4-[(E)-2-(2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzopentaoxacyclopentadecin-15-yl)-1-ethenyl]quinoline | 583854-93-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: 4-[(E)-2-(2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzopentaoxacyclopentadecin-15-yl)-1-ethenyl]quinoline
• 英文别名: 4-[(E)-2-(2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-pentaoxabenzocyclopentadecin-15-yl)ethen-1-yl]quinoline；4-[(E)-2-(2,5,8,11,14-pentaoxabicyclo[13.4.0]nonadeca-1(15),16,18-trien-17-yl)ethenyl]quinoline
• CAS: 583854-93-7
• 化学式: C₂₅H₂₇NO₅
• 分子量: 421.493
• InChiKey: FSYSXUMWAJGIHM-FNORWQNLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  31
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  59
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3H-2,1-苯并氧硫杂环戊烯 1,1-二氧化物 、 4-[(E)-2-(2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzopentaoxacyclopentadecin-15-yl)-1-ethenyl]quinoline 以99%的产率得到2-({4-[(E)-2-(2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzopentaoxacyclopentadecin-15-yl)-1-ethenyl]-1-quinoliniumyl}methyl)-1-benzenesulfonate
  参考文献：
  名称：

  Novel Photoswitchable Receptors:  Synthesis and Cation-Induced Self-Assembly into Dimeric Complexes Leading to Stereospecific [2+2]-Photocycloaddition of Styryl Dyes Containing a 15-Crown-5 Ether Unit

  摘要：

  Styryl dyes 4a-e containing a 15-crown-5 ether unit and a quinoline residue with a sulfonatoalkyl or sulfonatobenzyl N-substituent were synthesized. The relationship between the photochemical behavior of these dyes and their aggregates derived from complexation with Mg2+ in MeCN was studied using H-1 NMR and absorption spectroscopy. The E-isomers of 4a-e were shown to form highly stable dimeric (2:2) complexes with Mg2+. Upon irradiation with visible light, the dimeric complexes undergo two competing photoreactions, viz., geometric E --> Z isomerization, resulting in an anion-capped 1:1 complex of the Z-isomer with Mg2+ and stereospecific syn-head-to-tail [2+2]-cycloaddition, affording a single isomer of bis-crown-containing cyclobutane. The N-substituent in the dye has a dramatic effect on the photochemical behavior of the dimeric complex. Molecular dynamics and semiempirical quantum-chemical calculations were carried out to interpret the observed photocycloaddition in the dimer. Conformational equilibria for the dimer of (E)-4b were analyzed using H-1 NMR spectroscopy.

  DOI：

  10.1021/jo034460x
• 作为产物：
  描述：

  4-甲基喹啉 、 4-甲酰-15-冠-5 在 potassium tert-butylate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 以38%的产率得到4-[(E)-2-(2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzopentaoxacyclopentadecin-15-yl)-1-ethenyl]quinoline
  参考文献：
  名称：

  Synthesis and structures of azine-based crown-containing hetarylphenylethenes

  摘要：

  甲基取代的含一个或两个氮原子的六元杂芳香族化合物与苯并-15-冠醚衍生的醛在 DMF 和 ButOK 的存在下缩合，得到了含有 15-冠-5-的 hetarylphenylethenes。根据核磁共振光谱的结果，这些化合物在溶液（MeCN-d3）中以同构和反构的混合物形式存在。通过 X 射线衍射分析确定了两种化合物的结构。

  DOI：

  10.1007/s11172-006-0025-5

文献信息

• Synthesis and structures of azine-based crown-containing hetarylphenylethenes
  作者：E. N. Andryukhina、M. M. Mashura、O. A. Fedorova、L. G. Kuz'mina、J. A. K. Howard、S. P. Gromov

  DOI：10.1007/s11172-006-0025-5

  日期：2005.7

  Condensation of methyl-substituted six-membered heteroaromatics containing one or two nitrogen atoms with aldehyde derived from benzo-15-crown-5 ether in DMF in the presence of ButOK afforded 15-crown-5-containing hetarylphenylethenes. According to the results of NMR spectroscopy, these compounds exist as mixtures of syn and anti conformers in solution (MeCN-d3). The structures of two compounds were established by X-ray diffraction analysis.

  甲基取代的含一个或两个氮原子的六元杂芳香族化合物与苯并-15-冠醚衍生的醛在 DMF 和 ButOK 的存在下缩合，得到了含有 15-冠-5-的 hetarylphenylethenes。根据核磁共振光谱的结果，这些化合物在溶液（MeCN-d3）中以同构和反构的混合物形式存在。通过 X 射线衍射分析确定了两种化合物的结构。
• Novel Photoswitchable Receptors:  Synthesis and Cation-Induced Self-Assembly into Dimeric Complexes Leading to Stereospecific [2+2]-Photocycloaddition of Styryl Dyes Containing a 15-Crown-5 Ether Unit
  作者：Sergey P. Gromov、Evgeny N. Ushakov、Olga A. Fedorova、Igor I. Baskin、Alexei V. Buevich、Elena N. Andryukhina、Michael V. Alfimov、Dan Johnels、Ulf G. Edlund、James K. Whitesell、Marye Anne Fox

  DOI：10.1021/jo034460x

  日期：2003.8.1

  Styryl dyes 4a-e containing a 15-crown-5 ether unit and a quinoline residue with a sulfonatoalkyl or sulfonatobenzyl N-substituent were synthesized. The relationship between the photochemical behavior of these dyes and their aggregates derived from complexation with Mg2+ in MeCN was studied using H-1 NMR and absorption spectroscopy. The E-isomers of 4a-e were shown to form highly stable dimeric (2:2) complexes with Mg2+. Upon irradiation with visible light, the dimeric complexes undergo two competing photoreactions, viz., geometric E --> Z isomerization, resulting in an anion-capped 1:1 complex of the Z-isomer with Mg2+ and stereospecific syn-head-to-tail [2+2]-cycloaddition, affording a single isomer of bis-crown-containing cyclobutane. The N-substituent in the dye has a dramatic effect on the photochemical behavior of the dimeric complex. Molecular dynamics and semiempirical quantum-chemical calculations were carried out to interpret the observed photocycloaddition in the dimer. Conformational equilibria for the dimer of (E)-4b were analyzed using H-1 NMR spectroscopy.