3,3′-dinitro-4,4′-di(N-ethylamino)diphenylmethane | 101588-67-4

• 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: 3,3′-dinitro-4,4′-di(N-ethylamino)diphenylmethane
• 英文别名: 3,3'-dinitro-4,4'-bis(N-ethylamino)diphenylmethane；4,4'-bis(N-ethylamino)-3,3'-dinitrodiphenylmethane；3,3'-dinitro-4,4-bis(ethylamino)diphenylmethane；bis[3-nitro-4-(N-ethylamino)phenyl]methane；4,4'-Methylen-bis-(N-aethyl-2-nitro-anilin)；N-ethyl-4-[[4-(ethylamino)-3-nitrophenyl]methyl]-2-nitroaniline
• CAS: 101588-67-4
• 化学式: C₁₇H₂₀N₄O₄
• 分子量: 344.37
• InChiKey: CJGYXUZJKBLXKL-UHFFFAOYSA-N

物化性质

• 熔点：
  120-122 °C(Solv: ethanol (64-17-5))
• 沸点：
  558.0±50.0 °C(Predicted)
• 密度：
  1.302±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.96
• 重原子数：
  25.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  110.34
• 氢给体数：
  2.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  3,3′-dinitro-4,4′-di(N-ethylamino)diphenylmethane 在 sodium hydroxide 、 锌 作用下， 以 乙醇 为溶剂， 反应 1.0h， 以80%的产率得到3,3'-diamino-4,4'-bis(N-ethylamino)diphenylmethane
  参考文献：
  名称：

  由金属离子立体化学偏好控制的双螺旋和三螺旋的自组装

  摘要：

  双核双齿配体双[5-(l-methyl-2-(6'-methyl-2'-pyridyl)benzimidazolyl)]methane (bismbmp, 3) 及其单核类似物6-methyl-2-( 1 -甲基苯并咪唑-2-基)吡啶(mbmp，1)被报道。配体 mbmp (1) 与铜 (I) 反应生成 [Cu(mbmp)₂]ClO₄，其晶体结构 (CuC₂₈H₂₆ N₆ClO₄, z = 7.877 (1) A, b = 13.810 (2) A, c = 25.090 (7) A, s = 95.29 (1)°, 单斜晶系, P2₁/c, Z = 4) 显示了一个单核结构，其中 Cu(I) 假四面体由两个双齿 '-二亚胺供体基团配位。在通过铜（I）与bismbmp反应获得的双核络合物[Cu 2 (bismbmp) 2 ](ClO 4 ) 2 -H 2 O中，发现每种铜离子具有相同的发色

  DOI：

  10.1021/ja00045a016
• 作为产物：
  描述：

  聚合甲醛 、 N-乙基-2-硝基苯胺 在 盐酸 、 水 作用下， 以66%的产率得到3,3′-dinitro-4,4′-di(N-ethylamino)diphenylmethane
  参考文献：
  名称：

  有效浓度的简单化学调节：单链，双链和三链双核镧系元素螺旋的选择

  摘要：

  更换终端2-苯并咪唑-6-羧基吡啶（两个内部旋转自由度）与2-苯并咪唑-8-羟基喹啉（一个内部的旋转自由度）到节段性双-三齿配体在从去L2和[ L3 -2 H] 2−至[ L12 b -2 H] 2−不会显着影响所得双核镧系三链螺旋络合物[Ln 2（L2）3 ] 6+，[Ln 2（L3-2 H）3 ]和[Ln 2（L12 b -2 H）3]（回文螺旋，金属间接触距离≈9Å，螺旋间距≈1.4nm /圈）。但是，它们的热力学组装在溶液中完全不同，这可以通过[ L12 b -2 H] 2−的有效浓度急剧下降两个数量级来证明。[Ln 2（L12 b -2 H）n ]（n = 2，3）络合物中的这个关键参数进一步沿着镧系元素序列（Ln = La到Lu）突然调制，这为1）调谐提供了前所未有的工具最终螺旋结构中配体链的数量； 2）选择性配位各种络合物中的镧系元素； 3）控制含镧系元素的聚合物与离散组装体的比例。

  DOI：

  10.1002/chem.200902026

文献信息

• Implementing Liquid‐Crystalline Properties in Single‐Stranded Dinuclear Lanthanide Helicates
  作者：Emmanuel Terazzi、Amir Zaïm、Bernard Bocquet、Johan Varin、Laure Guénée、Thibault Dutronc、Jean‐François Lemonnier、Sébastien Floquet、Emmanuel Cadot、Benoît Heinrich、Bertrand Donnio、Claude Piguet

  DOI：10.1002/ejic.201300176

  日期：2013.7

  Invited for the cover of this issue is the group of Emmanuel Terazzi at the University of Geneva, Switzerland. The cover image shows how single-stranded dinuclear lanthanide helicates (green) survive immersion into a drop of less polar solvent (e.g. CH2Cl2) and their eventual self-organization into a liquid-crystalline material.

  瑞士日内瓦大学的 Emmanuel Terazzi 小组受邀为本期封面。封面图片展示了单链双核镧系元素螺旋体（绿色）如何在浸入一滴极性较小的溶剂（例如 CH2Cl2）中幸存下来，并最终自组织成液晶材料。
• Effect of a halogenide substituent on the stability and photophysical properties of lanthanide triple-stranded helicates with ditopic ligands derived from bis(benzimidazolyl)pyridine †
  作者：Carlos Platas Iglesias、Mourad Elhabiri、Marcel Hollenstein、Jean-Claude G. Bünzli、Claude Piguet

  DOI：10.1039/b001818j

  日期：——

  Bis1-ethyl-2-[6-(N,N-diethylcarbamoyl)-4-halogenopyridin-2-yl]benzimidazol-5-yl}methane (halogeno = chloro, LE; bromo, LF) have been synthesized as ditopic receptors for the development of lanthanide-containing helicates able to couple with biological material and to test the influence of the halogeno substituent on the wrapping process, the structure of the resulting dimetallic edifices, and the photophysical properties of the encapsulated ions. The stability of the [Eu2(L)3]6+ helicates, as determined by NMR competitive titrations, decreases by respectively one (LF) and three (LE) orders of magnitude compared to the value found for the unsubstituted ligand (LB) although it remains large, log β23 = 23.8 (LF) and 21.8 (LE) in acetonitrile. The [Ln2(LE)3]6+ helicates are shown to be isostructural in acetonitrile over the lanthanide series (Pr to Yb) and the crystal structure of [Tb2(LB)3]6+ appears to be a good model for their solution structure, as demonstrated by paramagnetic NMR measurements (lanthanide induced shift method) and relaxation time determination. Ligand LE appears to be a fair sensitiser of EuIII, the quantum yield of [Eu2(LE)3]6+ being 25% larger than that found for [Eu2(LB)3]6+, but the ligand 3ππ* state and Tb(5D4) excited level are in resonance, which limits the sensitisation of TbIII. High resolution luminescence spectra of [Eu2(LE)3]6+, both in solution and in the solid state, are presented and discussed in terms of site symmetry and vibronic coupling mechanisms.

  合成了双1-乙基-2-[6-(N,N-二乙基氨基甲酰基)-4-卤代吡啶-2-基]苯并咪唑-5-基}甲烷（卤素=氯，LE；溴，LF）作为双位受体，用于开发能够与生物材料耦合的含镧元素的螺旋体，并测试卤代取代基对包裹过程、所形成的双金属构筑物结构以及封装离子的光物理特性的影响。通过NMR竞争滴定法确定的[Eu2(L)3]6+螺旋体的稳定性与未取代配体（LB）相比，分别下降了一个（LF）和三个（LE）数量级，尽管其仍然较大，在乙腈中log β23为23.8（LF）和21.8（LE）。在乙腈中，[Ln2(LE)3]6+螺旋体在镧系元素（Pr到Yb）间显示出同构性，[Tb2(LB)3]6+的晶体结构似乎是它们溶液结构的良好模型，通过顺磁性NMR测量（镧诱导位移法）和弛豫时间测定得以证明。配体LE对EuIII的灵敏度相当，其量子产率比[Eu2(LB)3]6+大25%。但 ligand 3ππ*状态与Tb(5D4)激发态之间存在共振，这限制了TbIII的敏化。在溶液和固态下，[Eu2(LE)3]6+的高分辨率发光光谱被呈现并讨论，涉及位点对称性和声子耦合机制的问题。
• Monitoring helical twists and effective molarities in dinuclear triple-stranded lanthanide helicates
  作者：Patrick E. Ryan、Laure Guénée、Claude Piguet

  DOI：10.1039/c3dt50941a

  日期：——

  The replacement of terminal benzimidazole–pyridine binding units in the neutral di-tridentate segmental ligand L1 with phenanthroline in L10 reduces the number of torsional degrees of freedom by two units. Reactions of these ligands with trivalent europium or lutetium cations yield structurally similar self-assembled dinuclear triple-stranded [Ln2(Lkkk)3]6+ complexes, thus demonstrating that the increased rigidity of the strand in L10 is compatible with its helical twist. With the larger lanthanum cations, the metallic coordination spheres are completed with two terminal axial triflate counter-anions to give [La2(L10)3(CF3SO3)2]4+. Thermodynamic investigations in acetonitrile confirm the minor constraints produced by the planar phenanthroline unit in L10 leading to comparable effective molarities EMEu,L1L1L1 ≈ EMEu,L10L10L10 = 10−3.9(4) M with mid-range EuIII cations. The striking minute effective molarities EMLn,LnLnLn-2H ≈ 10−6–10−9 M obtained upon the replacement of terminal phenanthrolines with structurally analogous fused hydroxyquinolines in L9 can be thus unambiguously assigned to solvation effects, a new tool for controlling complexity in metal-induced self-assembly processes.

  L10 中的菲罗啉取代了中性二三叉分段配体 L1 中的末端苯并咪唑-吡啶结合单元，使扭转自由度减少了两个单元。这些配体与三价铕或镥阳离子的反应产生了结构相似的自组装双核三链[Ln2(Lkkk)3]6+复合物，从而证明 L10 中增加的链刚性与其螺旋扭转是相容的。在较大的镧阳离子中，金属配位球通过两个末端轴向三酸盐反阴离子完成，得到 [La2(L10)3(CF3SO3)2]4+。在乙腈中进行的热力学研究证实，L10 中的平面菲罗啉单元产生了微小的限制，导致 EuIII 中阳离子的有效摩尔值 EMEu,L1L1L1 ≈ EMEu,L10L10L10 = 10-3.9(4) M。因此，在 L9 中用结构类似的融合羟基喹啉取代末端菲罗啉时获得的惊人的微小有效摩尔值 EMLn,LnLnLn-2H ≈ 10-6-10-9 M 可以明确地归因于溶解效应，这是控制金属诱导的自组装过程复杂性的一种新工具。
• The First Self-Assembled Trimetallic Lanthanide Helicates Driven by Positive Cooperativity
  作者：Sébastien Floquet、Nadjet Ouali、Bernard Bocquet、Gérald Bernardinelli、Daniel Imbert、Jean-Claude G. Bünzli、Gérard Hopfgartner、Claude Piguet

  DOI：10.1002/chem.200390214

  日期：2003.4.14

  the two terminal EuN(6)O(3) sites in [Eu(3)(L7)(3)](9+). New multicenter equations have been developed for investigating the solution structure of [Ln(3)(L7)(3)](9+) by paramagnetic NMR spectroscopy and linear correlations for Ln=Ce-Tb imply isostructurality for these larger lanthanides. NMR spectra point to the triple helical structure being maintained in solution, but an inversion of the magnitude

  分段三三齿配体L7与化学计量的Ln（III）（Ln = La-Lu）在乙腈中反应，得到配合物[Ln（2）（L7）（3）]（6+）和[Ln（3 ）（L7）（3）]（9+）。形成常数指向沿镧系的尺寸区分作用可忽略不计，但是Scatchard图表明三金属三链螺旋结构[Ln（3）（L7）（3）]（9+）的自组装被驱动完成尽管有很强的金属间静电排斥力，但仍具有积极的合作性。结晶定量提供[Ln（3）（L7）（3）]（CF（3）SO（3））（9）（Ln = La，Eu，Gd，Tb，Lu）和[ Eu（3）（L7）（3）]（CF（3）SO（3））（9）。（CH（3）CN）（9）。（H（2）O）（2）（Eu（3 C（216）H（226）N（48）O（35）F（27）S（9），三斜晶系，P1，Z = 2）表示三根配体链缠绕在假三轴周围，假三轴由刚性固定在约9 A的三种金属离子定义。每种金属离子由九个施主原子以伪
• Allosteric Effects in Binuclear Homo- and Heterometallic Triple-Stranded Lanthanide Podates
  作者：Patrick E. Ryan、Gabriel Canard、Sylvain Koeller、Bernard Bocquet、Claude Piguet

  DOI：10.1021/ic301631n

  日期：2012.9.17

  This work illustrates a simple approach for deciphering and exploiting the various free energy contributions to the global complexation process leading to the binuclear triple-stranded podates [Ln(2)(L9)](6+) (Ln is a trivalent lanthanide). Despite the larger microscopic affinities exhibited by the binding sites for small Ln(3+), the stability constants measured for [Ln(2)(L9)](6+) decrease along the lanthanide series; a phenomenon which can be ascribed to the severe enthalpic penalty accompanying the intramolecular cyclization around small Ln(III), combined with increasing anticooperative allosteric interligand interactions. Altogether, the microscopic thermodynamic characteristics predict beta(La,Lu,L9)(1,1,1)/beta(Lu,La,L9)(1,1,1) = 145 for the ratio of the formation constants of the target heterobimetallic [LaLu(L9)](6+) and [LuLa(L9)](6+) microspecies, a value in line with the quantitative preparation (>90%) of [LaLu(L9)](6+) at millimolar concentrations. Preliminary NMR titrations indeed confirm the rare thermodynamic programming of a pure heterometallic f-f' complex.