3,6,9,17,20,23,29,30-octaazatricyclo<23.3.1.1^11,15>triaconta-1(29),11,13,15(30),25,27-hexaene-2,10,16,24-tetraone | 168773-89-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酰胺类
• 英文名称: 3,6,9,17,20,23,29,30-octaazatricyclo<23.3.1.1^11,15>triaconta-1(29),11,13,15(30),25,27-hexaene-2,10,16,24-tetraone
• 英文别名: 3,6,9,17,20,23,29,30-Octazatricyclo[23.3.1.111,15]triaconta-1(29),11(30),12,14,25,27-hexaene-2,10,16,24-tetrone
• CAS: 168773-89-5
• 化学式: C₂₂H₂₈N₈O₄
• 分子量: 468.516
• InChiKey: MPGZJDLGVCHAJO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.2
• 重原子数：
  34
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  166
• 氢给体数：
  6
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  二氧化碳 、 3,6,9,17,20,23,29,30-octaazatricyclo<23.3.1.1^11,15>triaconta-1(29),11,13,15(30),25,27-hexaene-2,10,16,24-tetraone 以 氘代二甲亚砜 为溶剂， 反应 0.02h， 生成 2,10,12,20-tetraoxo-3,6,9,13,16,19-hexaaza-1,11(2,6)-dipyridinacycloicosaphane-6-carboxylic acid
  参考文献：
  名称：

  Macrocyclic Influences in CO₂ Uptake and Stabilization

  摘要：

  Two 24-member diamine-tetraamido macrocycles (R = H and CH3), readily synthesized in one or two steps, were found to react with CO, rapidly and efficiently (100% conversion within 1 min at rt). The resulting carbamate formation was demonstrated by H-1, C-13 NMR, ESI-MS, and X-ray crystallography. The crystal structure clearly showed the carbamate group (N-CO2-) formed was tightly bound within the macrocyclic cavity, held by five internal hydrogen bonds, and stabilized by intramolecular carbamate-ammonium salt-bridge formation.

  DOI：

  10.1021/ol501812u
• 作为产物：
  描述：

  2,6-氯甲酰吡啶 在 三乙胺 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 29.0h， 生成 3,6,9,17,20,23,29,30-octaazatricyclo<23.3.1.1^11,15>triaconta-1(29),11,13,15(30),25,27-hexaene-2,10,16,24-tetraone
  参考文献：
  名称：

  被困的氟化物。

  摘要：

  DOI：

  10.1002/anie.200504066

文献信息

• Tricyclic Host for Linear Anions
  作者：Sung Ok Kang、Victor W. Day、Kristin Bowman-James

  DOI：10.1021/ic1013297

  日期：2010.9.20

  tricyclic host for anions consisting of two tetraamide monocycles attached by two ethylene chains was designed and synthesized. Structural and binding results indicate that the receptor is selective for linear triatomic anions. Crystallographic data for two hydrated free bases, along with FHF−, N3−, and SO42− complexes indicate that there are at least two preferred gross conformations for the host, one

  设计并合成了由两个被两个乙烯链连接的两个四酰胺单环组成的阴离子三环主体。结构和结合结果表明该受体对线性三原子阴离子具有选择性。两个水合游离碱晶体学数据，具有沿着FHF -，N 3 -和SO 4个2-络合物表明有至少两个优选的毛构象为主机，其中一个具有伪d 2对称性和其他伪- c ^ 2 ħ对称性。既FHF -和N 3 -封装在伪d 2对称的络合物，将两个四酰胺基大环半桥连接起来。伪C 2 h八水合物结构显示了嵌入宿主腔中的水样冰状H键（H 2 O）6阵列。SO 4 2-的结构几乎与八水合物重叠，但SO 4 2-的阴离子位于主体之外。在DMSO-结合研究d 6表明选择性FHF - ，与其他无机阴离子较小亲和性。
• Formation Equilibrium of a Copper(II)-Binuclear Complex of a New Pyridyl-Containing Tetraoxo Octaaza Macrocyclic Ligand and Its Polarographic Reduction Behavior
  作者：Mutsuo Kodama、Tohru Koike、Eiichi Kimura

  DOI：10.1246/bcsj.68.1627

  日期：1995.6

  It accomodates two copper(II) ions in its macrocyclic cavity with a simultaneous dissociation of the four amide protons to yield a binuclear complex designated as [Cu2H−4L]°. The formation constant of [Cu2H−4L]°, KCu2H−4L ( = [Cu2H−4L°][H+]4/[Cu2+]2[L]), was found to be (3.5 ± 0.2) × 10−12 mol2 dm−6. At the dropping mercury electrode the Cu(II) binuclear complex gave two reduction steps of equal height

  我们研究了新合成的 26 元八氮杂大环 3,6,9,17,20,23,29,30-octaazatricyclo[23.3.1.1.11,15]triaconta-1(29),11 的络合反应,13,15(30),25,27-hexaene-2,10,16,24-tetraone (TOBP, L)，通过 pH 计量滴定得到 Cu(II) 离子。它在其大环腔中容纳两个铜 (II) 离子，同时四个酰胺质子解离以产生指定为 [Cu2H-4L]° 的双核复合物。[Cu2H−4L]°, KCu2H−4L ( = [Cu2H−4L°][H+]4/[Cu2+]2[L]) 的形成常数为 (3.5 ± 0.2) × 10−12 mol2 dm-6。在滴汞电极上，Cu(II) 双核配合物在硼酸盐缓冲溶液中产生两个等高的还原步骤，对应于以下还原方案：
• Structural Insight on Supramolecular Polyion Salts: Inositol Hexaphosphate Enclosed in Cationic Macrocyclic Clusters
  作者：Subhamay Pramanik、Ryan M. Steinert、Katie R. Mitchell‐Koch、Kristin Bowman‐James

  DOI：10.1002/chem.202301764

  日期：2023.10.23

  Supramolecular macrocyclic forces have been used to trap phytate, myo‐inositol‐1,2,3,4,5,6‐hexakisphosphate, a key bioanion with multiple roles in metabolic processes. Due to the complex chemistry of six multivalent phosphates surrounding the small, cyclic inositol framework, crystallographic information of simple phytate salts has been elusive. This report represents a combined crystallographic, theoretical, and solution binding investigation of a supramolecular macrocyclic complex of phytate. Together, the results provide significant insight to phytate's intramolecular and intermolecular interactions at the microenvironment level. The macrocycle‐phytate aggregates consist of phytate anionic pairs, each partly sandwiched by two 24‐membered, amide/amine‐based cationic macrocycles. The phytate ion pairs hold the tetrameric macrocyclic array together by six strong intermolecular hydrogen bonds. Both phytates crystallize in 1a5e phosphate conformations (one axial (P2) and five equatorial phosphates). Solution NMR binding studies in 1 : 1 DMSO‐d₆ : D₂O indicate 2 : 1 macrocycle:phytate associations, suggesting that the sandwich‐like nature of the complex holds together in solution. DFT studies indicate the likely occurrence of dynamic intramolecular interchange of phosphate protons, as well as important roles for the axial (P2) phosphate in both intramolecular and intermolecular hydrogen bonding interactions.

  摘要超分子大环力已被用于捕获植酸（肌醇-1,2,3,4,5,6-六次磷酸），这是一种在新陈代谢过程中起多种作用的关键生物离子。由于围绕小环状肌醇框架的六个多价磷酸盐的化学性质复杂，简单植酸盐类的晶体学信息一直难以捉摸。本报告对植酸盐的超分子大环复合物进行了晶体学、理论和溶液结合的综合研究。研究结果为了解植酸盐在微环境水平上的分子内和分子间相互作用提供了重要依据。大环-植酸聚合体由植酸阴离子对组成，每个阴离子对部分被两个 24 元酰胺/胺基阳离子大环夹住。植酸盐离子对通过六个强分子间氢键将四元大环阵列固定在一起。两种植酸盐都以 1a5e 磷酸构象（一种轴向磷酸（P2）和五种赤道磷酸）结晶。在 1 ：1 DMSO-d6 ：D2O 中进行的溶液核磁共振结合研究表明，2 ：1 的大环：植酸盐结合，表明该复合物的三明治性质在溶液中保持在一起。DFT 研究表明，磷酸质子很可能在分子内发生动态交换，轴向 (P2) 磷酸在分子内和分子间氢键相互作用中也起着重要作用。