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

• 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-49,50,51,52,53,54,55,56-octakis<(4-methylbenzyl)oxy>calix<8>arene
• 英文别名: 5,11,17,23,29,35,41,47-Octa-tert-butyl-49,50,51,52,53,54,55,56-octakis[(4-methylbenzyl)oxy]calix[8]arene；5,11,17,23,29,35,41,47-Octatert-butyl-49,50,51,52,53,54,55,56-octakis[(4-methylphenyl)methoxy]nonacyclo[43.3.1.13,7.19,13.115,19.121,25.127,31.133,37.139,43]hexapentaconta-1(48),3,5,7(56),9,11,13(55),15,17,19(54),21,23,25(53),27(52),28,30,33(51),34,36,39(50),40,42,45(49),46-tetracosaene
• 化学式: C₁₅₂H₁₇₆O₈
• 分子量: 2131.06
• InChiKey: XOPWAZYJQXKVQR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  43.4
• 重原子数：
  160
• 可旋转键数：
  32
• 环数：
  17.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  73.8
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  4-叔丁基杯[8]芳烃 、 4-甲基苄溴 在 sodium hydride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 70.0h， 以78%的产率得到5,11,17,23,29,35,41,47-Octa-tert-butyl-49,50,51,52,53,54,55,56-octakis<(4-methylbenzyl)oxy>calix<8>arene
  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

• "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.