tetraphenylporphinatoMg | 13007-95-9

• 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: tetraphenylporphinatoMg
• 英文别名: magnesium porphyrazine；magnesium(II)porphine；Mg(II)-porphine；Mg(II)porphine；magnesium(II) porphine
• CAS: 13007-95-9
• 化学式: C₂₀H₁₂MgN₄
• 分子量: 332.647
• InChiKey: KIQQAJNFBLKFPO-QDJBTJTOSA-N

物化性质

• 熔点：
  >370 °C(Solv: ethanol (64-17-5); water (7732-18-5))

计算性质

• 辛醇/水分配系数(LogP)：
  3.53
• 重原子数：
  25.0
• 可旋转键数：
  0.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  53.98
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  tetraphenylporphinatoMg 在 sodium acetate 、 cobalt(II) diacetate tetrahydrate 作用下， 以 苯甲腈 为溶剂， 反应 2.5h， 以36%的产率得到porphyrin‐Co(II)
  参考文献：
  名称：

  Proton-Coupled Oxygen Reduction at Liquid−Liquid Interfaces Catalyzed by Cobalt Porphine

  摘要：

  Cobalt porphine (COP) dissolved in the organic phase of a biphasic system is used to catalyze O-2 reduction by an electron donor, ferrocene (Fc). Using voltammetry at the interface between two immiscible electrolyte solutions (ITIES), it is possible to drive this catalytic reduction at the interface as a function of the applied potential difference, where aqueous protons and organic electron donors combine to reduce O-2. The current signal observed corresponds to a proton-coupled electron transfer (PCET) reaction, as no current and no reaction can be observed in the absence of either the aqueous acid, COP, c, or O-2.

  DOI：

  10.1021/ja904569p
• 作为产物：
  描述：

  5-溴-3-氯吲唑 、 magnesium bromide 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲苯 为溶剂， 反应 6.0h， 以40%的产率得到tetraphenylporphinatoMg
  参考文献：
  名称：

  METHOD OF MAKING PORPHYRINS

  摘要：

  将公式I的化合物制备方法是通过将两种公式II的化合物（这两种化合物可以相同也可以不同）或者将公式III的化合物与公式IV的化合物进行缩合，从而产生公式I的化合物。缩合步骤可以在碱性条件下使用金属盐进行。

  公开号：

  US20080221319A1

文献信息

• Effects of <i>meso</i>-diarylamino group of porphyrins on optical and electrochemical properties
  作者：Tomohiro Higashino、Yamato Fujimori、Issei Nishimura、Hiroshi Imahori

  DOI：10.1142/s1088424619500652

  日期：2020.1

  Introduction of an electron-donating meso-diarylamino group into a porphyrin core affords its broadened and red-shifted absorption and raises the HOMO level of the porphyrin. In this regard, porphyrins with multiple meso-diarylamino groups are expected to show unique optical and electrochemcial properties depending on the number of the meso-diarylamino groups. Herein, we report a series of porphyrins with a different number of the meso-diarylamino groups. They were prepared by the iodine(III)-mediated oxidative amination reaction of the corresponding meso-free porphyrins. With increasing the number of the meso-diarylamino groups, both red shifts and broadening in the absorption and negative shifts in the oxidation potential were observed. Notably, the oxidation potential of the porphyrin with four meso-diarylamino groups is comparable to that of tetrathiafulvalene, which is one of representative electron donors, suggesting the potential utility of multiply meso-aminated porphyrins as hole-transporting materials and as electron donors forming charge-transfer complexes with electron acceptors. We believe that this study sheds light on porphyrins with multiple electron-donating groups as organic functional materials.

  在卟啉核心中引入一个供电子的介二叉氨基，可使卟啉的吸收变宽、变红，并提高卟啉的 HOMO 水平。因此，具有多个间位二芳基氨基的卟啉有望根据间位二芳基氨基的数量显示出独特的光学和电化学性质。在此，我们报告了一系列具有不同数量介观二芳基氨基的卟啉。这些卟啉是通过碘（III）介导的相应无间氨基卟啉的氧化胺化反应制备的。随着介基-二芳基氨基基团数量的增加，可观察到吸收的红移和展宽以及氧化电位的负移。值得注意的是，含有四个间位二酰胺基团的卟啉的氧化电位与具有代表性的电子供体之一的四硫富勒烯的氧化电位相当，这表明多重间位酰胺卟啉作为空穴传输材料和电子供体与电子受体形成电荷转移复合物的潜在用途。我们认为这项研究揭示了具有多个电子供体基团的卟啉作为有机功能材料的前景。
• A novel, high-yielding synthesis of meso-substituted porphyrins via the direct arylation of porphine
  作者：Dong-Fang Shi、Richard T. Wheelhouse

  DOI：10.1016/s0040-4039(02)02339-0

  日期：2002.12

  A new method for the synthesis of meso-substituted porphyrins is described: reaction of 5,10,15,20-tetrabromoporphine magnesium complex with aryl or heteroaryl boronic acids in the presence of Pd(PPh3)4 gave meso-substituted porphyrins in yields up to 70%.

  描述了一种合成内消旋卟啉的新方法：在Pd（PPh 3）4存在下，5,10,15,20-四溴卟啉镁配合物与芳基或杂芳基硼酸反应生成了内消旋卟啉，收率较高高达70％。
• Direct Synthesis of Magnesium Porphine via 1-Formyldipyrromethane
  作者：Dilek Kiper Dogutan、Marcin Ptaszek、Jonathan S. Lindsey

  DOI：10.1021/jo070532z

  日期：2007.6.1

  The reaction of 1-formyldipyrromethane (100 mM) in toluene at 115 °C containing DBU (10 mol equiv) and MgBr2 (3 mol equiv) in the presence of air affords the magnesium chelate Mg(II) porphine in 30−40% yield. The advantages of the new method include simplicity, high concentration, chromatography-free purification, gram-scale synthesis, and avoidance of the poorly soluble free base porphine. Mg(II)

  含有DBU（10摩尔当量）和MgBr 2（3摩尔当量）的1-甲酰基二吡咯甲烷（100 mM）在甲苯中于115°C在空气中存在下反应，制得30-40％的螯合镁Mg（II）卟啉镁屈服。新方法的优点包括简单，高浓度，无色谱纯化，克级合成，以及避免了难溶的游离碱吗啡。Mg（II）卟啉在普通有机溶剂中表现出良好的溶解性，并且是衍生化的有价值的核心支架。
• Electrosynthesis and X‐ray Crystallographic Structure of Zn ^II <i>meso</i> ‐Triaryltriphenylphosphonium Porphyrin and Structural Comparison with Mg ^II <i>meso</i> ‐Triphenylphosphonium Porphine
  作者：Abdou K. D. Dimé、Hélène Cattey、Dominique Lucas、Charles H. Devillers

  DOI：10.1002/ejic.201801142

  日期：2018.12.2

  triphenylphosphine (PPh3) leads to the meso‐substituted triphenylphosphonium porphyrin, coordinated by one P(O)Ph3 molecule [1‐Zn‐PPh3+,PF6–·P(O)Ph3] in good yield (84 %). This cationic porphyrin was characterized by NMR, MALDI‐TOF mass spectrometry, UV/Vis. absorption spectroscopy and X‐ray diffraction analyses. The molecular structure of this compound was compared with already published meso‐ and β‐triphenylphosphonium

  锌的电化学氧化II 5，15 -二（p -甲苯基） - 10 -phenylporphyrin（1-Zn系）在三苯基膦的存在下（PPH 3）通向内消旋取代的三苯基卟啉，由一个P协调（O） Ph 3分子[ 1 -Zn-PPh 3 +，PF 6 – ·P（O）Ph 3 ]收率良好（84％）。通过NMR，MALDI-TOF质谱，UV / Vis对这种阳离子卟啉进行了表征。吸收光谱和X射线衍射分析。将该化合物的分子结构与已发表的内消旋体进行了比较β-和β-三苯基phosph卟啉，也具有以前通过电合成获得的未公开的Mg II 5-三苯基phenyl卟啉（MgP-PPh 3 +，PF 6 –）X射线晶体结构。
• Evaluation of Ruthenium-Based Assemblies as Carriers of Photosensitizers to Treat Rheumatoid Arthritis by Photodynamic Therapy
  作者：Manuel Gallardo-Villagrán、Lucie Paulus、Jean-Louis Charissoux、Sylvain Sutour、Pascale Vergne-Salle、David Yannick Leger、Bertrand Liagre、Bruno Therrien

  DOI：10.3390/pharmaceutics13122104

  日期：——

  For the first time, ruthenium-based assemblies have been used as carriers for photosensitizers in the treatment of rheumatoid arthritis by photodynamic therapy (PDT). These metallacages are totally soluble in physiological media and can transport photosensitizers (PS) in their cavity. After an incubation period, the PS is released in the cytoplasm and irradiation can take place. This strategy allows photosensitizers with low or null solubility in biological media to be evaluated as PDT agents in rheumatoid arthritis. The systems in which 21H,23H-porphine and 29H,31H-phthalocyanine are encapsulated show excellent photocytotoxicity and no toxicity in the dark. On the other hand, systems in which metalated derivatives such as Mg(II)-porphine and Zn(II)-phthalocyanine are used show good photocytotoxicity, but to a lesser extent than the previous two. Furthermore, the presence of Zn(II)-phthalocyanine significantly increases the toxicity of the system. Overall, fifteen different host–guest systems have been evaluated, and based on the results obtained, they show high potential for treating rheumatoid arthritis by PDT.

  首次使用基于钌的组装体作为光敏剂的载体，通过光动力疗法（PDT）治疗类风湿性关节炎。这些金属笼可以完全溶解在生理介质中，并能在其腔中运输光敏剂（PS）。经过孵育后，PS释放到细胞质中，辐射才能进行。这种策略允许对生物介质中溶解度低或无效的光敏剂在类风湿性关节炎的PDT治疗中进行评估。其中21H，23H-卟啉和29H，31H-酞菁被包封的系统表现出优异的光细胞毒性，而在黑暗中则没有毒性。另一方面，使用镁（II）-卟啉和锌（II）-酞菁等金属化衍生物的系统表现出良好的光细胞毒性，但程度不如前两种。此外，锌（II）-酞菁的存在显著增加了系统的毒性。总体而言，评估了十五种不同的宿主-客体系统，并基于所获得的结果，它们表现出通过PDT治疗类风湿性关节炎的高潜力。