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 | 125065-73-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 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
• 英文别名: 5,17-bis(chloromethyl)-25,26,27,28-tetramethoxycalix<4>arene；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；5,17-bis(chloromethyl)-25,26,27,28-tetramethoxypentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9(27),10,12,15(26),16,18,21,23-dodecaene
• CAS: 125065-73-8；129568-41-8
• 化学式: C₃₄H₃₄Cl₂O₄
• 分子量: 577.548
• InChiKey: HSDIDJMARWXYOE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.88
• 重原子数：
  40.0
• 可旋转键数：
  6.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  36.92
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  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 、 三乙二醇 在 sodium hydride 、 sodium iodide 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以13%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
• 作为产物：
  描述：

  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-5,17-dimethanol 在 氯化亚砜 作用下， 以 氯仿 为溶剂， 生成 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
  参考文献：
  名称：

  杯[4]芳烃在上缘的选择性功能化

  摘要：

  描述了通过转移功能和在苯酚环对位的选择性取代在上边缘对杯[4]芳烃进行选择性径向官能化的方法。描述了26,28-二甲氧基-11,23-二硝基杯[4]芳烃的晶体结构。

  DOI：

  10.1016/s0040-4039(00)99097-x

文献信息

• Selective functionalization of calix[4]arenes at the upper rim
  作者：Jan Dirk Van Loon、Arturo Arduini、Laura Coppi、Willem Verboom、Andrea Pochini、Rocco Ungaro、Sybolt Harkema、David N. Reinhoudt

  DOI：10.1021/jo00308a024

  日期：1990.10
• VAN, LOON J. -D.;ARDUINI, A.;VERBOOM, W.;UNGARO, R.;VAN, HUMMEL G. J.;HAR+, TETRAHEDRON LETT., 30,(1989) N0, C. 2693-2696
  作者：VAN, LOON J. -D.、ARDUINI, A.、VERBOOM, W.、UNGARO, R.、VAN, HUMMEL G. J.、HAR+

  DOI：——

  日期：——
• VAN, LOON JAN-DIRK;ARDUINI, ARTURO;COPPI, LAURA;VERBOOM, WILLEM;POCHINI, +, J. ORG. CHEM., 55,(1990) N1, C. 5639-5646
  作者：VAN, LOON JAN-DIRK、ARDUINI, ARTURO、COPPI, LAURA、VERBOOM, WILLEM、POCHINI, +

  DOI：——

  日期：——