| 132774-93-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• CAS: 132774-93-7
• 化学式: C₃₆H₃₈O₆
• 分子量: 566.694
• InChiKey: AYOQGMINZQTBAF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.44
• 重原子数：
  42.0
• 可旋转键数：
  4.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  55.38
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为产物：
  描述：

  5,17-Bis(chloromethyl)-25,26,27,28-tetramethoxypentacyclo<19.3.1.1^3,7.1^9,13.1^15,19>octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecaene 、 乙二醇 在 sodium hydride 、 sodium iodide 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以72%的产率得到
  参考文献：
  名称：

  Upper rim calixcrowns: elucidation of the mechanism of conformational interconversion of calix[4]arenes by quantitative 2-D EXSY NMR spectroscopy

  摘要：

  Tetramethoxycalix[4]arenes (4-8) bridged by a polyether chain at the upper rim (upper rim calixcrowns) were synthesized by reaction of 5,17-bis(chloromethyl)-25,26,27,28-tetramethoxycalix[4]arene (3) with poly(oxyethylene) glycols of different length (mono to penta). In CDCl3 solution at -20-degrees-C, these compounds exist as a mixture of two conformations, viz. the partial cone (P) and the cone (C). The P/C ratio varies between 4.0 and 1.7 depending on the length of the bridge. The upper rim calixcrowns are flexible molecules according to temperature-dependent H-1 NMR spectroscopy. For the first time the mechanism of conformational interconversion of calix[4]arenes (4 and 5) was elucidated by quantitative 2-D EXSY NMR spectroscopy. It proves that there are two different pathways (a slow and a fast process) by which the two P conformational topomers can interconvert. One interconversion proceeds via C (slow process), and the other process proceeds most likely via a short-lived 1,3-alternate (A) intermediate (fast process). The rate constants for both pathways were determined; calix[4]crown-2 4, k(PA) = 0.58, k(PC) = 0.054, and k(CP) = 0.27 s-1 at 298 K, and calix[4]crown-3 5, k(PA) = 5.4, k(PC) = 0.07, and k(CP) = 0.18 s-1 at 253 K. The overall rate diminishes dramatically going from a nine-atom bridge in 5 to a six-atom bridge in 4. Furthermore, shortening of the bridge has a much larger decelerating effect on the P --> A than on the P --> C process.

  DOI：

  10.1021/ja00007a005