5,10,15,20-四(1-甲基-4-吡啶基)卟啉铜 | 48242-70-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 中文名称: 5,10,15,20-四(1-甲基-4-吡啶基)卟啉铜
• 英文名称: copper(II) 5,10,15,20-tetrakis(1-methyl-4-pyridyl)-21H,23H-porphine
• 英文别名: (5,10,15,20-tetrakis(1-methylpyridin-1-ium-4-yl)-21H,23H-porphinato)copper(II)；copper(5,10,15,20-tetrakis(N-methyl-pyridinium-4-yl)-porphyrinato) tetracation；meso-tetrakis(N-methylpyridinium-4-yl)porphinatocopper(II)；copper(II) tetra-(4-N-methylpyridinium) porphyrin(4+)；copper(II) tetrakis(4-N-methylpyridyl)porphyrin；Cu-II-TMPyP(4)；copper;5,10,15,20-tetrakis(1-methylpyridin-1-ium-4-yl)porphyrin-22,24-diide
• CAS: 48242-70-2
• 化学式: C₄₄H₃₆CuN₈
• 分子量: 740.369
• InChiKey: IWBZPROSINYBFE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.36
• 重原子数：
  53
• 可旋转键数：
  3
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  53
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5,10,15,20-四(1-甲基-4-吡啶基)卟啉铜 以 水 、 异丙醇 为溶剂， 生成 tetrakis(N-methyl-4-pyridyl)porphyrinato copper(II)(3+)
  参考文献：
  名称：

  One-electron reduction and demetallation of copper porphyrins

  摘要：

  Reduction of water-soluble Cu(II) porphyrins has been studied by gamma-radiolysis and pulse radiolysis at various pH values. In neutral and alkaline solutions, the transient species produced by one-electron reduction were identified as the pi-radical anions, based on their broad absorption spectra at 600-800 nm, and the two-electron reduction products were either Cu(II) phlorins or Cu(II) chlorins, depending on pH and on porphyrin structure. Reduction in acidic solution, however, often led to demetallation of these otherwise stable complexes. The pH at which demetallation became apparent was <4 and dependent on porphyrin structure. Under these conditions, pulse radiolytic reduction gave the spectra of the products of protonation of Cu(I) porphyrin. It is concluded that the pi-radical anions of Cu(II) porphyrins have some Cu(I) character, which in acidic solutions results in protonation and demetallation due to the large ionic radius of Cu(I). For comparison, a study of the acid-catalyzed solvolysis of a Mg porphyrin was carried out both by pulse radiolysis and by classical methods.

  DOI：

  10.1021/j100202a091
• 作为产物：
  描述：

  copper(II) hexahydrate 、 tetrakis-(N-methyl-4-pyridiniumyl)porphyrin tetranitrate 以 水 为溶剂， 生成 5,10,15,20-四(1-甲基-4-吡啶基)卟啉铜
  参考文献：
  名称：

  Kinetics of the reactions of divalent copper, zinc, cobalt, and nickel with a deformed water soluble centrally monoprotic porphyrin

  摘要：

  The kinetics of incorporation of Cu2+, Zn2+,Co2+, and Ni2+ into the free base H-2-BrP(4)(4+) and centrally monoprotic H-BrP(4)(3+) forms of the deformed and water soluble beta-octabromo-tetrakis(N-methyl-4-pyridyl)porphyrin were studied at 25degreesC, I=0.10 (NaNO3/HNO3). Below pH 7, the reactions were first-order in porphyrin and metal, and the rate constants increased with an increase in pH. The monocation H-3-BrP(4)(5+) did not incorporate metal ions, and H-BrP(4)(3+) reacted several hundred times faster than H-2-BrP(4)(4+). The incorporation rate constants for the pre-deformed H-2-BrP(4)(4+) were similar to10(3) times larger as compared to the more planar tetrakis(N-methyl-4-pyridyl)porphyrin. For both porphyrins, the reactivity order was Cu2+>Zn2+>Co2+> Ni2+. While Cu2+ reacted similar to10(4) times more rapidly than did Ni2+ the ratios of the metalation rate constants of H-BrP(4)(3+) to the water exchange rate constants of the metal ions varied by no more than a factor of 4 across the series. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(02)01323-3

文献信息

• Tetra(<i>p</i>-<i>t</i>-butyl)thiacalix[4]arenetetrol Forms 4:1 Complex with Tetrakis(1-methyl-4-pyridinio)porphyrin
  作者：Kazutaka Hirakawa、Hiroshi Segawa

  DOI：10.1246/bcsj.20100058

  日期：2010.7.15

  A liquid–liquid extraction of cationic porphyrin (tetrakis(1-methyl-4-pyridinio)porphyrin, TMPyP) by tetra(p-t-butyl)thiacalix[4]arenetetrol (TCA) from an aqueous phase to a dichloromethane phase was performed. TCA stoichiometrically formed 4:1 complexes with TMPyP in dichloromethane phase within a few seconds. On the other hand, tetra(p-t-butyl)calix[4]arenetetrol did not form the complex with TMPyP.

  四（对-丁基）硫杂[4]萘四醇（TCA）对阳离子卟啉（四（1-甲基-4-吡啶）卟啉，TMPyP）进行了液-液萃取。在二氯甲烷相中，TCA 与 TMPyP 在几秒钟内就按比例形成了 4:1 的复合物。另一方面，四（对叔丁基）钙[4]萘四醇没有与 TMPyP 形成络合物。
• Electrochemical characterization of ordered arrays of metallo-porphyrins in aqueous solution
  作者：Giovanni Tabbì、Giovanna Di Mauro、Roberto Purrello、Raffaele P. Bonomo

  DOI：10.1039/c0dt01538e

  日期：——

  programming the right stoichiometric addition of the proper porphyrin. The redox potentials of these supramolecular complexes in aqueous media, as well as those of the parent metalloporphyrins, have been characterized by using square wave voltammetry technique. The use of the simulation procedure leads us to establish the electrochemical steps involved in the redox processes for each supramolecular

  金属化的内消旋-四（N-甲基-4-吡啶基）卟啉（M TMPyP）和5,11,17,23-四磺酸钠-25,26,27,28-四-（羟羰基甲氧基）-杯[4]芳烃（C从模板物种M TMPyP：C 4 TsTc（1：4，M = Cu，Zn）的形成开始，使用4 TsTc）作为关键成分来构建离散的超分子实体。逐步添加更多量的卟啉允许离散的超分子实体（2：4和3：4）的简便非共价合成，只需通过编程正确的化学计量添加适当的卟啉即可建立。这些超分子配合物在水性介质中的氧化还原电势以及母体金属卟啉的氧化还原电势已通过使用方波伏安法进行了表征。模拟程序的使用使我们建立了每个超分子物种在氧化还原过程中涉及的电化学步骤，证明了多步电子还原，由于它们的紧密性，在实验上无法清楚地解决。最惊人的结果是，这些超分子复合物中每种的电化学都不同于母体组分的电化学。仅将这些超分子络合物中的每一个视为唯一实体，才能解释这种“异常”
• Assembly of Positively Charged Porphyrins Driven by Metal Ions:  A Novel Polymeric Arrangement of Cationic Metalloporphyrin
  作者：Silvano Geremia、Luigi Di Costanzo、Giorgio Nardin、Lucio Randaccio、Roberto Purrello、Domenico Sciotto、Rosaria Lauceri、Fabio Pichierri

  DOI：10.1021/ic049336q

  日期：2004.11.1

  saddle conformation of the porphyrin reveals pi-like interactions between the peripheral pyrrole Cb-Cb- "double bond" and the metal center. DFT calculations on the isolated porphyrins clearly show the HOMO orbitals with the correct topology to yield a bonding interaction among the stacked porphyrin units. To our knowledge, a slipped stack chain of positively charged porphyrins has never been previously

  三阳离子或四阳离子铜卟啉的氯水合物的结晶和晶体结构分析，即铜（5,10,15-三（N-甲基-吡啶-4-基）-20-吡啶-卟啉铜）（1）和铜（分别进行了5,10,15,20-四（N-甲基-吡啶-4-基）-卟啉。后者在不同的制备条件下获得了两种结晶形式2和3。已检测到这些阳离子卟啉的新型滑动堆叠链。卟啉的显着的鞍状构象揭示了在外围吡咯Cb-Cb-“双键”和金属中心之间的类似pi的相互作用。对孤立的卟啉的DFT计算清楚地显示了具有正确拓扑结构的HOMO轨道，可在堆叠的卟啉单元之间产生键相互作用。据我们所知，
• Catalytic Unfolding and Proteolysis of Cytochrome <i>c</i> Induced by Synthetic Binding Agents
  作者：Kevin Groves、Andrew J. Wilson、Andrew D. Hamilton

  DOI：10.1021/ja0317731

  日期：2004.10.1

  A class of polyanionic copper porphyrin dimers is shown to selectively increase the susceptibility of cytochrome c to proteolysis through binding-induced disruption of tertiary and secondary structure. The free energy of the protein conformation leading to proteolytic attack is stabilized by about 2.4 kcal/mol in the bound state. The proteolytic acceleration is catalytic in nature, requiring only a fraction of an equivalent of metalloporphyrin to effect complete, rapid digestion in the presence of a protease.
• Reaction of copper(<scp>II</scp>) with a metalloporphyrin. A type of supramolecular-driven porphyrin metallation
  作者：Rosario A. Vilaplana、Francisco González-Vílchez

  DOI：10.1039/dt9930001779

  日期：——

  The reaction of the transfer of copper(II) from a chelating environment to a porphyrin core, accelerated by cadmium(II) previously inserted into the porphyrin, shows an unusual kinetic profile which is interpreted as being the result of supramolecular assembly formation.