1,21,23,25-Tetramethyl-2,20:3,19-dimetheno-1H,21H,23H,25H-bis[1,3]dioxocino[5,4-i:5'-i']benzo[1,2-d:5,4-d']bis[1,3]benzodioxocin-7,11,15,28-tetrol | 169219-15-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 1,21,23,25-Tetramethyl-2,20:3,19-dimetheno-1H,21H,23H,25H-bis[1,3]dioxocino[5,4-i:5'-i']benzo[1,2-d:5,4-d']bis[1,3]benzodioxocin-7,11,15,28-tetrol
• 英文别名: 25,29,33,37-Tetramethyl-2,4,8,10,14,16,20,22-octaoxanonacyclo[21.15.1.124,38.05,36.07,34.011,32.013,30.017,28.019,26]tetraconta-1(39),5,7(34),11,13(30),17(28),18,23,26,31,35,38(40)-dodecaene-6,12,18,39-tetrol
• CAS: 169219-15-2
• 化学式: C₃₆H₃₂O₁₂
• 分子量: 656.643
• InChiKey: CLLPMAFBZKEXKC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  48
• 可旋转键数：
  0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  155
• 氢给体数：
  4
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  4-氯甲基吡啶盐酸盐 、 1,21,23,25-Tetramethyl-2,20:3,19-dimetheno-1H,21H,23H,25H-bis[1,3]dioxocino[5,4-i:5'-i']benzo[1,2-d:5,4-d']bis[1,3]benzodioxocin-7,11,15,28-tetrol 在 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 18.0h， 以80%的产率得到4-[[25,29,33,37-Tetramethyl-12,18,39-tris(pyridin-4-ylmethoxy)-2,4,8,10,14,16,20,22-octaoxanonacyclo[21.15.1.124,38.05,36.07,34.011,32.013,30.017,28.019,26]tetraconta-1(39),5,7(34),11,13(30),17(28),18,23,26,31,35,38(40)-dodecaen-6-yl]oxymethyl]pyridine
  参考文献：
  名称：

  分子间和分子内金属夹持产生超分子胶囊和碗之间的动态平衡。

  摘要：

  金属诱导的间苯二酚[4]芳烃衍生物1的自组装，其具有四个作为侧基的吡啶单元和两个当量的[M（dppp）（OTf）（2）]（M = Pd，Pt）尽管夹层胶囊3形成为在氯仿/甲醇中的唯一加合物，并且夹层碗4仅在水相中形成，但是夹层的超分子胶囊3和夹层碗4之间在硝基甲烷中具有动态平衡。这证明了如何通过溶剂系统中的细微变化来调节金属诱导的自组装。通过NMR光谱和冷喷雾电离质谱（CSI-MS）表征了硝基甲烷中两种结构的共存。由两个单元的配体1和四个Pt（II）离子组成的夹层胶囊3b的晶体结构，揭示胶囊腔具有15x20 A的纳米尺度尺寸。NMR谱显示3和4之间的动态平衡取决于浓度和温度。在273至343 K范围内进行了温度依赖性（1）H NMR光谱分析，以验证控制动态平衡过程的热力学参数；从夹杂的超分子胶囊3a到夹杂的碗4a的转化在熵上是有利的并且在焓上是不利的。通过线形分析确定内夹钳碗4中吡啶单元的受限旋转的旋转屏障。在273至343

  DOI：

  10.1002/chem.200400801
• 作为产物：
  描述：

  7,11,15,28-tetrabromo-1,21,23,25-tetramethyl-2,20:3,19-dimetheno-1H,21H,23H,25H-bis[1,3]dioxocino[5,4-i:5',4'-i']benzo[1,2-d:5,4-d']bis[1,3]benzodioxocin 在 sodium hydroxide 、 正丁基锂 、 硼酸三甲酯 、 双氧水 作用下， 生成 1,21,23,25-Tetramethyl-2,20:3,19-dimetheno-1H,21H,23H,25H-bis[1,3]dioxocino[5,4-i:5'-i']benzo[1,2-d:5,4-d']bis[1,3]benzodioxocin-7,11,15,28-tetrol
  参考文献：
  名称：

  An Asymmetric Carceplex and New Crystal Structure Yield Information Regarding a 1 Million-Fold Template Effect

  摘要：

  We report the incorporation of methyl ''feet'' as pendant groups in cavitands and carceplexes and their use in the creation of an asymmetric carceplex and the facilitation of the determination of the crystal structure of a carceplex. From the asymmetric carceplex, we have determined a 19 kcal/mol energy barrier to rotation of the guest pyrazine about the host's pseudo-C-2 axes, which demonstrates a high degree of complementarity between the shell of the carceplex and the guest pyrazine. The crystal structure reveals the extensive conjugation of the aryl ethers into the aromatic rings of the host when pyrazine is the guest. This result helps explain why pyrazine is, to date, the best template for the reaction to form the carceplex and thus provides insight to the powerful template effect that is the hallmark of this carceplex reaction. Thus, the investigation of this template effect provides a sensitive probe into noncovalent interactions in general and may be useful in the understanding of recognition in both natural systems such as enzyme/substrate complexes and in non-natural systems such as designed self-assembling structures.

  DOI：

  10.1021/jo00110a025

文献信息

• Highly Organized Spherical Hosts That Bind Organic Guests in Aqueous Solution with Micromolar Affinity: Microcalorimetry Studies
  作者：Evgueni L. Piatnitski、Robert A. Flowers II、Kurt Deshayes

  DOI：10.1002/(sici)1521-3765(20000317)6:6<999::aid-chem999>3.0.co;2-y

  日期：2000.3.17

  cavities of 11 A diameter that are soluble in aqueous solution were constructed. The binding of xylenes, aryl ethers, polyaromatic compounds, ferrocene derivatives, and bicyclic aliphatic compounds were examined by NMR spectroscopy and microcalorimetry. NMR binding studies indicated that binding depended upon guest hydrophobicity and shape. No binding was detected for guests in which a charge must

  构造了两个新颖的，具有11 A直径球形空腔且可溶于水溶液的闭壳半癌状宿主。二甲苯，芳基醚，聚芳族化合物，二茂铁衍生物和双环脂族化合物的结合通过NMR光谱法和微量量热法进行了检查。NMR结合研究表明结合取决于客体疏水性和形状。未检测到必须将电荷作为内含物的一部分去溶剂化的客人或无法放入宿主腔内的客人的结合。分离出三种配合物2.萘，2。对二甲苯和2.二茂铁，发现它们在固相和水溶液中无限稳定。这些复合物的结合常数估计大于10（8）M-1。通过微量量热法测定了十三位客人，结合常数在10（7）和10（3）M-1之间。将此处获得的结果与以前对β-环糊精和环烷主体的研究结果进行比较，以及对熵-焓补偿数据的分析，表明与开壳宿主相比，该宿主结构的客体去溶剂化程度更高。这至少部分解释了与这些封闭壳宿主观察到的亲和力增加。用氢原子取代宿主门户中的羟基不会影响结合常数，这一发现与深埋在宿主腔体内的客体一致。据观察
• The first water-soluble hermicarceplexes
  作者：Juyoung Yoon、Donald J. Cram

  DOI：10.1039/a607353k

  日期：——

  The synthesis of the first water-soluble hemicarcerand and its spectral and binding properties with 14 guests in water are described.

  本文描述了第一种水溶性半包合物的合成及其光谱特性，以及其在水中与14种客体结合的特性。
• Efficient Coupling of Amino Acid Derivatives to Rigid Organic Scaffolds: Model Syntheses for De Novo Proteins.
  作者：Bruce C. Gibb、Adam R. Mezo、Ashley S. Causton、Janet R. Fraser、Frank C.S. Tsai、John C. Sherman

  DOI：10.1016/0040-4020(95)00485-q

  日期：1995.8

  We describe the coupling of amino acid derivatives to four different rigid organic macrocycles. The couplings were achieved in high yields, which augurs well for the coupling of polypeptides to the rigid macrocycles to create a new family of de novo proteins. We discuss the structure of the model compounds based on the hydrogen bonding patterns that are evident from their NMR and IR spectra.
• Templation in the Formation of Carceplexes
  作者：Robert G. Chapman、John C. Sherman

  DOI：10.1021/jo9803582

  日期：1998.6.1

  The formation of carceplexes and hemicarceplexes involves an assembly process whereby a molecular template is entrapped between two bowl-shaped molecules. The process can be highly selective such that a million-fold range in template recognition has been realized. The relative template abilities, or template ratios, for 34 molecules in forming carceplex a guest is described. Species with one, two, and three bridges linking the two "bowls" are reported and were used to delineate the guest-determining step of the reaction. The effect of base and solvent on the reaction are also described, and a discussion of the reaction mechanism is presented.
• Cavitands bearing four fluorophores
  作者：Moonhor Ree、Jong-Seong Kim、Jae Jung Kim、Byeang Hyean Kim、Juyoung Yoon、Heesoo Kim

  DOI：10.1016/j.tetlet.2003.09.070

  日期：2003.11

  The synthesis of novel cavitands containing four fluorophores [tort-butoxycarbonyl protected 2,2'-bis(furyl)benzidine (t-BOC FurylBZ) or 5,5'-bis(4-aminophenyl)-2,2'-bifuryl (t-BOC PFDA)] and ionophoric functional groups on the upper rim is reported. The cavitands bearing the four fluorophores emit blue light photoluminescence. In particular, the cavitand containing PFDA moieties exhibits a high photoluminescence quantum yield. (C) 2003 Elsevier Ltd. All rights reserved.