4,4',4'',4'''-(3,7,11,15-tetraaza-1,5,9,13(1,4)-tetrabenzenacyclohexadecaphane-3,7,11,15-tetracarbonyl)tetrabenzoyl chloride | 111457-61-5

• 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: 4,4',4'',4'''-(3,7,11,15-tetraaza-1,5,9,13(1,4)-tetrabenzenacyclohexadecaphane-3,7,11,15-tetracarbonyl)tetrabenzoyl chloride
• CAS: 111457-61-5
• 化学式: C₆₄H₄₈Cl₄N₄O₈
• 分子量: 1142.92
• InChiKey: LQQXJCMTMOWVOF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.89
• 重原子数：
  80.0
• 可旋转键数：
  8.0
• 环数：
  15.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  149.52
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  4,4',4'',4'''-(3,7,11,15-tetraaza-1,5,9,13(1,4)-tetrabenzenacyclohexadecaphane-3,7,11,15-tetracarbonyl)tetrabenzoyl chloride 、 N-甲基苄胺 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以75%的产率得到N,N',N'',N'''-tetrakis<4-(N-benzyl-N-methylcarbamoyl)benzoyl>-2,11,20,29-tetraaza<3.3.3.3>paracyclophane
  参考文献：
  名称：

  Syntheses of macrocyclic enzyme models. 8. Conformational mobility and molecular recognition by the internal cage of kyuphane

  摘要：

  Temperature-dependent H-1 NMR measurements in CDCl3-CS2 (3:7 v/v) and DMF-d7 in concert with MM2 conformational analysis reveal that the molecular framework of "Kyuphane" (1), a cage-type cubical molecule with six faces each consisting of a 2,11,20,29-tetraaza[3.3.3.3]paracyclophane ring, is significantly more rigid than the corresponding noncage host (2), but still conformationally flexible. A slow rate of interconversion among degenerated conformers of the lowest energy C(i) conformation accounts for the observed NMR line broadening. Hosts 1 and 2 are soluble in acidic aqueous media below pH 4 and behave as polycationic species. Electrostatic field solvation analysis of the tetraprotonated salt of Kyuphane suggests a square-planar proton placement (11a) to predominate in solution. Line broadening for the tetracation appears to arise from both conformer interconversion and proton exchange. Guest recognition behavior of these hosts under acidic conditions was studied by means of H-1 NMR and fluorescence spectroscopy. Kyuphane demonstrates a pH-dependent guest-binding ability due to changes in the specific microenvironmental polarity of its three-dimensional cavity upon variable protonation of the nitrogen atoms. The host also shows size-sensitive and regioselective molecular discrimination originating from the semirigid geometry of the hydrophobic cavity and the specific protonation geometry. The specific molecular discrimination evidenced by 1 was analyzed by MM2 molecular mechanics and applied to selective transport of hydrophobic molecules between organic phases across an aqueous phase in which 1 was present as a carrier. It is noteworthy that the proton NMR signals of guest molecules naphthalene-2,6-disulfonate, 8-anilinonaphthalene-1-sulfonate, and 6-p-toluidinonaphthalene-2-sulfonate completely disappear upon complexation with Kyuphane, whereas the identical guest naphthalene-2,6-disulfonate shows normal upfield shifts of its NMR proton signals upon complexation with 2.

  DOI：

  10.1021/ja00022a006
• 作为产物：
  描述：

  N,N',N'',N'''-tetrakis(4-carboxybenzoyl)-2,11,20,29-tetraaza<3.3.3.3>paracyclophane 在 氯化亚砜 作用下， 反应 14.0h， 以100%的产率得到4,4',4'',4'''-(3,7,11,15-tetraaza-1,5,9,13(1,4)-tetrabenzenacyclohexadecaphane-3,7,11,15-tetracarbonyl)tetrabenzoyl chloride
  参考文献：
  名称：

  Syntheses of macrocyclic enzyme models. 8. Conformational mobility and molecular recognition by the internal cage of kyuphane

  摘要：

  Temperature-dependent H-1 NMR measurements in CDCl3-CS2 (3:7 v/v) and DMF-d7 in concert with MM2 conformational analysis reveal that the molecular framework of "Kyuphane" (1), a cage-type cubical molecule with six faces each consisting of a 2,11,20,29-tetraaza[3.3.3.3]paracyclophane ring, is significantly more rigid than the corresponding noncage host (2), but still conformationally flexible. A slow rate of interconversion among degenerated conformers of the lowest energy C(i) conformation accounts for the observed NMR line broadening. Hosts 1 and 2 are soluble in acidic aqueous media below pH 4 and behave as polycationic species. Electrostatic field solvation analysis of the tetraprotonated salt of Kyuphane suggests a square-planar proton placement (11a) to predominate in solution. Line broadening for the tetracation appears to arise from both conformer interconversion and proton exchange. Guest recognition behavior of these hosts under acidic conditions was studied by means of H-1 NMR and fluorescence spectroscopy. Kyuphane demonstrates a pH-dependent guest-binding ability due to changes in the specific microenvironmental polarity of its three-dimensional cavity upon variable protonation of the nitrogen atoms. The host also shows size-sensitive and regioselective molecular discrimination originating from the semirigid geometry of the hydrophobic cavity and the specific protonation geometry. The specific molecular discrimination evidenced by 1 was analyzed by MM2 molecular mechanics and applied to selective transport of hydrophobic molecules between organic phases across an aqueous phase in which 1 was present as a carrier. It is noteworthy that the proton NMR signals of guest molecules naphthalene-2,6-disulfonate, 8-anilinonaphthalene-1-sulfonate, and 6-p-toluidinonaphthalene-2-sulfonate completely disappear upon complexation with Kyuphane, whereas the identical guest naphthalene-2,6-disulfonate shows normal upfield shifts of its NMR proton signals upon complexation with 2.

  DOI：

  10.1021/ja00022a006

文献信息

• Cubic Azaparacyclophane
  作者：Yukito Murakami、Jun-ichi Kikuchi、Takayuki Hirayama

  DOI：10.1246/cl.1987.161

  日期：1987.1.5

  A cubic macrocycle, each face being constructed with the 2,11,20,29-tetraaza[3.3.3.3]paracyclophane ring, was prepared as a novel host molecule which provides a relatively rigid and hydrophobic three-dimensional cavity, and its guest-binding behavior was examined in acidic aqueous media.

  我们制备了一种立方大环，其每个面都由 2,11,20,29- 四氮杂[3.3.3.3]对位环构成，作为一种新型宿主分子，它提供了一个相对坚硬和疏水的三维空腔，并在酸性水介质中对其客体结合行为进行了研究。