5-methyl-5-(4-nitrophenyl)dipyrromethane | 951032-07-8

• 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: 5-methyl-5-(4-nitrophenyl)dipyrromethane
• 英文别名: 2-[1-(4-nitrophenyl)-1-(1H-pyrrol-2-yl)ethyl]-1H-pyrrole
• CAS: 951032-07-8
• 化学式: C₁₆H₁₅N₃O₂
• 分子量: 281.314
• InChiKey: PZWFXNPZTGTDHN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5-methyl-5-(4-nitrophenyl)dipyrromethane 在 palladium 10% on activated carbon 、 一水合肼 、 三氟乙酸 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 4-(5,10,10,15,15,20,20-Heptamethyl-21,22,23,24-tetrahydroporphyrin-5-yl)aniline
  参考文献：
  名称：

  Drug Delivery with a Calixpyrrole–trans-Pt(II) Complex

  摘要：

  A meso-p-nitroaniline-calix[4]pyrrole derivative trans-coordinated to a Pt(II) center was synthesized and its structure solved by X-ray analysis. Adenosine monophosphate (AMP) was used as a model compound to evaluate the potential for the assisted delivery of the metal to the DNA nucleobases via the phosphate anion-binding properties of the calix[4]pyrrole unit. An NMR investigation of the kinetics of AMP complexation in the absence of an H-bonding competing solvent (dry CD3CN) was consistent with this hypothesis, but we could not detect the interaction of the calix[4]pyrrole with phosphate in the presence of water. However, in vitro tests of the new trans-calixpyrrole- Pt(II) complex on different cancer cell lines indicate a cytotoxic activity that is unquestionably derived from the coexistence of both the trans-Pt(II) fragment and the calix[4]pyrrole unit.

  DOI：

  10.1021/ja307791j
• 作为产物：
  描述：

  吡咯 、 对硝基苯乙酮 在 L-酒石酸 、 1,3-二甲基脲 作用下， 以 neat (no solvent) 为溶剂， 以78%的产率得到5-methyl-5-(4-nitrophenyl)dipyrromethane
  参考文献：
  名称：

  一种用于合成多种功能化二吡咯甲烷 (DPM) 和杯 [4] 吡咯 (C4P) 的催化和无溶剂方法

  摘要：

  毋庸置疑，在新千年发展绿色和可持续反应介质，而不是使用挥发性有机溶剂以及腐蚀性和/或昂贵的催化剂，正不断吸引科学界的高度关注，以应对保护人类和环境的挑战同时保持商业可行性。为了克服现有的用于合成各种二吡咯甲烷 (DPM) 和杯 [4] 吡咯 (C4P) 的对环境有害且经济昂贵的合成方案的缺点，迫切需要在绿色条件下合成这些有价值的超分子受体。因此，我们在此首次报道，一种简单但非常有效的绿色方案，用于以可观的产率构建各种功能化的 DPM 和 C4P，而无需涉及额外的催化剂或常规有机溶剂。在我们的研究中，测试了一系列深共晶混合物，但低熔点混合物N , N '-二甲基脲 (DMU) 和 l-(+)-酒石酸 (TA) 在 70 °C 下以 7:3 的比例被发现是最佳选择。有趣的是，这种方法同样适用于这些系统的大规模合成，而不会显着降低产率，从工业角度来看，这似乎是值得注意的。

  DOI：

  10.1039/d1gc01515j

文献信息

• Thermodynamic Characterization of Halide−π Interactions in Solution Using “Two-Wall” Aryl Extended Calix[4]pyrroles as Model System
  作者：Louis Adriaenssens、Guzmán Gil-Ramírez、Antonio Frontera、David Quiñonero、Eduardo C. Escudero-Adán、Pablo Ballester

  DOI：10.1021/ja412098v

  日期：2014.2.26

  interactions in solution. We base this research on the thermodynamic characterization of a series of 1:1 complexes formed between halides (Cl(-), Br(-), and I(-)) and several α,α-isomers of "two-wall" calix[4]pyrrole receptors bearing two six-membered aromatic rings in opposed meso positions. The installed aromatic systems feature a broad range of electron density as indicated by the calculated values for their

  在此，我们报告了我们对溶液中卤化物-π 相互作用的最新实验研究。我们的研究基于卤化物（Cl(-)、Br(-) 和 I(-)）与“双壁”杯的几种 α,α-异构体之间形成的一系列 1:1 配合物的热力学表征[4]吡咯受体在相反的中间位置带有两个六元芳环。已安装的芳烃系统具有广泛的电子密度范围，如环中心静电表面电位的计算值所示。我们表明，芳香壁的电子性质与 X(-)⊂ 受体复合物的热力学稳定性之间存在相关性。我们提供了 π 系统和溶液中卤化物阴离子之间存在排斥和吸引相互作用的证据（在 1 和 -1 kcal/mol 之间）。我们将测量的氯化物和溴化物与受体系列结合的自由能分解为它们的焓和熵热力学量。在乙腈溶液中，结合焓值在整个受体系列中几乎保持不变，并且自由能的差异完全由结合过程的熵项的变化引起。最有可能的是，这种意想不到的行为是由于强溶剂化效应，这些效应构成了结合焓和熵的测量量级的重要组成部分
• Tuning the anion binding properties of calixpyrroles by means of p-nitrophenyl substituents at their meso-positions
  作者：Giuseppe Bruno、Grazia Cafeo、Franz H. Kohnke、Francesco Nicolò

  DOI：10.1016/j.tet.2007.07.060

  日期：2007.10

  Extended cavity calix[4]pyrroles and a calix[6]pyrrole were synthesized by cyclization of 5-methyl-5-(4-nitrophenyl)dipyrromethane with acetone in the presence of acid. The solid-state structures of the novel macrocycles were determined by X-ray crystallography. The host–guest chemistry of these receptors towards halide ions was investigated in solution by 1H NMR titration techniques and compared with

  在酸存在下，通过丙酮将5-甲基-5-（4-硝基苯基）二吡咯甲烷环化，合成了长腔杯杯[4]吡咯和杯[6]吡咯。新型大环化合物的固态结构通过X射线晶体学测定。这些受体对卤离子的主客体化学是通过在溶液中研究1种1 H NMR滴定技术，并与那些的内消旋-octamethylcalix [4]吡咯和内消旋-dodecamethylcalix [6]吡咯。在这里描述的新型杯[6]吡咯衍生物的两个面上观察到氯阴离子的结合发生了不同的亲和力。
• Efficient organocatalysis with a calix[4]pyrrole derivative
  作者：Grazia Cafeo、Margherita De Rosa、Franz H. Kohnke、Placido Neri、Annunziata Soriente、Luca Valenti

  DOI：10.1016/j.tetlet.2007.10.148

  日期：2008.1

  The 10 alpha,20 beta-bis(4-nitrophenyl)-calix[4]pyrrole was found to act as an effective organocatalyst for the hetero Diets-Alder reaction of Danishefsky's diene with aromatic aldehydes. This discovery is the first reported case of a calixpyrrole that exhibits organocatalytic activity. (c) 2007 Elsevier Ltd. All rights reserved.
• Quantification of Nitrate−π Interactions and Selective Transport of Nitrate Using Calix[4]pyrroles with Two Aromatic Walls
  作者：Louis Adriaenssens、Carolina Estarellas、Andreas Vargas Jentzsch、Marta Martinez Belmonte、Stefan Matile、Pablo Ballester

  DOI：10.1021/ja4021793

  日期：2013.6.5

  Herein we disclose the results investigations regarding the interactions between the biologically relevant nitrate oxoanion and several "two-wall" aryl-extended calix[4]pyrroles. There exists a clear relationship between the electronic nature of the aromatic walls of the calix[4]pyrroles and the stability of the nitrate subset of calix[4]pyrrole complex. This suggests that NO3--pi interactions have an important electrostatic component. We provide energetic estimates for the interaction of nitrate with several phenyl derivatives. Additionally, we report solid-state evidence for a preferred binding geometry of the nitrate anion included in the calix[4]pyrroles. Finally, the "two-wall" aryl-extended calix[4]-pyrroles show excellent activity in ion transport through lipid-based lamellar membranes. Notably the best anion transporters are highly selective for transport of nitrate over other anions.
• Drug Delivery with a Calixpyrrole–<i>trans</i>-Pt(II) Complex
  作者：Grazia Cafeo、Grazia Carbotti、Angela Cuzzola、Marina Fabbi、Silvano Ferrini、Franz H. Kohnke、Georgia Papanikolaou、Maria Rosaria Plutino、Camillo Rosano、Andrew J. P. White

  DOI：10.1021/ja307791j

  日期：2013.2.20

  A meso-p-nitroaniline-calix[4]pyrrole derivative trans-coordinated to a Pt(II) center was synthesized and its structure solved by X-ray analysis. Adenosine monophosphate (AMP) was used as a model compound to evaluate the potential for the assisted delivery of the metal to the DNA nucleobases via the phosphate anion-binding properties of the calix[4]pyrrole unit. An NMR investigation of the kinetics of AMP complexation in the absence of an H-bonding competing solvent (dry CD3CN) was consistent with this hypothesis, but we could not detect the interaction of the calix[4]pyrrole with phosphate in the presence of water. However, in vitro tests of the new trans-calixpyrrole- Pt(II) complex on different cancer cell lines indicate a cytotoxic activity that is unquestionably derived from the coexistence of both the trans-Pt(II) fragment and the calix[4]pyrrole unit.