[5,10,15,20-tetrakis(4-methoxycarbonyl-3,5-bis(4-methoxycarbonyldecyloxy)phenyl)porphyrinato]zinc(II) | 254966-15-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: [5,10,15,20-tetrakis(4-methoxycarbonyl-3,5-bis(4-methoxycarbonyldecyloxy)phenyl)porphyrinato]zinc(II)
• CAS: 254966-15-9
• 化学式: C₁₄₈H₂₁₂N₄O₃₂Zn
• 分子量: 2624.71
• InChiKey: ZMODSNMZPRTLRC-AWOROLCUSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [5,10,15,20-tetrakis(4-methoxycarbonyl-3,5-bis(4-methoxycarbonyldecyloxy)phenyl)porphyrinato]zinc(II) 、 potassium hydroxide 以 四氢呋喃 、 甲醇 、 水 为溶剂， 以79%的产率得到[5,10,15,20-tetrakis(4-carboxy-3,5-bis(4-carboxydecyloxy)phenyl)porphyrinato]zinc(II) potassium salt
  参考文献：
  名称：

  Porphyrin Receptors for Amines, Amino Acids, and Oligopeptides in Water

  摘要：

  A series of water-soluble porphyrin receptors having a hydrophobic binding pocket, a Lewis acidic site (Zn), and an electrostatic recognition site (COO- groups) were prepared. All the porphyrin receptors have a [meso-tetrakis(p-carboxyphenyl)porphyrinato]zinc (Zn . TCPP) as a common structural unit, and eight omega-carboxyalkyloxy groups (alkyloxy = methoxy (1), butoxy (2), decyloxy (3)) at the ortho positions of the phenyl groups. These receptors bind amines, a-amino acid esters, and oligopeptides in water with significant selectivity. For binding of hydrophilic guests, 1, 2, and 3 bind histamine in pH 8 buffer at 25 degrees C with binding constants of 157000, 31000, and 18200 M-1, respectively, where the coordination (Imd-Zn) and the salt bridge (NH3+--OOC) stabilized the complex. The large dependence of the binding constants on the ionic strength indicated that the electrostatic interaction between the ammonium group of histamine and the carboxylate groups of receptor contributes significantly to tight binding in water. Receptors 1-3 also bind a cationic guest, Arg-OMe, with a binding constant of 440-11000 M-1. The effective charge of the receptors for electrostatic recognition of Arg-OMe in pH 9 Borax (I = 0.1 M) at 25 degrees C was evaluated by the Debye-Huckel limiting law as 4.2, 4.3, and 3.0 for 1, 2, and 3, respectively. These observations indicate that a salt bridge, which is exposed to water and involves hydrogen bonding, as seen in the 1-histamine and 1-Arg-OMe complexes, can be used as a significant recognition force. Binding of Arg-OMe by 2 and 3 was entropically driven, and binding of Arg-OMe by 1 was enthalpically driven. Therefore, the driving force of binding is desolvation from the ionic groups in the former case and the electrostatic attraction in the latter case. For binding of hydrophobic guests, 3 binds Trp-OMe or pyridine in water with binding constants of 7000-8000 M-1, while 1 and Zn . TCPP bind these guests less tightly with binding constants of 20-500 M-1, indicating the importance of the long alkyl chains to provide a hydrophobic binding pocket above the porphyrin plane.

  DOI：

  10.1021/ja9922126
• 作为产物：
  描述：

  zinc diacetate 、 5,10,15,20-tetrakis(4-methoxycarbonyl-3,5-bis(10-methoxycarbonyldecyloxy)phenyl)porphyrin 以 甲醇 、 氯仿 为溶剂， 以80%的产率得到[5,10,15,20-tetrakis(4-methoxycarbonyl-3,5-bis(4-methoxycarbonyldecyloxy)phenyl)porphyrinato]zinc(II)
  参考文献：
  名称：

  Porphyrin Receptors for Amines, Amino Acids, and Oligopeptides in Water

  摘要：

  A series of water-soluble porphyrin receptors having a hydrophobic binding pocket, a Lewis acidic site (Zn), and an electrostatic recognition site (COO- groups) were prepared. All the porphyrin receptors have a [meso-tetrakis(p-carboxyphenyl)porphyrinato]zinc (Zn . TCPP) as a common structural unit, and eight omega-carboxyalkyloxy groups (alkyloxy = methoxy (1), butoxy (2), decyloxy (3)) at the ortho positions of the phenyl groups. These receptors bind amines, a-amino acid esters, and oligopeptides in water with significant selectivity. For binding of hydrophilic guests, 1, 2, and 3 bind histamine in pH 8 buffer at 25 degrees C with binding constants of 157000, 31000, and 18200 M-1, respectively, where the coordination (Imd-Zn) and the salt bridge (NH3+--OOC) stabilized the complex. The large dependence of the binding constants on the ionic strength indicated that the electrostatic interaction between the ammonium group of histamine and the carboxylate groups of receptor contributes significantly to tight binding in water. Receptors 1-3 also bind a cationic guest, Arg-OMe, with a binding constant of 440-11000 M-1. The effective charge of the receptors for electrostatic recognition of Arg-OMe in pH 9 Borax (I = 0.1 M) at 25 degrees C was evaluated by the Debye-Huckel limiting law as 4.2, 4.3, and 3.0 for 1, 2, and 3, respectively. These observations indicate that a salt bridge, which is exposed to water and involves hydrogen bonding, as seen in the 1-histamine and 1-Arg-OMe complexes, can be used as a significant recognition force. Binding of Arg-OMe by 2 and 3 was entropically driven, and binding of Arg-OMe by 1 was enthalpically driven. Therefore, the driving force of binding is desolvation from the ionic groups in the former case and the electrostatic attraction in the latter case. For binding of hydrophobic guests, 3 binds Trp-OMe or pyridine in water with binding constants of 7000-8000 M-1, while 1 and Zn . TCPP bind these guests less tightly with binding constants of 20-500 M-1, indicating the importance of the long alkyl chains to provide a hydrophobic binding pocket above the porphyrin plane.

  DOI：

  10.1021/ja9922126

文献信息

• Molecular Recognition of Amines and Amino Esters by Zinc Porphyrin Receptors:  Binding Mechanisms and Solvent Effects
  作者：Tadashi Mizutani、Kenji Wada、Susumu Kitagawa

  DOI：10.1021/jo000557x

  日期：2000.9.1

  (CH(2)Cl(2)) and in a polar solvent (water) but loose in a solvent of intermediate polarity (H(2)O-MeOH (1:1)), demonstrating that two competitive driving forces are operating: (1) attractive electrostatic forces between host and guest such as coordination of the amino group to the zinc atom, and (2) entropic forces stemming from desolvation as well as enthalpic forces due to the host-guest dispersion forces

  制备了在内消旋苯基（1-3）中带有12个酯基的锌卟啉受体，并重点研究了胺和α-氨基酯的结合。5,10,15,20-四（2,6-双（羰基甲氧基甲氧基）-4-羰基甲氧基苯基）卟啉（游离碱为1）的X射线晶体分析表明，该受体在卟啉平面上方具有一个结合口袋。紫外可见滴定实验表明，卟啉锌受体结合胺和α-氨基酯，其结合常数（K（a））在CH（2）Cl（2）中于25度范围为0.5至52 700 M（-1） C。1的酯官能团有助于在25°C下CH（2）Cl（2）中的芳族α-氨基酯（K（a）= 8 000-23 000 M（-1）在CH（2）Cl（2）中）的结合。庞大的脂肪族α-氨基酯（在25°C下CH（2）Cl（2）中的Leu-OMe的K（a）= 460 M（-1）），表明CH-pi型相互作用和位阻控制选择性。胺和α-氨基酯的结合在非极性溶剂（CH（2）Cl（2））和极性溶剂（水）中均很紧密，但在中等极性的溶剂（H（2）O-MeOH中则较松散）