5,11,17,23,29,35,41,47-Octa-tert-butyl-49,51,53-tris[(4-methylbenzyl)oxy]calix[8]arene-50,52,54,55,56-pentol

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5,11,17,23,29,35,41,47-Octa-tert-butyl-49,51,53-tris[(4-methylbenzyl)oxy]calix[8]arene-50,52,54,55,56-pentol
• 英文别名: 5,11,17,23,29,35,41,47-Octatert-butyl-52,54,56-tris[(4-methylphenyl)methoxy]nonacyclo[43.3.1.13,7.19,13.115,19.121,25.127,31.133,37.139,43]hexapentaconta-1(48),3(56),4,6,9(55),10,12,15,17,19(54),21,23,25(53),27,29,31(52),33,35,37(51),39(50),40,42,45(49),46-tetracosaene-49,50,51,53,55-pentol
• 化学式: C₁₁₂H₁₃₆O₈
• 分子量: 1610.31
• InChiKey: STBBKUFKWZVHOI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  32.5
• 重原子数：
  120
• 可旋转键数：
  17
• 环数：
  12.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  129
• 氢给体数：
  5
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  4-甲基苄溴 、 5,11,17,23,29,35,41,47-Octa-tert-butyl-49,53-bis[(4-methylbenzyl)oxy]calix[8]arene-50,51,52,54,55,56-hexol 在 cesium fluoride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 以41%的产率得到5,11,17,23,29,35,41,47-Octa-tert-butyl-49,51,53-tris[(4-methylbenzyl)oxy]calix[8]arene-50,52,54,55,56-pentol
  参考文献：
  名称：

  "Alternate Alkylation" of p-tert-Butylcalix[8]arene in the Presence of Weak Bases

  摘要：

  Alkylation of p-tert-butylcalix[8]arene in the presence of weak bases has been investigated using p-methylbenzyl bromide as an electrophile and CsF as a weak base in THF/DMF. Initially, a sequence of monoalkylation steps on progressively more alkylated compounds has been carried out, leading to the isolation and characterization of 13 p-methylbenzyl ethers ranging from mono- to octasubstituted. Successively, the time course of the composition of the reaction mixture has been determined at regular time intervals by chromatographic analysis and products isolation, in order to have a semiquantitative dynamic picture of the whole process. The reaction path goes mainly through the formation of mono-, 1,3-di-, 1,3,5-tri-, 1,3,5,7-tetra-, 1,2,3,5,7-penta-, 1,2,3,4,5,7- and 1,2,3,5,6,7-hexa-, and heptasubstituted derivatives. This result agrees with an ''alternate alkylation'' mechanism based on the preferential formation of monoanions stabilized by two flanking hydrogen bonds. However, the isolation of appreciable amounts of 1,2,4-tris(p-methylbenzyl) ether indicates that less stable monoanions can also be formed, possibly due to either temporary conformational preferences or the conformational mobility of the calix[8]arene macrocycle, resulting in a less effective hydrogen-bonding stabilization of anionic intermediates.

  DOI：

  10.1021/jo00118a033

文献信息

• Alkylation Products of a Calix[8]arene Trianion. Effect of Charge Redistribution in Intermediates
  作者：Placido Neri、Grazia M. L. Consoli、Francesca Cunsolo、Concetta Rocco、Mario Piattelli

  DOI：10.1021/jo970029u

  日期：1997.6.1

  well-defined calix[8]arene trianion under alkylation conditions was investigated by reacting the tetraethylammonium salt of p-tert-butylcalix[8]arene trianion with p-methylbenzyl bromide. Chromatography of the reaction mixture afforded the following derivatives in order of decreasing yields: 1,3,5,7-tetrakis-, 1,3-bis-, 1,3,5-tris-, 1,2,4-tris-, and mono(p-methylbenzyl)-p-tert-butylcalix[8]arene, besides

  通过使对叔丁基杯杯[8]芳烃三阴离子的四乙基铵盐与对甲基苄基溴反应，研究了烷基化条件下的杯[8]芳烃三芳基阴离子的行为。对反应混合物进行色谱分离，以递减的顺序提供以下衍生物：1,3,5,7-四-，1,3-双-，1,3,5-三-，1,2,4-三- ，以及单（对甲基苄基）-对叔丁基杯[8]芳烃，以及痕量的1,4-和1,5-二取代的化合物。使用对叔丁基苄基溴可获得可比较的结果。通过假设在每个烷基化步骤后，通过交换平衡将剩余的负电荷重新分布，可以解释观察到的区域选择性。在剩余的酚基上具有优先的位置，在那些位置上可以进行连续的H键稳定化，并使静电排斥最小。质子/去质子平衡的发生允许形成1,3,5,7-四取代的杯[8]芳烃。
• "Alternate Alkylation" of p-tert-Butylcalix[8]arene in the Presence of Weak Bases
  作者：Placido Neri、Corrada Geraci、Mario Piattelli

  DOI：10.1021/jo00118a033

  日期：1995.6

  Alkylation of p-tert-butylcalix[8]arene in the presence of weak bases has been investigated using p-methylbenzyl bromide as an electrophile and CsF as a weak base in THF/DMF. Initially, a sequence of monoalkylation steps on progressively more alkylated compounds has been carried out, leading to the isolation and characterization of 13 p-methylbenzyl ethers ranging from mono- to octasubstituted. Successively, the time course of the composition of the reaction mixture has been determined at regular time intervals by chromatographic analysis and products isolation, in order to have a semiquantitative dynamic picture of the whole process. The reaction path goes mainly through the formation of mono-, 1,3-di-, 1,3,5-tri-, 1,3,5,7-tetra-, 1,2,3,5,7-penta-, 1,2,3,4,5,7- and 1,2,3,5,6,7-hexa-, and heptasubstituted derivatives. This result agrees with an ''alternate alkylation'' mechanism based on the preferential formation of monoanions stabilized by two flanking hydrogen bonds. However, the isolation of appreciable amounts of 1,2,4-tris(p-methylbenzyl) ether indicates that less stable monoanions can also be formed, possibly due to either temporary conformational preferences or the conformational mobility of the calix[8]arene macrocycle, resulting in a less effective hydrogen-bonding stabilization of anionic intermediates.