[10](1,8)pyrenophane | 1351958-56-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 芘
• 英文名称: [10](1,8)pyrenophane
• 英文别名: Pentacyclo[16.6.2.04,23.07,22.019,24]hexacosa-1(24),2,4(23),5,7(22),18,20,25-octaene
• CAS: 1351958-56-9
• 化学式: C₂₆H₂₈
• 分子量: 340.508
• InChiKey: YTECJXSNTVEWMX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.7
• 重原子数：
  26
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  2,4-二甲基溴苯 在 bis-triphenylphosphine-palladium(II) chloride 、 potassium permanganate 、 copper(l) iodide 、 lithium aluminium tetrahydride 、 硫酸 、 palladium 10% on activated carbon 、 Na₂S/Al₂O₃ 、 氢气 、 三溴化磷 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 119.0h， 生成 [10](1,6)pyrenophane 、 [10](1,8)pyrenophane
  参考文献：
  名称：

  Synthesis, Crystal Structure, and Resolution of [10](1,6)Pyrenophane: An Inherently Chiral [n]Cyclophane

  摘要：

  A synthetic approach to a set of three inherently chiral [n] cyclophanes, [n] (1,6)pyrenophanes (29a-c, n = 8-10) was investigated. Progress toward 29a was thwarted by the failure of the key dithiacyclophane-forming reaction. For the next higher homologue, the synthesis was completed, but the desired [9](1,6)pyrenophane (29b) could only be partially separated from an isomeric pyrenophane, [9](1,8)pyrenophane (28b), and an unidentified byproduct. Work aimed at the synthesis of the next higher homologue resulted in the isolation of a 7:4 mixture of [10](1,8)pyrenophane (28c) and [10](1,6)pyrenophane (29c), which could not be separated by column chromatography or crystallization. However, single-crystal X-ray structures of 28c and 29c were obtained after manual separation of two crystals with different morphologies from the same batch of crystals obtained from the 7:4 mixture of 28c and 29c. The pyrene system of 29c was found to have a gentle end-to-end bend as well as a significant longitudinal twist. Short intermolecular C(sp(3))-H center dot center dot center dot pi contacts (2.64 to 2.76 angstrom) between H-atoms on the bridge and the centroids of three of the four six-membered rings of the pyrene system of a neighboring pyrenophane of like chirality give rise to the formation of single enantiomer columns. From a DNMR study of the mixture of 28c and 29c, the bridge in [10](1,8)pyrenophane (28c) was found to undergo a conformational flip from one side of the pyrene system to the other with Delta G double dagger = 14.9 +/- 0.2 kcal/mol. A two-stage preparative HPLC protocol was subsequently developed for the separation of 28c and 29c (Chiralpalc AD-H column) and then the enantiomers of 29c (Chiralcel OJ-H column). This enabled the measurement of their optical rotations and CD spectra.

  DOI：

  10.1021/jo201013q

文献信息

• Synthesis, Crystal Structure, and Resolution of [10](1,6)Pyrenophane: An Inherently Chiral [<i>n</i>]Cyclophane
  作者：Yixi Yang、Michael R. Mannion、Louise N. Dawe、Christina M. Kraml、Robert A. Pascal、Graham J. Bodwell

  DOI：10.1021/jo201013q

  日期：2012.1.6

  A synthetic approach to a set of three inherently chiral [n] cyclophanes, [n] (1,6)pyrenophanes (29a-c, n = 8-10) was investigated. Progress toward 29a was thwarted by the failure of the key dithiacyclophane-forming reaction. For the next higher homologue, the synthesis was completed, but the desired [9](1,6)pyrenophane (29b) could only be partially separated from an isomeric pyrenophane, [9](1,8)pyrenophane (28b), and an unidentified byproduct. Work aimed at the synthesis of the next higher homologue resulted in the isolation of a 7:4 mixture of [10](1,8)pyrenophane (28c) and [10](1,6)pyrenophane (29c), which could not be separated by column chromatography or crystallization. However, single-crystal X-ray structures of 28c and 29c were obtained after manual separation of two crystals with different morphologies from the same batch of crystals obtained from the 7:4 mixture of 28c and 29c. The pyrene system of 29c was found to have a gentle end-to-end bend as well as a significant longitudinal twist. Short intermolecular C(sp(3))-H center dot center dot center dot pi contacts (2.64 to 2.76 angstrom) between H-atoms on the bridge and the centroids of three of the four six-membered rings of the pyrene system of a neighboring pyrenophane of like chirality give rise to the formation of single enantiomer columns. From a DNMR study of the mixture of 28c and 29c, the bridge in [10](1,8)pyrenophane (28c) was found to undergo a conformational flip from one side of the pyrene system to the other with Delta G double dagger = 14.9 +/- 0.2 kcal/mol. A two-stage preparative HPLC protocol was subsequently developed for the separation of 28c and 29c (Chiralpalc AD-H column) and then the enantiomers of 29c (Chiralcel OJ-H column). This enabled the measurement of their optical rotations and CD spectra.