5,17,29-tris(1,1-dimethylethyl)-37,39,41-trimethoxy-38,40,42-tris<(3-nitrobenzyl)oxy>calix<6>arene

• 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: 5,17,29-tris(1,1-dimethylethyl)-37,39,41-trimethoxy-38,40,42-tris<(3-nitrobenzyl)oxy>calix<6>arene
• 英文别名: 5,17,29-tris(1,1-dimethylethyl)-37,39,41-trimethoxy-38,40,42-tris[(3-nitrobenzyl)oxy]calix[6]arene；5,17,29-Tritert-butyl-38,40,42-trimethoxy-37,39,41-tris[(3-nitrophenyl)methoxy]heptacyclo[31.3.1.13,7.19,13.115,19.121,25.127,31]dotetraconta-1(37),3,5,7(42),9,11,13(41),15(40),16,18,21(39),22,24,27(38),28,30,33,35-octadecaene
• 化学式: C₇₈H₈₁N₃O₁₂
• 分子量: 1252.51
• InChiKey: MBMPGQUCEHEMIL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  20.3
• 重原子数：
  93
• 可旋转键数：
  15
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  193
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为产物：
  描述：

  1,3,5-trimethoxy-p-tert-butylcalix[6]arene 在 三氯化铝 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 18.17h， 生成 5,17,29-tris(1,1-dimethylethyl)-37,39,41-trimethoxy-38,40,42-tris<(3-nitrobenzyl)oxy>calix<6>arene
  参考文献：
  名称：

  Control of Calix[6]arene Conformations by Self-Inclusion of 1,3,5-Tri-O-alkyl Substituents: Synthesis and NMR Studies

  摘要：

  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.

  DOI：

  10.1021/ja00092a036

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.