5,35-Dibromo-9,14,19,24,26,28,30,32-octamethoxyhexacyclo[21.2.2.23,6.28,11.213,16.218,21]pentatriaconta-1(26),3,5,8,10,13,15,18(29),19,21(28),23(27),24,30,32,34-pentadecaene-4,34-diol | 1616090-12-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 5,35-Dibromo-9,14,19,24,26,28,30,32-octamethoxyhexacyclo[21.2.2.23,6.28,11.213,16.218,21]pentatriaconta-1(26),3,5,8,10,13,15,18(29),19,21(28),23(27),24,30,32,34-pentadecaene-4,34-diol
• 英文别名: 5,35-dibromo-9,14,19,24,26,28,30,32-octamethoxyhexacyclo[21.2.2.23,6.28,11.213,16.218,21]pentatriaconta-1(26),3,5,8,10,13,15,18(29),19,21(28),23(27),24,30,32,34-pentadecaene-4,34-diol
• CAS: 1616090-12-0
• 化学式: C₄₃H₄₄Br₂O₁₀
• 分子量: 880.624
• InChiKey: MLYQHLHMSBPFKP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10
• 重原子数：
  55
• 可旋转键数：
  8
• 环数：
  15.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  114
• 氢给体数：
  2
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  5,35-Dibromo-9,14,19,24,26,28,30,32-octamethoxyhexacyclo[21.2.2.23,6.28,11.213,16.218,21]pentatriaconta-1(26),3,5,8,10,13,15,18(29),19,21(28),23(27),24,30,32,34-pentadecaene-4,34-diol 在 哌嗪 、 四(三苯基膦)钯 、 1,3-二甲基巴比妥酸 、 氧气 、 potassium carbonate 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 丙酮 为溶剂， 120.0 ℃ 、400.01 kPa 条件下， 反应 32.0h， 生成 4-(30-Amino-29-hydroxy-4,9,14,19,31,33,35,37-octamethoxy-25-oxa-27-azaheptacyclo[21.5.2.23,6.28,11.213,16.218,21.024,28]octatriaconta-1(29),3,5,8,10,13(34),14,16(33),18(32),19,21(31),23(30),24(28),26,35,37-hexadecaen-26-yl)benzaldehyde
  参考文献：
  名称：

  Amino-Functionalized Pillar[5]arene

  摘要：

  AbstractThe recently introduced pillar[n]arenes have provided chemists with receptors that, when incorporated into materials, confer unique properties upon them. The symmetrical rims and cylindrical shape of pillar[5]arene begs the question—can these pillar‐like receptors be linked covalently end‐to‐end in order to create tubular structures by a growth‐from‐template approach? In our efforts to produce these one‐dimensional extended structures, we have developed a new method of functionalizing pillar[5]arene in which one of the five hydroquinone units is converted into a diaminobenzoquinone analogue. The resulting diaminopillar[5]arene derivative, which undergoes a stereochemical inversion process that is slow on the 1H NMR timescale, can be chemically modified yet further in a direction that is orthogonal to the plane of its methylene bridging carbons through the formation of oxazole heterocycles. This strategy has been employed to create rigid oligomers that resemble one‐dimensional tubular arrays. As a proof‐of‐principle, a rigid pillar[5]arene dimer has been isolated and characterized in the solution state as a 1:1 complex with an extended viologen for which it acts as a receptor.

  DOI：

  10.1002/chem.201403235
• 作为产物：
  描述：

  pillar[4]arene[1]quinone 在 溴 、 溶剂黄146 、 锌 作用下， 以 丙酮 为溶剂， 生成 5,35-Dibromo-9,14,19,24,26,28,30,32-octamethoxyhexacyclo[21.2.2.23,6.28,11.213,16.218,21]pentatriaconta-1(26),3,5,8,10,13,15,18(29),19,21(28),23(27),24,30,32,34-pentadecaene-4,34-diol
  参考文献：
  名称：

  Amino-Functionalized Pillar[5]arene

  摘要：

  AbstractThe recently introduced pillar[n]arenes have provided chemists with receptors that, when incorporated into materials, confer unique properties upon them. The symmetrical rims and cylindrical shape of pillar[5]arene begs the question—can these pillar‐like receptors be linked covalently end‐to‐end in order to create tubular structures by a growth‐from‐template approach? In our efforts to produce these one‐dimensional extended structures, we have developed a new method of functionalizing pillar[5]arene in which one of the five hydroquinone units is converted into a diaminobenzoquinone analogue. The resulting diaminopillar[5]arene derivative, which undergoes a stereochemical inversion process that is slow on the 1H NMR timescale, can be chemically modified yet further in a direction that is orthogonal to the plane of its methylene bridging carbons through the formation of oxazole heterocycles. This strategy has been employed to create rigid oligomers that resemble one‐dimensional tubular arrays. As a proof‐of‐principle, a rigid pillar[5]arene dimer has been isolated and characterized in the solution state as a 1:1 complex with an extended viologen for which it acts as a receptor.

  DOI：

  10.1002/chem.201403235

文献信息

• Stereochemical inversion in difunctionalised pillar[5]arenes
  作者：Nathan L. Strutt、Severin T. Schneebeli、J. Fraser Stoddart

  DOI：10.1080/10610278.2013.822973

  日期：2013.9.18

  Pillar[5]arenes constitute a class of macrocycles which display planar chirality on account of the methylene bridges that link five disubstituted para-phenylene rings together. Dynamic H-1 NMR spectroscopy indicates that A1/A2-dihydroxypillar[5]arene undergoes conformational inversion between its enantiomers with an energy barrier of 11.9kcalmol(-1). This process involving an oxygen-through-the-annulus rotation by all five hydroquinone rings is associated with the breaking of two intramolecular hydrogen bonds between phenolic hydroxyl and methoxyl groups on neighbouring phenylene rings. A combination of molecular mechanics and quantum mechanical calculations reveals that the conformational inversion undergone by A1/A2-dihyroxypillar[5]arene involves the breaking of one of these hydrogen bonds in the rate-limiting step of the process. Not only does the calculated energy of activation (13.8kcalmol(-1)) using density functional theory agree well with the experimentally determined value (13.0 kcal mol(-1)), it also leads to the identification of the lowest energy pseudorotational pathway involving four intermediates and five transition states. While replacing the two hydroxyl groups in A1/A2-dihydroxypillar[5]arene with carbonyl groups leads to much more rapid conformational inversion, placing bromine atoms ortho to the two phenolic hydroxyl groups increases the strength of the intramolecular hydrogen bonds, raising the energy barrier to inversion by 3.9kcalmol(-1).
• Amino-Functionalized Pillar[5]arene
  作者：Nathan L. Strutt、Huacheng Zhang、Severin T. Schneebeli、J. Fraser Stoddart

  DOI：10.1002/chem.201403235

  日期：2014.8.25

  AbstractThe recently introduced pillar[n]arenes have provided chemists with receptors that, when incorporated into materials, confer unique properties upon them. The symmetrical rims and cylindrical shape of pillar[5]arene begs the question—can these pillar‐like receptors be linked covalently end‐to‐end in order to create tubular structures by a growth‐from‐template approach? In our efforts to produce these one‐dimensional extended structures, we have developed a new method of functionalizing pillar[5]arene in which one of the five hydroquinone units is converted into a diaminobenzoquinone analogue. The resulting diaminopillar[5]arene derivative, which undergoes a stereochemical inversion process that is slow on the 1H NMR timescale, can be chemically modified yet further in a direction that is orthogonal to the plane of its methylene bridging carbons through the formation of oxazole heterocycles. This strategy has been employed to create rigid oligomers that resemble one‐dimensional tubular arrays. As a proof‐of‐principle, a rigid pillar[5]arene dimer has been isolated and characterized in the solution state as a 1:1 complex with an extended viologen for which it acts as a receptor.