5α,10α,15α,20β-tetrakis[2-(octanoylamino)phenyl]-21H,23H-porphyrin | 134153-60-9

• 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
• 英文名称: 5α,10α,15α,20β-tetrakis[2-(octanoylamino)phenyl]-21H,23H-porphyrin
• CAS: 134153-60-9
• 化学式: C₇₆H₉₀N₈O₄
• 分子量: 1179.6
• InChiKey: ZRGOPGMFEYTMQB-IAPFGHMISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  20.52
• 重原子数：
  88.0
• 可旋转键数：
  32.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  173.76
• 氢给体数：
  6.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  copper(II) perchlorate hexahydrate 、 5α,10α,15α,20β-tetrakis[2-(octanoylamino)phenyl]-21H,23H-porphyrin 以 N,N-二甲基甲酰胺 为溶剂， 生成
  参考文献：
  名称：

  Steric and stereoelectronic effects on metal ion incorporation into picket fence porphyrins in homogeneous solution: the relationship of molecular conformation to reactivity

  摘要：

  Rate constants for the incorporation of Cu(II) and Zn(II) using the perchlorate salts were measured for the four atropisomers of C2 and C-16 derivatives of meso-tetrakis(o-alkylamidophenyl)porphyrin, the "picket fence" porphyrins (PFPs) in N,N-dimethylformamide (DMF). A 156-fold variation in rate constants is noted for Cu(II) incorporation into the 25 PFPs studied in DMF which are 56.5-8800 times less reactive than meso-tetraphenylporphyrin (TPP). For Cu(II) incorporation, the reactivity order is 4,0 > 3,1 > cis 2,2 > trans 2,2 in all cases. The span of metalation rate constants for individual isomers as a function of side chain length follows the opposite order, consistent with increasing steric exclusion of metal ion as the number of substituents (0-2) about the less hindered face of the porphyrin increases. A 2.2 x 10(5)-fold range of facial metalation rate constants calculated for TPP and the PFPs indicates that metalation of the 4,0 isomer occurs predominantly (> 99%) from the unsubstituted face. Increased perpendicularity between the phenyl rings and the porphyrin core with increasing side chain bulk, attributed to (1) steric interactions between ortho substituents and the porphyrin core and (2) transannular side chain interactions, is postulated to result in enhanced core rigidity for the 4,0 isomer and consequent decreased metalation rates. This postulate is supported by H-1 NMR and UV-visible spectral data for the set of compounds studied, relative basicities, and molecular models. For the 4,0 isomer, whose metalation is controlled by such stereoelectronic factors, side chain branching more effectively inhibits metalation (range of k(Cu2+) = 4.7 M-1 s-1) than linear side chain extension (range of k(Cu2+) = 2.2 M-1 s-1). The results of this study are relevant to the spectroscopy, chemistry, and solution structure of tetraarylporphyrins.

  DOI：

  10.1021/j100182a034
• 作为产物：
  描述：

  tetrakis-5,10,15,20-(o-aminophenyl)porphyrin 、 辛酰氯 在 吡啶 作用下， 以 苯 为溶剂， 生成 5α,10α,15α,20β-tetrakis[2-(octanoylamino)phenyl]-21H,23H-porphyrin
  参考文献：
  名称：

  Atropisomer-specific formation of premicellar porphyrin J-aggregates in aqueous surfactant solutions

  摘要：

  The 4,0-atropisomer of intermediate (C6 or C7) to long (C16) chain length picket fence porphyrins (PFPs) exhibit red-shifted absorption and reduced singlet and triplet lifetimes in dilute aqueous surfactant solutions (i.e. below the critical micelle concentration). The spectral and photophysical behavior of these species is consistent with formation of premicellar aggregates containing two or more porphyrin chromophores lying in an offset, face-to-face arrangement (lambda-max approximately 436 nm, v sharp, for C6 or C7 compounds), which differ from normal aqueous porphyrin aggregates (lambda-max approximately 426 nm, broad) or monomeric porphyrin in homogeneous or micellar solution (lambda-max = 418-420 nm, sharp). The most characteristic behavior is noted at intermediate chain lengths for the free base or Pd(II) complex of 4,0-meso-tetrakis(2-hexanamidophenyl)porphyrin (4,0-THex) and for the free base of 4,0-THept, suggesting an optimal molecular hydrophobicity, side-chain length, and molecular topology for complex formation. The premicellar surfactant-porphyrin complexes are formed selectively from the 4,0-atropisomer and exhibit an SDS/porphyrin ratio of 3.2 for 4,0-THex. Acid-base titration behavior of the 4,0-THex J-aggregates suggests a structure in which the porphyrin core is isolated from the anionic surfactant head groups in a relatively hydrophobic microenvironment. Addition of alcohols or surfactant to disorganized aqueous aggregates of short- and long-chain 4,0-PFPs, respectively, apparently results in a modest reorganization of porphyrin chromophores (lambda-max approximately 436-438 nm) indicative of an inherent tendency toward J-aggregation for the 4,0-isomer.

  DOI：

  10.1021/j100163a035

文献信息

• Nappa, Mario J.; Tolman, Chadwick A., Inorganic Chemistry, <hi>1985</hi>, vol. 24, # 26, p. 4711 - 4719
  作者：Nappa, Mario J.、Tolman, Chadwick A.

  DOI：——

  日期：——