cryptophane-111 | 946078-66-6

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: cryptophane-111
• 英文别名: 9,11,29,31,41,43-Hexaoxadecacyclo[19.19.3.38,35.315,28.112,16.132,36.03,38.018,23.05,46.025,49]henpentaconta-1,3(38),5(46),6,8(47),12(51),13,15,18(23),19,21,25(49),26,28(48),32(44),33,35,39-octadecaene
• CAS: 946078-66-6
• 化学式: C₄₅H₃₆O₆
• 分子量: 672.777
• InChiKey: AVMAIVPEJPKDFH-UHFFFAOYSA-N

物化性质

• 熔点：
  >200 °C
• 密度：
  1.265±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  11
• 重原子数：
  51
• 可旋转键数：
  0
• 环数：
  20.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  cryptophane-111 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 氯仿 为溶剂， 反应 312.0h， 以60%的产率得到
  参考文献：
  名称：

  Synthesis of a Functionalizable Water-Soluble Cryptophane-111

  摘要：

  The development of optimized xenon host systems is of crucial importance for the success of molecular imaging using hyperpolarized Xe-129 MRI. Cryptophane-111 is a promising candidate because of its encapsulation properties. The synthesis of cryptophane-111-based biosensors requires both water-solubilizing and chemically activatable groups. An expeditious synthesis of a water-soluble and functionalizable cryptophane-111 is described.

  DOI：

  10.1021/ol4012019
• 作为产物：
  描述：

  溴氯甲烷 、 10,15-dihydro-5H-tribenzo[a,d,g][9]annulene-2,7,12-triol 在 caesium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以11%的产率得到cryptophane-111
  参考文献：
  名称：

  A Cryptophane Core Optimized for Xenon Encapsulation

  摘要：

  The smallest cryptophane ever synthesized, cryptophane-1.1.1 (1), whose internal volume is estimated to be 81 A(3), exhibits the highest binding constant (10000 M-1 at 293 K) in organic solution for xenon encapsulation determined to date. The very slow kinetics of decomplexation on the NMR time scale results in an extremely sharp Xe-129 NMR signal for the Xe@1 complex, which shows an unexpected low-frequency shift. The free energy of activation for decomplexation of xenon at 293 K is Delta G(out) = 64.9 +/- 3 kJ mol(-1) (Delta H-out = 43.2 +/- 1.6 kJ mol(-1); Delta S-out = -74 +/- 3 J mol(-1) K-1). These properties suggest that the cryptophane core of 1 is optimized for use in sensing applications in combination with laser-polarized xenon.

  DOI：

  10.1021/ja073771c

文献信息

• A Water-Soluble Xe@cryptophane-111 Complex Exhibits Very High Thermodynamic Stability and a Peculiar ¹²⁹Xe NMR Chemical Shift
  作者：Robert M. Fairchild、Akil I. Joseph、K. Travis Holman、Heather A. Fogarty、Thierry Brotin、Jean-Pierre Dutasta、Céline Boutin、Gaspard Huber、Patrick Berthault

  DOI：10.1021/ja1071515

  日期：2010.11.10

  [(Cp*Ru)(6)1]Cl(6) ([2]Cl(6)). [2]Cl(6) exhibits a very high affinity for xenon in water, with a binding constant of 2.9(2) × 10(4) M(-1) as measured by hyperpolarized (129)Xe NMR spectroscopy. The (129)Xe NMR chemical shift of the aqueous Xe@[2](6+) species (308 ppm) resonates over 275 ppm downfield of the parent Xe@1 species in (CDCl(2))(2) and greatly broadens the practical (129)Xe NMR chemical shift

  已知的氙结合 (±)-cryptophane-111 (1) 已用六个 [(η(5)-C(5)Me(5))Ru(II)](+) ([Cp*Ru] (+)) 部分以 89% 的产率得到第一个水溶性cryptophane-111衍生物，即[(Cp*Ru)(6)1]Cl(6) ([2]Cl(6))。[2]Cl(6) 对水中的氙具有非常高的亲和力，结合常数为 2.9(2) × 10(4) M(-1)，由超极化 (129)Xe NMR 光谱测量。含水 Xe@[2](6+) 物质 (308 ppm) 的 (129)Xe NMR 化学位移与 (CDCl(2))(2) 中母体 Xe@1 物质的 275 ppm 低场共振，并大大拓宽由氙结合分子主体提供的实用 (129) Xe NMR 化学位移范围。[2][CF(3)SO(3)](6)·xsolvent 和 0.75H(2)O@1·2CHCl(3) 的单晶结构揭示了cryptophane-111
• Extreme Confinement of Xenon by Cryptophane-111 in the Solid State
  作者：Akil I. Joseph、Saul H. Lapidus、Christopher M. Kane、K. Travis Holman

  DOI：10.1002/anie.201409415

  日期：2015.1.26

  exceptionally stable, retaining xenon at temperatures of up to about 300 °C. The high kinetic stability is attributable not only to the high xenon affinity and cage‐like nature of the host, but also to the crystal packing of the clathrate, wherein each window of the molecular container is blocked by the bridges of adjacent containers, effectively imprisoning the noble gas in the solid state. The results highlight

  吸收，捕获和/或储存较重的稀有气体的固体是令人关注的，因为它们具有转化性稀有气体分离/生产，储存或回收技术的潜力。在这里，我们报告了一系列（±）-cryptophane-111（111）的氙气和cl气包合物的分离，晶体结构和热稳定性。一种三角晶形式，氙@ 111⋅ ÿ（溶剂）非常稳定，可在高达约300°C的温度下保留氙气。较高的动力学稳定性不仅归因于宿主的高氙亲和力和笼状性质，而且归因于包合物的晶体堆积，其中分子容器的每个窗口被相邻容器的桥所阻挡，从而有效地监禁固态的稀有气体。结果突出显示了具有固有微腔或零维孔的离散分子材料的潜力。
• Temperature Controls Guest Uptake and Release from Zn₄L₄ Tetrahedra
  作者：Dawei Zhang、Tanya K. Ronson、Songül Güryel、John D. Thoburn、David J. Wales、Jonathan R. Nitschke

  DOI：10.1021/jacs.9b07307

  日期：2019.9.18

  We report the preparation of triazatruxene-faced tetrahedral cage 1, which exhibits two diastereomeric configurations (T1 and T2) that differ in the handedness of the ligand faces relative to that of the octahedrally coordinated metal centers. At lower temperatures, T1 is favored, whereas T2 predominates at higher temperatures. Host-guest studies show that T1 binds small aliphatic guests, whereas T2 binds larger aromatic molecules, with these changes in binding preference resulting from differences in cavity size and degree of enclosure. Thus, by a change in temperature the cage system can be triggered to eject one bound guest and take up another.
• Cryptophane-Xenon Complexes in Organic Solvents Observed through NMR Spectroscopy
  作者：Gaspard Huber、Lætitia Beguin、Hervé Desvaux、Thierry Brotin、Heather A. Fogarty、Jean-Pierre Dutasta、Patrick Berthault

  DOI：10.1021/jp807425t

  日期：2008.11.13

  The interaction of xenon with cryptophane derivatives is analyzed by NMR by using either thermal or hyperpolarized. noble gas. Twelve hosts differing by their stereochemistry, cavity size, and the nature and the number of the substituents on the aromatic rings have been included in the study, in the aim of extracting some clues for the optimization of Xe-129-NMR based biosensors derived from these cage molecules. Four important properties have been examined: xenon-host binding constant, in-out exchange rate of the noble gas, chemical shift, and relaxation of caged xenon. This work aims at understanding the main characteristics of the host-guest interaction in order to choose the best candidate for the biosensing approach. Moreover, rationalizing xenon chemical shift as a function of structural parameters would also help for setting up multiplexing applications. Xenon exhibits the highest affinity for the smallest cryptophane, namely cryptophane-111, and a long relaxation time inside it, convenient for conservation of its hyperpolarization. However, very slow in-out xenon exchange could represent a limitation for its future applicability for the biosensing approach, because the replenishment of the cage in laser-polarized xenon, enabling a further gain in sensitivity, cannot be fully exploited.
• [EN] CRYPTOPHANE DERIVATIVES AND METHODS OF USE THEREOF<br/>[FR] DÉRIVÉS DE CRYPTOPHANE ET PROCÉDÉS D'UTILISATION DE CEUX-CI
  申请人：UNIV GEORGETOWN

  公开号：WO2012051323A2

  公开（公告）日：2012-04-19

  The present invention relates to the cryptophane derivatives of formula (I) capable of encapsulating small molecules such as noble gases for biological and environmental use. In particular, the invention relates to cryptophane derivatives with high affinity for xenon, which can be used as biosensors in clinical imaging. Formula (I)