bis-roof porphyrin | 142780-86-7

• 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: bis-roof porphyrin
• CAS: 142780-86-7
• 化学式: C₉₂H₈₂N₈O₁₂
• 分子量: 1491.71
• InChiKey: JMSSZXFDSOIUMA-XEPYMRCESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  20.1
• 重原子数：
  112.0
• 可旋转键数：
  0.0
• 环数：
  23.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  247.6
• 氢给体数：
  6.0
• 氢受体数：
  14.0

反应信息

• 作为反应物：
  描述：

  zinc(II) chloride 、 bis-roof porphyrin 在 2,6-二甲基吡啶 、 氯仿 、 水 作用下， 以 四氢呋喃 为溶剂， 以95%的产率得到zinc bis-roof porphyrin * chloroform * 2H2O
  参考文献：
  名称：

  Recognition of axial ligands by a zinc porphyrin host on the basis of nonpolar interligand interaction

  摘要：

  A porphyrin host with a preorganized cavity on each face has been synthesized and characterized. The constants for association of the zinc complex of the porphyrin with various amine ligands were determined and compared with those of [meso-tetrakis(p-methylphenyl)porphyrinato]zinc(II) and of a "picket-fence" porphyrin zinc(II) complex. The selectivity for the amine ligands was not observed for the picket-fence porphyrin complex. Contrary to this, small secondary amines, such as azetidine, pyrrolidine, and diethylamine, that fit the shape of the cavity of the synthesized host complex bind more strongly to the host than less hindered amines, such as butylamine and propylamine; the recognition parameters for azetidine versus butylamine were found to be K = 22, DELTA-H-degrees = -2.6 kcal/mol, and T-DELTA-S-degrees = -0.8 kcal/mol at 25-degrees-C in toluene. However, the binding of the larger secondary amines such as dipropylamine and diisopropylamine to the host was weakened due to greater steric repulsions from the cavity. It was concluded that, in this case, the stabilization of the ligand binding by the geometrical complementarity between the amines and the cavity of the host is ascribed mainly to attractive interligand interactions such as the London force or CH-pi interaction.

  DOI：

  10.1021/ja00043a016
• 作为产物：
  描述：

  tetrakis-5,10,15,20-(o-aminophenyl)porphyrin 、 2,8,14,20-Tetraoxatricyclo[19.3.1.19,13]hexacosa-1(25),9(26),10,12,21,23-hexaene-11,23-dicarbonyl chloride 在 N-甲基吗啉 作用下， 以 二氯甲烷 为溶剂， 反应 20.0h， 以32%的产率得到bis-roof porphyrin
  参考文献：
  名称：

  Recognition of axial ligands by a zinc porphyrin host on the basis of nonpolar interligand interaction

  摘要：

  A porphyrin host with a preorganized cavity on each face has been synthesized and characterized. The constants for association of the zinc complex of the porphyrin with various amine ligands were determined and compared with those of [meso-tetrakis(p-methylphenyl)porphyrinato]zinc(II) and of a "picket-fence" porphyrin zinc(II) complex. The selectivity for the amine ligands was not observed for the picket-fence porphyrin complex. Contrary to this, small secondary amines, such as azetidine, pyrrolidine, and diethylamine, that fit the shape of the cavity of the synthesized host complex bind more strongly to the host than less hindered amines, such as butylamine and propylamine; the recognition parameters for azetidine versus butylamine were found to be K = 22, DELTA-H-degrees = -2.6 kcal/mol, and T-DELTA-S-degrees = -0.8 kcal/mol at 25-degrees-C in toluene. However, the binding of the larger secondary amines such as dipropylamine and diisopropylamine to the host was weakened due to greater steric repulsions from the cavity. It was concluded that, in this case, the stabilization of the ligand binding by the geometrical complementarity between the amines and the cavity of the host is ascribed mainly to attractive interligand interactions such as the London force or CH-pi interaction.

  DOI：

  10.1021/ja00043a016