7,16-diacetoxy-(6α,8α,15α,17α)-6,8,15,17-tetrahydro-6,17:8,15-dimethanoheptacene | 288625-16-1

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 7,16-diacetoxy-(6α,8α,15α,17α)-6,8,15,17-tetrahydro-6,17:8,15-dimethanoheptacene
• 英文别名: [(1S,5R,16S,20R)-18-acetyloxy-3-nonacyclo[18.10.1.15,16.02,19.04,17.06,15.08,13.021,30.023,28]dotriaconta-2,4(17),6,8,10,12,14,18,21,23,25,27,29-tridecaenyl] acetate
• CAS: 288625-16-1
• 化学式: C₃₆H₂₆O₄
• 分子量: 522.6
• InChiKey: AMGJFAOXCREKOE-LPOKLPNDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.6
• 重原子数：
  40
• 可旋转键数：
  4
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  7,16-diacetoxy-(6α,8α,15α,17α)-6,8,15,17-tetrahydro-6,17:8,15-dimethanoheptacene 在 sodium hydroxide 、 三乙胺 、 苯肼 作用下， 以 乙醇 、 氯仿 为溶剂， 反应 1.5h， 生成 7,16-bis-trifluormethylsulfonoxy-(6α,8α,15α,17α)-6,8,15,17-tetrahydro-6,17:8,15-dimethanoheptacene
  参考文献：
  名称：

  Synthesis and supramolecular structures of molecular clips

  摘要：

  The syntheses of the novel dimethylene-bridged clips 4a-e and 5b are reported. They selectively bind electron-deficient neutral and cationic aromatic substrates comparable to the tetramethylene-bridged tweezers 1 and 2. The geometry of the noncovalently bound complexes with 4b-d as receptors derived from the single-crystal structure analyses is, however, different from that of the complexes with 2 as receptor. In clip complexes the plane of the included aromatic substrate molecule is orientated almost parallel to the naphthalene sidewalls of the clip, whereas in the tweezer complex the substrate is orientated parallel to the central arene spacer-unit. TCNB 19 as substrate is placed inside the cavity of the hydroquinone clip 4c in solution as well as in the cocrystal. In contrast it was found for the cocrystal with the diacetate clip 4b that the TCNB 19, is placed between the naphthalene side-wall of two different clip molecules whereas in solution 19 is included into the cavity of 4b. Finally, 19 forms a (1:2) complex with dinaphthonorbornadiene 20 in solution as well as in the crystalline state. The findings reported here are instructive for the understanding of the weak; noncovalent binding forces particularly the arene-arene interaction. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)00230-7
• 作为产物：
  描述：

  四溴对烯 、 9,10-Diacetoxy-1,4,5,8-tetrahydro-1,4:5,8-dimethanoanthracene 在 calcium carbonate 、 sodium iodide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 5.5h， 以83%的产率得到7,16-diacetoxy-(6α,8α,15α,17α)-6,8,15,17-tetrahydro-6,17:8,15-dimethanoheptacene
  参考文献：
  名称：

  Synthesis and supramolecular structures of molecular clips

  摘要：

  The syntheses of the novel dimethylene-bridged clips 4a-e and 5b are reported. They selectively bind electron-deficient neutral and cationic aromatic substrates comparable to the tetramethylene-bridged tweezers 1 and 2. The geometry of the noncovalently bound complexes with 4b-d as receptors derived from the single-crystal structure analyses is, however, different from that of the complexes with 2 as receptor. In clip complexes the plane of the included aromatic substrate molecule is orientated almost parallel to the naphthalene sidewalls of the clip, whereas in the tweezer complex the substrate is orientated parallel to the central arene spacer-unit. TCNB 19 as substrate is placed inside the cavity of the hydroquinone clip 4c in solution as well as in the cocrystal. In contrast it was found for the cocrystal with the diacetate clip 4b that the TCNB 19, is placed between the naphthalene side-wall of two different clip molecules whereas in solution 19 is included into the cavity of 4b. Finally, 19 forms a (1:2) complex with dinaphthonorbornadiene 20 in solution as well as in the crystalline state. The findings reported here are instructive for the understanding of the weak; noncovalent binding forces particularly the arene-arene interaction. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)00230-7

文献信息

• Effect of Substituents on the Complexation of Aromatic and Quinoid Substrates with Molecular Tweezers and Clips
  作者：Frank-Gerrit Klärner、Jolanta Polkowska、Jens Panitzky、Uta P. Seelbach、Ulrich Burkert、Markus Kamieth、Michael Baumann、Arne E. Wigger、Roland Boese、Dieter Bläser

  DOI：10.1002/ejoc.200300704

  日期：2004.4

  and ΔG) of complex formation between the new receptors and aromatic substrates such as DCNB 21, TCNB 22, TCNQ 24 and Kosower salt 25 and the maximum complexation-induced 1H NMR shifts (Δδmax.) were determined by 1H NMR titration experiments. It was found that the presence of substituents OH, OAc and OCONHPh in the central spacer units of the tweezers and clips 1−3 favours complex formation, whereas that

  在中心间隔单元中被 OAc、OH、OCONHPh、OMe、OCH2COOR 和 OCH2CONHR 基团取代的 1-3 型分子镊子和夹子已通过标准方法通过修饰合成，已知的双乙酰氧基取代衍生物 1b、2b 和3b，或相应取代的双亲二烯体 4b 和 5b。二甲氧基-双乙酰氧基取代的镊子 1d 的合成可以通过压力诱导的双亲二烯体 4b 和新制备的二烯 6b 之间的重复 Diels-Alder 反应以及随后的 DDQ 氧化来完成。新受体与芳香族底物如 DCNB 21、TCNB 22、TCNQ 24 和 Kosower salt 25 之间形成复合物的热力学参数（Ka 和 ΔG）以及最大络合诱导的 1H NMR 位移（Δδmax.）由 1H NMR 确定滴定实验。发现在镊子和夹子 1-3 的中央间隔单元中存在取代基 OH、OAc 和 OCONHPh 有利于复合物的形成，而取代基 OMe、OCH2COOR