁的封装和释放到 DPA 中。除了二茂铁之外，低聚二茂铁也可能被困在 DPA
• Knoevenagel, Journal fur praktische Chemie (Leipzig 1954), 1914, vol. <2>89, p. 45
  作者：Knoevenagel

  DOI：——

  日期：——
• First Synthesis of Phenylazomethine Dendrimer Ligands and Structural Studies
  作者：Masayoshi Higuchi、Satoshi Shiki、Katsuhiko Ariga、Kimihisa Yamamoto

  DOI：10.1021/ja004239r

  日期：2001.5.1

  Novel dendritic polyphenylazomethines (DPAs), which consist of pi -conjugated backbone, were synthesized up to the fourth generation by the convergent method via dehydration of aromatic kt tones with aromatic amines in the presence of titanium(IV) tetrachloride. The obtained dendrimers, DPA G1-4 (designated as GX, where X is the generation number), show high thermostability (Td(10%) 521 degreesC in DPA G4) and high solubility for the common solvents such as chloroform, THF, and DMSO unlike the conventional linear polyphenylazomethines, which have very low solubilities. The DPA G4 molecule was confirmed to have a spherelike structure by GPC measurement and a molecular model based on the crystal structure of DPA G2. Crystal data for DPA G2: monoclinic space group P2(1)/a, a = 25.352(4) Angstrom. b = 8.577(7) Angstrom c = 16.151(2) Angstrom, beta = 106.25(1)degrees V = 3371.6(10) Angstrom (3), Z = 2, D-calc = 1.168 g/cm(3), mu (Cu K alpha) = 0.536 cm(-1), final R = 0.089, and R-w = 0.287. The molecular modeling reveals that a DPA G4 molecule has a spherelike structure, in which the height, width, and depth are 2.3, 2.9, and 2.5 nm, respectively. The TEM and AFM pictures show the DPA G4 molecules to have a spherelike structure (the diameter: 1.3 nm) and are regularly assembled on a plate by casting. The occupied area of one DPA G4 molecule in a monolayer on water was estimated by pi -A measurements to be 3.8-4.2 nm(2) (the calculated diameter 2.2-2.3 nm. which agreed with the TEM result). NMR studies (H-1 NMR at 130 degreesC and T-1 measurements) supported a conformational rigidity of DPA G4 in solution.