5,11,17,23,29,35-hexa-tert-butyl-37,39,41-trimethoxy-38,40,42-tris(tert-butoxycarbonylmethoxy)calix<6>arene | 150652-76-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 5,11,17,23,29,35-hexa-tert-butyl-37,39,41-trimethoxy-38,40,42-tris(tert-butoxycarbonylmethoxy)calix<6>arene
• 英文别名: 5,11,17,23,29,35-hexakis(1,1-dimethylethyl)-37,39,41-tris<(((1,1-dimethylethyl)oxy)carbonyl)methoxy>-38,40,42-trimethoxycalix<6>arene；Tert-butyl 2-[[5,11,17,23,29,35-hexatert-butyl-38,40,42-trimethoxy-39,41-bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethoxy]-37-heptacyclo[31.3.1.13,7.19,13.115,19.121,25.127,31]dotetraconta-1(36),3,5,7(42),9,11,13(41),15,17,19(40),21(39),22,24,27(38),28,30,33(37),34-octadecaenyl]oxy]acetate
• CAS: 150652-76-9
• 化学式: C₈₇H₁₂₀O₁₂
• 分子量: 1357.9
• InChiKey: YWSNXEULQNTJAA-UHFFFAOYSA-N

物化性质

• 沸点：
  1095.0±65.0 °C(Predicted)
• 密度：
  1.044±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  24.1
• 重原子数：
  99
• 可旋转键数：
  24
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  134
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  5,11,17,23,29,35-hexa-tert-butyl-37,39,41-trimethoxy-38,40,42-tris(tert-butoxycarbonylmethoxy)calix<6>arene 在 三氟乙酸 作用下， 以60%的产率得到37,39,41-tris(carboxylmethoxy)-5,11,17,23,29,35-hexakis(1,1-dimethylethyl)-38,40,42-trimethoxycalix<6>arene
  参考文献：
  名称：

  Conformational freezing of p-tert-butylcalix[6]arene in the cone structure by selective functionalization at the lower rim: synthesis of new preorganized ligands

  摘要：

  首次实现了对对叔丁基杯[6]芳烃1的选择性和对称性1,3,5-甲基化；随后在三甲氧基对叔丁基杯[6]芳烃2上引入酯基和酰胺结合基团，将杯状结构固定在锥形构象中，从而获得新的预组织阳离子配体。

  DOI：

  10.1039/c39910001413
• 作为产物：
  描述：

  溴乙酸叔丁酯 、 1,3,5-trimethoxy-p-tert-butylcalix[6]arene 在 sodium hydride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 以80%的产率得到5,11,17,23,29,35-hexa-tert-butyl-37,39,41-trimethoxy-38,40,42-tris(tert-butoxycarbonylmethoxy)calix<6>arene
  参考文献：
  名称：

  Conformational freezing of p-tert-butylcalix[6]arene in the cone structure by selective functionalization at the lower rim: synthesis of new preorganized ligands

  摘要：

  首次实现了对对叔丁基杯[6]芳烃1的选择性和对称性1,3,5-甲基化；随后在三甲氧基对叔丁基杯[6]芳烃2上引入酯基和酰胺结合基团，将杯状结构固定在锥形构象中，从而获得新的预组织阳离子配体。

  DOI：

  10.1039/c39910001413

文献信息

• Control of Calix[6]arene Conformations by Self-Inclusion of 1,3,5-Tri-O-alkyl Substituents: Synthesis and NMR Studies
  作者：John P. M. van Duynhoven、Rob G. Janssen、Willem Verboom、Sybille M. Franken、Alessandro Casnati、Andrea Pochini、Rocco Ungaro、Javier de Mendoza、Pedro M. Nieto

  DOI：10.1021/ja00092a036

  日期：1994.6

  Hexa-O-alkylated p-tert-butylcalix[6]arenes with an alternate 1,3,5-R(1)-2,4,6-R(2)-substitution pattern have been prepared and studied by NMR spectroscopy. When R(1) = CH3 and R(2) is a bulky substituent, the calix[6]arene moiety adopts predominantly a flattened cone conformation. At room temperature this conformation slowly interconverts with a 1,2,3-alternate conformation (Delta G(double dagger) = 70-88 kJ mol(-1), T = 328 K, CDCl3). The Gibbs free energy between these two conformations at T = 303 K in CDCl3 varies from 2 to 7 kJ mol(-1). From quantitative NOE data (obtained for 1,3,5-trimethoxy-2,4,6-tris[(3-nitrobenzyl)oxyl-p-tert-butylcalix[6]arene (10) three-dimensional structures of the flattened cone and the 1,2,3-alternate conformers were calculated. In both conformers the methoxy groups are accommodated in the annulus of the calix [6] arene skeleton, indicating specific interactions with the aromatic calixarene moiety. Compared to the hexasubstituted analogues, this structural feature slightly increases the activation Gibbs free energy for the interconversion process (13-21 kJ mol(-1)). Even with substituents that are too large to rotate through the annulus, there is still slow interconversion (Delta G(double dagger) = 88 kJ mol(-1), T = 328 K, CDCl3). This is attributed to a very slow transannular motion of the p-tert-butyl moiety. Also the ethoxy (16) or propoxy (17) derivatives of 2,4,6-tris(N,N-diethylacetamido)-p-tert-butylcalix[6]arene predominantly adopt flattened cone (16) and 1,2,3-alternate (17) conformations, respectively. The self-inclusion of the larger alkyl groups also contributes to the overall conformational freezing of the p-tert-butylcalix[6]arenes.