5,17-Di-tert-butyl-11,23-bis(cyanomethyl)calix[4]arene-25,26,27,28-tetrol | 170940-14-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 5,17-Di-tert-butyl-11,23-bis(cyanomethyl)calix[4]arene-25,26,27,28-tetrol
• 英文别名: 2-[11,23-Ditert-butyl-17-(cyanomethyl)-25,26,27,28-tetrahydroxy-5-pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaenyl]acetonitrile
• CAS: 170940-14-4
• 化学式: C₄₀H₄₂N₂O₄
• 分子量: 614.784
• InChiKey: XKTBWPATGBWCCQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.9
• 重原子数：
  46
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  129
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5,17-Di-tert-butyl-11,23-bis(cyanomethyl)calix[4]arene-25,26,27,28-tetrol 在 硫酸 、 水 、 溶剂黄146 作用下， 反应 6.0h， 以77%的产率得到2-[11,23-ditert-butyl-17-(carboxymethyl)-25,26,27,28-tetrahydroxy-5-pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaenyl]acetic acid
  参考文献：
  名称：

  Upper Rim Substitution of Calixarenes: Carboxylic Acids

  摘要：

  单取代（5a）、双取代（4a 和 4b）以及四取代（1a）对位氰基甲基卡利克斯[4]芳烃和双（氰基甲基）卡利克斯[6]芳烃（6a）经过酸和碱诱导的水解反应，转化为相应的对位羧基甲基卡利克斯[4]芳烃（5b、4c、4d、2a 和 6b），而这些产物又进一步转化为甲酯（5c、4e、4f、2b）和乙酯（5d、4g、2c）。然而，立体障碍化合物 7 和 8 及其对应的单体 10 和 11 中的氰基甲基在严格条件下对此反应表现出惰性，未能发生水解。甲酯 2b 可转化为 1,3-二苄基醚（3b）、1,3-二苄酸酯（3c）、四苄基醚（3a）和四苄酸酯（3d）。

  DOI：

  10.1055/s-1997-1359
• 作为产物：
  描述：

  5,17-Di-tert-butyl-11,23-bis<(dimethylamino)methyl>calix<4>arene-25,26,27,28-tetrol 以 二甲基亚砜 为溶剂， 反应 15.5h， 生成 5,17-Di-tert-butyl-11,23-bis(cyanomethyl)calix[4]arene-25,26,27,28-tetrol
  参考文献：
  名称：

  Calixarenes: Selective Functionalization and Bridge Building

  摘要：

  The scope of the quinone methide method for introducing functional groups into the upper rim of calix[4]arenes has been expanded by taking advantage of selective esterification at the lower rim. A variety of calix[4]arenes carrying two functional groups on the upper rim have been prepared in this fashion, including compounds 12-25. Compound 25, containing a pair of propargyl groups, undergoes intramolecular oxidative coupling to yield the bridged compound 26. In like fashion the tetrasubstituted propargyl compound 7b undergoes both intramolecular and intermolecular oxidative coupling to give the doubly bridged calix[4]arene 27 and the doubly bridged bis-calix[4]arene 28.

  DOI：

  10.1021/jo00124a017

文献信息

• Calixarene Anhydrides as Useful Synthetic Intermediates¹
  作者：Dejian Xie、C. David Gutsche

  DOI：10.1021/jo962044p

  日期：1997.4.1
• Upper Rim Substitution of Calixarenes: Carboxylic Acids
  作者：Shiv Kumar Sharma、Suseela Kanamathareddy、C. David Gutsche

  DOI：10.1055/s-1997-1359

  日期：1997.11

  The mono- (5a), bis- (4a and 4b), and tetrakis (1a)-p-cyanomethylcalix[4]arenes as well as the bis(cyanomethyl)calix[6]arene (6a) have been transformed both by acid and base induced hydrolysis to the corresponding p-carboxymethylcalix[4]arenes 5b, 4c, 4d, 2a, and 6b which, in turn, were converted to the methyl (5c, 4e, 4f, 2b) and ethyl (5d, 4g, 2c) esters. The cyanomethyl groups in the sterically hindered compounds 7 and 8 and their corresponding monomers 10 and 11, however, were inert to hydrolysis, even under strenuous conditions. The methyl ester 2b can be converted to the 1,3-dibenzyl ether (3b) and the 1,3-dibenzoate (3c) as well as the tetrabenzyl ether (3a) and tetrabenzoate (3d).

  单取代（5a）、双取代（4a 和 4b）以及四取代（1a）对位氰基甲基卡利克斯[4]芳烃和双（氰基甲基）卡利克斯[6]芳烃（6a）经过酸和碱诱导的水解反应，转化为相应的对位羧基甲基卡利克斯[4]芳烃（5b、4c、4d、2a 和 6b），而这些产物又进一步转化为甲酯（5c、4e、4f、2b）和乙酯（5d、4g、2c）。然而，立体障碍化合物 7 和 8 及其对应的单体 10 和 11 中的氰基甲基在严格条件下对此反应表现出惰性，未能发生水解。甲酯 2b 可转化为 1,3-二苄基醚（3b）、1,3-二苄酸酯（3c）、四苄基醚（3a）和四苄酸酯（3d）。
• Calixarenes: Selective Functionalization and Bridge Building
  作者：Suseela Kanamathareddy、C. David Gutsche

  DOI：10.1021/jo00124a017

  日期：1995.9

  The scope of the quinone methide method for introducing functional groups into the upper rim of calix[4]arenes has been expanded by taking advantage of selective esterification at the lower rim. A variety of calix[4]arenes carrying two functional groups on the upper rim have been prepared in this fashion, including compounds 12-25. Compound 25, containing a pair of propargyl groups, undergoes intramolecular oxidative coupling to yield the bridged compound 26. In like fashion the tetrasubstituted propargyl compound 7b undergoes both intramolecular and intermolecular oxidative coupling to give the doubly bridged calix[4]arene 27 and the doubly bridged bis-calix[4]arene 28.