[4]cavitand | 350037-85-3

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: [4]cavitand
• 英文别名: 6,12,18,39-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-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
• CAS: 350037-85-3
• 化学式: C₃₆H₃₂O₈
• 分子量: 592.645
• InChiKey: BLSSBXUOWNZTQD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.4
• 重原子数：
  44
• 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：
  73.8
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  [4]cavitand 在 N-溴代丁二酰亚胺(NBS) 、 过氧化苯甲酰 作用下， 以 四氯化碳 、 氯仿 为溶剂， 反应 4.0h， 以80%的产率得到
  参考文献：
  名称：

  Design and Preparation of Mesogenic Cavitands

  摘要：

  首次制备了介向空腔分子，它们形成了单轴无序柱状介质（D_hd）。已经确定了介质形成的结构要求：（i）宏环核心厚度低于5 Å，（ii）上缘有四个大的（3,4,5-三{[4-(十二烷氧基)苯基]氧基}苯甲酰）氧基基团。柱内分子的方向是随机的，排除了介质中分子尺寸的柱内空腔的形成。

  DOI：

  10.1135/cccc20041362
• 作为产物：
  描述：

  溴氯甲烷 、 Resorcin[4]arene 在 caesium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 8.0h， 以83%的产率得到[4]cavitand
  参考文献：
  名称：

  Expanding Cavitand Chemistry: The Preparation and Characterization of [n]Cavitands withn≥4

  摘要：

  The preparation of cavitands composed of 4, 5, 6, and 7 aromatic subunits ([n]cavitands, n = 4-7) is described. The simple, two-step synthetic procedure utilized readily available starting materials (2-methylresorcinol and diethoxymethane). The two cavitand products having 4 and 5 aromatic subunits exhibited highly symmetric cone conformations, while the larger cavitands (n = 6 and 7) adopt conformations of lower symmetry, H-1 NMR spectroscopic studies of [6]cavitand and [7]cavitand revealed that these hosts undergo exchange between equivalent conformations at room temperature. The departure of these two cavitands from cone conformations is related to steric crowding on their Ar-O-CH2-O-Ar bridges and is predicted by simple molecular mechanics calculations (MM2 force field). X-ray diffraction studies on single crystals of the [4]cavitand, [5]cavitand, and [6]cavitand hosts afforded additional experimental support for these conclusions.

  DOI：

  10.1002/1521-3765(20010417)7:8<1637::aid-chem16370>3.0.co;2-x

文献信息

• Supramolecular surface plasmon resonance (SPR) sensors for organophosphorus vapor detection
  作者：Susan M. Daly、Michele Grassi、Devanand K. Shenoy、Franco Ugozzoli、Enrico Dalcanale

  DOI：10.1039/b615516b

  日期：——

  We synthesized cavitands containing COOH moieties at the upper rim of the cavity and evaluated the interaction between these cavitands and the sarin nerve gas simulant, dimethylmethylphosphonate (DMMP) using surface plasmon resonance (SPR) spectroscopy. The carboxylic acid group on the cavitand is expected to form a hydrogen bond with the PO group of the organophosphorus vapors. Films of these cavitands produced a rapid and reversible SPR response to low concentrations of DMMP. We observed concentration dependent sorption of the DMMP molecule into the COOH containing layer in the ppb to ppm range. Spin-cast films and Langmuir–Blodgett (LB) depositions of bilayer thick cavitand films produced identical SPR shifts upon exposure to DMMP. The sensitivity of the sensor was enhanced via LB deposition of multiple bilayers. Eight-layer-thick films of the COOH cavitand showed sensitivity to DMMP concentrations as low as 16 ppb. The orientation of the COOH group into or out of the cavity did not affect DMMP binding, but strongly influenced the water uptake. In both cases the molecular recognition event responsible for the DMMP uptake has been elucidated via crystal structure analyses of the complexes of COOH in/out cavitands with DMMP. Furthermore, we demonstrated that the COOH containing cavitand had an SPR sensitivity to DMMP higher than the standard fluoropolyol sensing layer, and that the cavitand layer was less prone to water vapor and alcohol interferences. Hence, cavitand layers containing a COOH moiety are promising for use as sensitive and specific sensors for nerve gas agents.

  我们在空腔上缘合成了含有 COOH 部分的空配体，并使用表面等离子体共振 (SPR) 光谱评估了这些空配体与沙林神经毒气模拟物二甲基膦酸二甲酯 (DMMP) 之间的相互作用。空配体上的羧酸基团预计会与有机磷蒸气的 PO 基团形成氢键。这些空配体薄膜对低浓度的 DMMP 产生快速且可逆的 SPR 响应。我们观察到 DMMP 分子在 ppb 至 ppm 范围内吸附到含 COOH 层中的浓度依赖性。旋涂薄膜和双层厚空腔薄膜的朗缪尔-布洛杰特 (LB) 沉积在暴露于 DMMP 时产生相同的 SPR 位移。通过多个双层的LB沉积增强了传感器的灵敏度。八层厚的 COOH 空穴体薄膜显示出对低至 16 ppb 浓度的 DMMP 的敏感性。 COOH 基团进出空腔的方向不影响 DMMP 结合，但强烈影响水的吸收。在这两种情况下，通过 COOH 输入/输出空穴与 DMMP 复合物的晶体结构分析，阐明了负责 DMMP 吸收的分子识别事件。此外，我们还证明，含有 COOH 的空穴配体对 DMMP 的 SPR 敏感性高于标准含氟多元醇传感层，并且空穴配体层不易受到水蒸气和酒精的干扰。因此，含有 COOH 部分的空穴层有望用作神经毒气剂的敏感和特异性传感器。
• Inclusion of Cavitands and Calix[4]arenes into a Metallobridgedpara-(1H-Imidazo[4,5-f][3,8]phenanthrolin-2-yl)-Expanded Calix[4]arene
  作者：Enrique Botana、Eric Da Silva、Jordi Benet-Buchholz、Pablo Ballester、Javier de Mendoza

  DOI：10.1002/anie.200603180

  日期：2007.1