37,39,41-tris<((N,N-diethylamino)carbonyl)methoxy>-5,11,17,23,29,35-hexakis(1,1-dimethylethyl)calix<6>arene-38,40,42-triol | 156746-98-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 37,39,41-tris<((N,N-diethylamino)carbonyl)methoxy>-5,11,17,23,29,35-hexakis(1,1-dimethylethyl)calix<6>arene-38,40,42-triol
• 英文别名: 37,39,41-tris[[(N,N-diethylamino)carbonyl]methoxy]-5,11,17,23,29,35-hexakis(1,1-dimethylethyl)calix[6]arene-38,40,42-triol
• CAS: 156746-98-4
• 化学式: C₈₄H₁₁₇N₃O₉
• 分子量: 1312.87
• InChiKey: MABGWOIACIRQIG-UHFFFAOYSA-N

物化性质

• 沸点：
  1128.1±65.0 °C(predicted)
• 密度：
  1.070±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  17.19
• 重原子数：
  96.0
• 可旋转键数：
  15.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  149.31
• 氢给体数：
  3.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  碘乙烷 、 37,39,41-tris<((N,N-diethylamino)carbonyl)methoxy>-5,11,17,23,29,35-hexakis(1,1-dimethylethyl)calix<6>arene-38,40,42-triol 在 sodium hydride 作用下， 生成 37,39,41-tris<((N,N-diethylamino)carbonyl)methoxy>-5,11,17,23,29,35-hexakis(1,1-dimethylethyl)-38,40,42-triethoxycalix<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
• 作为产物：
  描述：

  1,3,5-trimethoxy-2,4,6-tris(N,N-diethylacetamido)-p-tert-butylcalix<6>arene 在 碘代三甲硅烷 作用下， 以 氯仿 为溶剂， 反应 8.0h， 以83%的产率得到37,39,41-tris<((N,N-diethylamino)carbonyl)methoxy>-5,11,17,23,29,35-hexakis(1,1-dimethylethyl)calix<6>arene-38,40,42-triol
  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