5,11,17,23-tetra-tert-butyl-25,26,27-tris(benzyloxy)-28-hydroxycalix<4>arene | 135501-37-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5,11,17,23-tetra-tert-butyl-25,26,27-tris(benzyloxy)-28-hydroxycalix<4>arene
• 英文别名: 5,11,17,23-tetra-t-butyl-26,27,28-tri-O-benzylcalix[4]arene；25,26,27-tris(benzyloxy)-28-hydroxy-p-t-butylcalix[4]arene；5,11,17,23-tetra-tert-butyl-25,26,27-tris(benzyloxy)-28-hydroxycalix[4]arene；5,11,17,23-tetratert-butyl-26,27,28-tris(phenylmethoxy)pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3(28),4,6,9,11,13(27),15,17,19(26),21(25),22-dodecaen-25-ol
• CAS: 135501-37-0；135394-95-5
• 化学式: C₆₅H₇₄O₄
• 分子量: 919.3
• InChiKey: JDAXTORUTYYKTN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.0
• 重原子数：
  69.0
• 可旋转键数：
  9.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  47.92
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  5,11,17,23-tetra-tert-butyl-25,26,27-tris(benzyloxy)-28-hydroxycalix<4>arene 在 10% Pd/C 、 氢气 、 lithium hydride 、 溶剂黄146 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 50.0~55.0 ℃ 、101.33 kPa 条件下， 反应 35.0h， 生成 5,11,17,23-tetra-t-butyl-25-O-(2-bromoethyl)calix[4]arene
  参考文献：
  名称：

  辛可宁衍生的杯芳烃基手性相转移催化剂的合成及其在不对称烷基化中的应用

  摘要：

  以对丁基杯芳烃[4]芳烃为原料，分四步合成了一种新型杯芳烃基手性相转移催化剂。通过用苄基溴进行 N-（二苯基亚甲基）甘氨酸叔丁酯的相转移烷基化，在一系列条件下评估其催化性能。在最佳条件下，烷基化产物的产率为 96%，ee 为 91%。

  DOI：

  10.3184/174751912x13418247519819
• 作为产物：
  描述：

  溴甲苯 在 sodium hydride 、 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 26.0h， 生成 5,11,17,23-tetra-tert-butyl-25,26,27-tris(benzyloxy)-28-hydroxycalix<4>arene
  参考文献：
  名称：

  Calixarenes. 25. Conformations and structures of the products of arylmethylation of calix[4]arenes

  摘要：

  The arylmethylations of calix[4]arenes reported in this paper serve as companion pieces to an earlier study of the effects of reaction conditions and the structure of the derivatizing agent on the conformational outcome of the aroylation of calix[4]arenes. In contrast to the aroylation reaction, where a significant and predictable relation is observed between the para substituent of the aroyl chloride and the ratio of conformers formed, the arylmethylation reaction shows only a small and much less easily predictable dependence of the conformer ratio on the para substituent of the arylmethyl halide. Also, whereas the products of aroylation are the cone and/or 1,3-alternate conformers, those of arylmethylation are the cone and/or partial cone conformers. While no rationale has yet emerged to explain this difference, a study of the benzylation of dibenzyl and tribenzyl ethers of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrahydroxycalix[4]arene has established that the conformations of the tetraethers are not completely established until the third step in some cases and the fourth step in others.

  DOI：

  10.1021/jo00015a039

文献信息

• Easy and Selective Method for the Synthesis of Mono-, Di-, Tri-, Tetra-O-Arylmethyl-P-T-Butylcalix[4]Arenes
  作者：Yuanyuan Xie、Wang Xia

  DOI：10.3184/174751912x13371837407801

  日期：2012.7

  Mono-, di-, tri- and tetra-O-arylmethyl-p-t-butylcalix[4]arenes were synthesised respectively from p-t-butylcalix[4]arene and arylmethyl bromide through an easy and selective one-step reaction. Mono- and di-arylmethyl ethers of p-t-butylcalix[4]arenes were prepared using LiH as a base, while tri- and tetra-arylmethyl derivatives were afforded in the presence of Ba(OH)₂ and BaO. These methods are remarkable for excellent selectivity, mild reaction conditions, moderate to good yields and easy purification.

  以对-叔丁基钙[4]炔和芳基甲基溴为原料，通过简单而有选择性的一步反应，分别合成了单芳基甲基对叔丁基钙[4]炔、二芳基甲基对叔丁基钙[4]炔、三芳基甲基对叔丁基钙[4]炔和四芳基甲基对叔丁基钙[4]炔。以 LiH 为碱制备了对叔丁基钙[4]炔的单芳基甲基醚和二芳基甲基醚，而在 Ba(OH)2 和 BaO 的存在下则得到了三芳基甲基衍生物和四芳基甲基衍生物。这些方法具有极佳的选择性、温和的反应条件、中等至良好的产率和易于纯化的特点。
• On the Origin of the Distal vs. Proximal Regioselectivity in Di-<i>O</i>-alkylation of Calix[4]arenes
  作者：Koji Araki、Koji Iwamoto、Satoshi Shigematsu、Seiji Shinkai

  DOI：10.1246/cl.1992.1095

  日期：1992.6

  basis of the distal vs. proximal regioselectivity in di-O-alkylation of calix[4]arene was investigated through the detailed product analyses. It was found that (i) the regioselectivity is profoundly affected by the residual intramolecular hydrogen-bonds and (ii) the distal isomer is more reactive for further O-alkylation than the proximal isomer, resulting in the “apparent” proximal selectivity.

  通过详细的产物分析研究了杯[4]芳烃二-O-烷基化中远端与近端区域选择性的机制基础。发现（i）区域选择性受残留分子内氢键的影响很大，（ii）远端异构体比近端异构体对进一步的 O-烷基化更具反应性，导致“表观”近端选择性。