2,3,7,8,12,13,17,18-octakis(propyl)porphyrazine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 2,3,7,8,12,13,17,18-octakis(propyl)porphyrazine
• 英文别名: octapropylporphyrazine；2,3,7,8,12,13,17,18-Octapropyl-5,10,15,20-tetraazaporphyrin；4,5,9,10,14,15,19,20-octapropyl-2,7,12,17,21,22,23,24-octazapentacyclo[16.2.1.13,6.18,11.113,16]tetracosa-1,3,5,7,9,11,13(22),14,16,18(21),19-undecaene
• 化学式: C₄₀H₅₈N₈
• 分子量: 650.954
• InChiKey: XLAMCAZQYLKTPJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.6
• 重原子数：
  48
• 可旋转键数：
  16
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  109
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,3,7,8,12,13,17,18-octakis(propyl)porphyrazine 在 iron(II) sulfate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 以32%的产率得到2,13,17,18-octakis(propyl)PzFe(II)
  参考文献：
  名称：

  Synthesis and Density Functional Theory Studies of Octakis(propyl) Porphyrazine and Its Fe(II) Complex

  摘要：

  由于金属化卟嗪类化合物具有多种功能，因此其合成和表征日益受到关注。本研究对 2,3,7,8,12,13,17,18-八(丙)卟嗪配体及其铁金属化配合物进行了合成和量子化学计算（采用 B3LYP/6-31G(d,p)方法），以确定金属化对配体电子和几何特性的影响。分析紫外-可见光谱时采用了时间相关密度泛函理论（TDDFT）方法。几何参数、HOMO-LUMO 间隙、偶极矩和 Mulliken 原子电荷的变化表明，金属化会引起显著的几何变化，这种变化取决于铁的自旋状态。卟吩配体与 2,3,7,8,12,13,17,18-辛基（丙基）卟吩配体的比较表明，烷基化对卟吩分子几何形状的影响微乎其微。

  DOI：

  10.14233/ajchem.2013.14280
• 作为产物：
  描述：

  3,4-dibromo-4-octene 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 34.0h， 生成 2,3,7,8,12,13,17,18-octakis(propyl)porphyrazine
  参考文献：
  名称：

  八丙基卟啉铁的μ-nitrido，μ-carbido和μ-oxo二聚体的合成与表征†

  摘要：

  制备了三种具有Fe III –O–Fe III，Fe +3.5 –N Fe +3.5和Fe IV C Fe IV结构单元的μX桥联二铁八丙基卟啉配合物，并通过紫外可见，EPR，X射线吸收光谱进行了表征和电化学方法。所有配合物的单晶均由苯乙腈制得，其结构通过X射线衍射确定。与μ-氧代络合物（6）相比，μ-nitrido（7）和μ-carbido（8）二聚体每2个双核络合物分子在Fe–C上与卟啉平面共面排列，每个苯中有一个苯分子结晶7和8的苯间距分别为3.435–3.725Å和3.352–3.669Å。较短的距离表明铁位点与苯π系统之间的相互作用，在具有较高路易斯酸度的Fe IV CFe IV单元的情况下更强。Fe–X–Fe角按6 – 7 – 8的顺序增加与Fe–X键序一致，分别从158.52°到168.5°和175.10°。但是，Fe–X键的长度不遵循这种趋势：Fe–O = 1.75 / 1

  DOI：

  10.1039/c4dt03207a

文献信息

• Synthesis and characterization of μ-nitrido, μ-carbido and μ-oxo dimers of iron octapropylporphyrazine
  作者：Cédric Colomban、Evgeny V. Kudrik、Dmitry V. Tyurin、Florian Albrieux、Sergei E. Nefedov、Pavel Afanasiev、Alexander B. Sorokin

  DOI：10.1039/c4dt03207a

  日期：——

  π-system which is stronger in the case of the FeIVCFeIV unit with a higher Lewis acidity. The Fe–X–Fe angle increases in the sequence 6–7–8 from 158.52° to 168.5° and 175.10°, respectively, in agreement with the Fe–X bond order. However, the lengths of the Fe–X bonds do not follow this trend: Fe–O = 1.75/1.76 Å > Fe–C = 1.67/1.67 Å > Fe–N = 1.65/1.66 Å indicating unexpectedly long Fe–C bonds. This observation

  制备了三种具有Fe III –O–Fe III，Fe +3.5 –N Fe +3.5和Fe IV C Fe IV结构单元的μX桥联二铁八丙基卟啉配合物，并通过紫外可见，EPR，X射线吸收光谱进行了表征和电化学方法。所有配合物的单晶均由苯乙腈制得，其结构通过X射线衍射确定。与μ-氧代络合物（6）相比，μ-nitrido（7）和μ-carbido（8）二聚体每2个双核络合物分子在Fe–C上与卟啉平面共面排列，每个苯中有一个苯分子结晶7和8的苯间距分别为3.435–3.725Å和3.352–3.669Å。较短的距离表明铁位点与苯π系统之间的相互作用，在具有较高路易斯酸度的Fe IV CFe IV单元的情况下更强。Fe–X–Fe角按6 – 7 – 8的顺序增加与Fe–X键序一致，分别从158.52°到168.5°和175.10°。但是，Fe–X键的长度不遵循这种趋势：Fe–O = 1.75 / 1
• Peripheral Metal-Ion Binding to Tris(thia−oxo crown) Porphyrazines
  作者：Sarah L. J. Michel、Anthony G. M. Barrett、Brian M. Hoffman

  DOI：10.1021/ic025639d

  日期：2003.2.1

  1b(H(2)) or 1c(Co) gives optical responses to Ni(2+), Zn(2+), Pb(2+), or Cu(2+) or to alkali (Li(+), Na(+), K(+), and Cs(+)) and alkaline earth (Mg(2+), Ca(2+), and Ba(2+)) metal ions. Nonetheless, "hard" ions are sensed electrochemically: Na(+) and Li(+) strongly shift the pz/pz(-) couple of 1b(H(2)()) and Co(III)/Co(II) couple of 1c(Co). For the addition of 4 equiv of Li(+) to 1c(Co), the Co(III)/Co(II)

  我们报告的制备和解决方案的无金属[1b（H（2））]和钴[1c（Co）]卟啉嗪（pz's），其中三个吡咯用S（2）O（3）冠醚官能化用于金属离子结合，并且在第四吡咯上附加有两种长链醇（双（（11-羟基十一烷基）硫代）），可用作表面固定剂。化合物1b（H（2）和1c（Co）在Ag（+）和Hg（2+）存在下表现出离子特异性的光学变化，Ag（+）与1b（H（2））的结合由1：1结合等温线，K（D）约为147 microM，而Hg（2+）与1b（H（2））的结合似乎更复杂；对于1c（Co），Ag（+）和Hg的结合（2+）也可以适合1：1等温线，K（D）分别约为109和83 microM。所有四种滴定都显示出非等吸收性，包括显然是由1：1等温线描述的那些。这表明存在多个离子结合的中间阶段。1b（H（2））或1c（Co）都不会对Ni（2 +），Zn（2 +），Pb（2+）或Cu（2+）或碱金属（Li（+），
• Synthesis and Density Functional Theory Studies of Octakis(propyl)porphyrazine and its Zn(II) Complex
  作者：M.K. Mongale、D.A. Isabirye、M.M. Kabanda、T.O. Aiyelabola、E.E. Ebenso

  DOI：10.14233/ajchem.2017.20205

  日期：——

  Metalloporphyrazine 2,3,7,8,12,13,17,18-octakis(propyl)porphyrazine Zn(II) was synthesized and characterized using elemental analysis, IR, 1H NMR and UV-visible spectroscopy. The kinetics of the incorporation of Zn(II) into the free base 2,3,7,8,12,13,17,18-octakis(propyl) porphyrazine was also investigated. Quantum chemical calculations (utilizing B3LYP/6-31G(d,p) method) was carried out on the free base and its Zn(II) complex to determine their electronic and geometric properties. Time-dependent Density Functional theory (TDDFT) approach was utilized for the analysis of the UV-visible spectra. The results indicated that both the experimental and theoretical results were in reasonable agreement. This showed that metallation and alkylation respectively had significant influence on the molecular and electronic properties of the porphyrazine moiety. It was proposed that the peripheral substituent, cavity size and the size of the metal ion incorporated are the main factors that determine metallation rate and consequently reactivity of the metalloporphyrazine complex.

  金属卟啉嗪 2,3,7,8,12,13,17,18-八(丙基)卟啉嗪锌(II)的合成和表征采用元素分析、红外光谱、1H核磁共振和紫外-可见光谱。还研究了锌(II)与游离碱2,3,7,8,12,13,17,18-八(丙基)卟啉嗪结合的动力学。对游离碱及其锌(II)络合物进行了量子化学计算（采用B3LYP/6-31G(d,p)方法），以确定其电子和几何性质。利用时变密度泛函理论（TDDFT）方法分析了紫外-可见光谱。结果表明，实验结果和理论结果基本一致。这表明金属化和烷基化分别对卟啉嗪部分的分子和电子性质有重大影响。有人提出，外围取代基、空穴大小和金属离子的结合大小是决定金属化速率和金属卟啉嗪络合物的反应性的主要因素。
• Synthesis and structural characterization of 2,3,7,8,12,13,17,18-octakis(propyl), N, N, N′, N′-tetramethylaminoporphyrazines and 2,3,9,10,16,17,23,24-octa substituted phthalocyanine and the kinetic studies of their Co(II) and Cu(II) metalated complexes
  作者：David A. Isabirye、Fanyana M. Mtunzi、Temitayo O. Aiyelabola

  DOI：10.1016/j.dyepig.2014.05.013

  日期：2014.10

  Three tetrapyrrole macrocyclic compounds 2,3,7,8,12,13,17,18-octakis(propyl)porphyrazine, N, N, N', N'-tetramethylamino porphyrazine hybrid and 2,3,9,10,16,17,23,24-octa substituted phthalocyanine were synthesized and characterized using elemental analysis, FTIR, H-1, C-13 NMR and UV-vis spectroscopic techniques. Kinetics of their metalation with Cu(II) and Co(II) and redox reaction of the complexes was studied and are reported here for the first time. It is suggested that deformation of the ring, which is a function of their peripheral functionalities, is essential for effective coordination of the ligands. The kinetic studies indicated metal based oxidation and ring based reduction for the reductants and oxidant respectively. The redox activity of the metal ions is dependent on the availability of their low energy level d-orbitals for charge transfer. It was therefore inferred that the nature of the metal ion and the peripheral substituents of these ligands and their complexes had significant effect on their reactivity. (C) 2014 Elsevier Ltd. All rights reserved.
• Montalban, Antonio Garrido; Michel, Sarah L. J.; Baum, Sven M., Journal of the Chemical Society, Dalton Transactions
  作者：Montalban, Antonio Garrido、Michel, Sarah L. J.、Baum, Sven M.、Vesper, Benjamin J.、White, Andrew J. P.、et al.

  DOI：——

  日期：——