methyl 4-formyl-3,5-bis(10-methoxycarbonyldecyloxy)benzoate | 254966-09-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl 4-formyl-3,5-bis(10-methoxycarbonyldecyloxy)benzoate
• 英文别名: Methyl 4-formyl-3,5-bis(11-methoxy-11-oxoundecoxy)benzoate
• CAS: 254966-09-1
• 化学式: C₃₃H₅₂O₉
• 分子量: 592.77
• InChiKey: JGVGLNONNMCVKF-UHFFFAOYSA-N

物化性质

• 沸点：
  665.9±55.0 °C(Predicted)
• 密度：
  1.063±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.4
• 重原子数：
  42
• 可旋转键数：
  29
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  114
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  吡咯 、 methyl 4-formyl-3,5-bis(10-methoxycarbonyldecyloxy)benzoate 在 三氟化硼乙醚 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 为溶剂， 反应 3.67h， 以16%的产率得到5,10,15,20-tetrakis(4-methoxycarbonyl-3,5-bis(10-methoxycarbonyldecyloxy)phenyl)porphyrin
  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：

  3,5-二羟基-4-甲基苯甲酸甲酯 在 溴 、 碳酸氢钠 、 potassium carbonate 、 二甲基亚砜 作用下， 以 四氯化碳 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 24.17h， 生成 methyl 4-formyl-3,5-bis(10-methoxycarbonyldecyloxy)benzoate
  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

• A New Strategy for the Design of Water-Soluble Synthetic Receptors: Specific Recognition of DNA Intercalators and Diamines.
  作者：Kenji Wada、Tadashi Mizutani、Hideki Matsuoka、Susumu Kitagawa

  DOI：10.1002/chem.200204481

  日期：2003.5.23

  For the binding of DNA intercalators, the following features are noteworthy: 1). Binding constants are similar between the zinc porphyrins and zinc-free porphyrins; 2). the binding constant is larger for the guest having the lower LUMO; this indicates the important contribution of charge-transfer interactions to binding; 3). the hydrophobic and cationic nature of DNA intercalators is substantially important

  制备了在疏水性环境中具有两个路易斯酸性位点（锌）的水溶性双卟啉锌受体1和2，其由烷基链和双卟啉骨架组成，并被亲水性外部（十二个或十八个羧基）覆盖。受体对水中的二胺和DNA嵌入剂表现出高亲和力，其结合常数K（a）分别为10（7）和10（8）M（-1）。二胺和DNA嵌入剂通过不同的机制与受体结合。二胺通过疏水相互作用和锌氮相互作用结合，而DNA嵌入剂通过疏水相互作用和电荷转移相互作用结合。柔性烷基链可以使范德华斯与客体接触，并通过诱导拟合型机制在结合的客体周围形成疏水环境。对于DNA嵌入剂的结合，应注意以下特征：1）。锌卟啉和无锌卟啉的结合常数相似。2）。对于具有较低LUMO的客人，结合常数较大；这表明电荷转移相互作用对结合的重要贡献；3）。DNA嵌入剂的疏水性和阳离子性非常重要，并且4）。较高的离子强度降低了结合亲和力；这表明了静电相互作用的适度贡献。受体的构象不稳定性也有助于紧密结合：在无