2,11,20,29-tetraaza<3.3.3.3>paracyclophane | 98001-24-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯啉
• 英文名称: 2,11,20,29-tetraaza<3.3.3.3>paracyclophane
• 英文别名: 3,10,17,24-Tetrazapentacyclo[24.2.2.25,8.212,15.219,22]hexatriaconta-1(29),5,7,12,14,19(32),20,22(31),26(30),27,33,35-dodecaene
• CAS: 98001-24-2
• 化学式: C₃₂H₃₆N₄
• 分子量: 476.665
• InChiKey: UCGBSXJKBISZAV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  36
• 可旋转键数：
  0
• 环数：
  11.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  48.1
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,11,20,29-tetraaza<3.3.3.3>paracyclophane 在 N,N'-二环己基碳二亚胺 作用下， 生成
  参考文献：
  名称：

  Preparation and characterization of water-soluble cyclophanes bearing three or four dipeptide moieties as cationic hosts

  摘要：

  Water-soluble cyclophanes bearing dipeptide residues were prepared by stepwise condensation of 2,11,20,29-tetraaza[3.3.3.3]paracyclophane or 2,11,20-triaza[3.3.3]paracyclophane with L-valine and L-lysine in this sequence and their conformational changes upon complexation with a hydrophobic guest were examined by circular dichroism spectroscopy.

  DOI：

  10.1016/0040-4039(95)01705-m
• 作为产物：
  描述：

  1,4-苯二甲胺 在 sodium tetrahydroborate 、 sodium hydride 作用下， 以 乙醚 为溶剂， 反应 3.5h， 生成 2,11,20,29-tetraaza<3.3.3.3>paracyclophane
  参考文献：
  名称：

  A Simple Synthetic Method for Tetraaza[3.3.3.3]meta- and paracyclopanes by Alkylation ofN-Substituted Trifluoroacetamide

  摘要：

  标题化合物1b和2b的一种简便实用的合成方法如下所述。在100°C下，在N,N-二甲基甲酰胺中，使用氢化钠，或将粉状氢氧化钾加入回流的丙酮中，使N-取代的三氟乙酰胺（5a和5b）与适当的二溴化物（6和9）进行烷基化反应，随后去除三氟乙酰基并使所得胺进行N-甲基化，分别以21%和19%的总产率得到了所需的1b和2b，同时还生成了其低级和高级同系物。

  DOI：

  10.1055/s-1993-26038

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。
• Preparation and host-guest interactions of novel cage-type cyclophanes bearing chiral binding sites provided by dipeptide residues
  作者：Akinori Tanaka、Setsuko Fujiyoshi、Koji Motomura、Osamu Hayashida、Yoshio Hisaeda、Yukito Murakami

  DOI：10.1016/s0040-4020(98)00218-x

  日期：1998.5

  behavior of the cage-type hosts toward fluorescent guests, such as 8-anilinonaphthalene-1-sulfonate and 6-p-toluidinonaphthalene-2-sulfonate, was examined in comparison with those demonstrated by the corresponding non-cage hosts in aqueous media. The microenvironmental polarity around the fluorescent guests and their fluorescence polarization values in the presence of the cage-type hosts revealed that

  新型笼型环烷，由两个刚性大环骨架，四氮杂[3.3.3.3]对环环烷和四个桥接片段组成，这些桥接片段由β-1-天冬氨酰基-1-天冬氨酰或β-d-天冬氨酰基-d-天冬氨酰残基组成准备[分别为（-）- 1和（+）- 1 ]。这些笼型环烷的结构和不对称性质通过1 H NMR和圆二色性（CD）光谱进行了表征。笼型宿主对荧光客体的客体结合行为，例如8-苯胺基萘-1-磺酸盐和6- p与对甲苯基萘-2-磺酸盐进行了比较，并与相应的非笼状基质在水性介质中的结果进行了比较。在笼型宿主存在下，荧光客体周围的微环境极性及其荧光极化值表明，这些客体分子被掺入非极性宿主腔中，并且其旋转运动受到很大限制。此外，通过CD光谱法检查了宿主与疏水性客体棕榈酸（PA）之间的手性宿主-客体相互作用。PA分别在（-）- 1和（+）- 1的情况下经历立体化学变化，以呈现P-和M-螺旋构型。
• Preparation and Characterization of Novel Cage-type Cyclophanes Having Three or Four Bridging Dipeptide Segments
  作者：Osamu Hayashida、Akinori Tanaka、Koji Motomura、Yoshio Hisaeda、Yukito Murakami

  DOI：10.1246/cl.1996.1057

  日期：1996.12

  Novel cage-type cyclophanes constructed with two rigid macrocyclic skeletons, triaza[3.3.3]paracyclophanes or tetraaza[3.3.3.3.]paracyclophanes, and three or four dipeptide moieties, α-L-aspartyl-L-aspartyl residues, were prepared. The guest-binding behavior of the cage-type hosts toward fluorescent guests, such as 8-anilinonaphthalene-1-sulfonate and 6-p-toluidinonaphthalene-2-sulfonate, was examined

  制备了由两个刚性大环骨架、三氮杂 [3.3.3.] 对环烷或四氮杂 [3.3.3.3.] 对环烷和三或四个二肽部分、α-L-天冬氨酰-L-天冬氨酰残基构成的新型笼型环芳。将笼型宿主对荧光客体（如 8-anilinonaphthalene-1-sulfonate 和 6-p-toluidinonaphthalene-2-sulfonate）的客体结合行为与非笼型宿主对相同客人。
• Binding of Acetylcholine and Tetramethylammonium to Flexible Cyclophane Receptors:  Improving on Binding Ability by Optimizing Host's Geometry
  作者：Paolo Sarri、Francesca Venturi、Francesco Cuda、Stefano Roelens

  DOI：10.1021/jo049899j

  日期：2004.5.1

  The structure of a cyclophanic tetraester (1), previously employed for investigations on the cation−π interaction, has been optimized to better accommodate acetylcholine (ACh) and tetramethylammonium (TMA) guests. Following indications from molecular modeling calculations, a flexible cyclophane receptor of significantly improved binding properties has been obtained by removing the four carbonyl groups

  先前用于研究阳离子-π相互作用的环烷四酸酯（1）的结构已进行了优化，以更好地容纳乙酰胆碱（ACh）和四甲基铵（TMA）来宾。根据分子模型计算的指示，已经通过除去母体宿主的四个羰基获得了结合性能显着改善的柔性环烷受体。通过改进的方法制备了2,11,20,29-四氧合[3.3.3.3]对环磷烷（2），该步骤经便利地设计以避免形成引起严重分离问题的连续的环寡聚物。协会2与TMA苦味酸盐是在CDCl测量3在Ť = 296 K内由1个1 H NMR滴定并与结合为一组参考主机获得的数据，包括父四酯1，相应的cyclophanic四胺，的开链对应物2，其从cyclooligomers五聚体八聚体到。通过主体的几何优化，实现了从15倍（相对于四酯和四胺）到超过80倍（相对于开链四醚）的结合增强。对于各种抗衡离子，研究了2与ACh和TMA的结合。恒定的结合近8千焦mol的自由能的增量- 1相对于1观察到，与
• Syntheses of macrocyclic enzyme models. 8. Conformational mobility and molecular recognition by the internal cage of kyuphane
  作者：Yukito Murakami、Junichi Kikuchi、Teruhisa Ohno、Takayuki Hirayama、Yoshio Hisaeda、Hiroshi Nishimura、James P. Snyder、Kosta Steliou

  DOI：10.1021/ja00022a006

  日期：1991.10

  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.