4-(1,4,7,10,13-pentaoxa-16-azacyclooctadecan-16-yl)benzaldehyde | 73171-36-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-(1,4,7,10,13-pentaoxa-16-azacyclooctadecan-16-yl)benzaldehyde
• 英文别名: 4'-formylphenylaza-18-crown-6-ether；4-(1,4,7,10,13-Pentaoxa-16-aza-cyclooctadec-16-yl)-benzaldehyde；4-(1,4,7,10,13-pentaoxa-16-azacyclooctadec-16-yl)benzaldehyde
• CAS: 73171-36-5
• 化学式: C₁₉H₂₉NO₆
• 分子量: 367.442
• InChiKey: VJICSPXLCFGHJX-UHFFFAOYSA-N

物化性质

• 熔点：
  43-45 °C
• 沸点：
  561.7±50.0 °C(Predicted)
• 密度：
  1.076±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  66.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  4-(1,4,7,10,13-pentaoxa-16-azacyclooctadecan-16-yl)benzaldehyde 在 ammonium acetate 、 三氟乙酸 、 三氯氧磷 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 150.75h， 生成
  参考文献：
  名称：

  Designing an Intracellular Fluorescent Probe for Glutathione: Two Modulation Sites for Selective Signal Transduction

  摘要：

  A selective probe for glutathione was designed and synthesized. The design incorporates spatial and photophysical constraints for the maximal emission signal. Thus, pHs, as well as the intracellular thiol concentrations, determine the emission signal intensity through a tight control of charge-transfer and PeT processes. The probe works satisfactorily inside the human breast adenocarcinoma cells, highlighting GSH distribution in the cytosol.

  DOI：

  10.1021/ol501272z
• 作为产物：
  描述：

  N,N-二羟乙基苯胺 在 sodium hydroxide 、 三氯氧磷 作用下， 以 1,4-二氧六环 为溶剂， 反应 30.67h， 生成 4-(1,4,7,10,13-pentaoxa-16-azacyclooctadecan-16-yl)benzaldehyde
  参考文献：
  名称：

  Dix, Johannes Peter; Voegtle, Fritz, Chemische Berichte, 1980, vol. 113, # 2, p. 457 - 470

  摘要：

  DOI：

文献信息

• Aggregation induced emission in the rotatable molecules: the essential role of molecular interaction
  作者：Zhipeng Yu、Yaya Duan、Longhuai Cheng、Zhili Han、Zheng Zheng、Hongping Zhou、Jieying Wu、Yupeng Tian

  DOI：10.1039/c2jm32405a

  日期：——

  Aggregation-induced emission (AIE) compounds, dye2 and dye3, with a rotatable N–N single bond and aza-crown-ether, have been synthesized. The fluorescence intensities of both dyes are very weak in THF, while become extraordinarily strong in a mixture of H2O–THF (v/v 95%). They are increased by 88.9 and 70.7 times, respectively, indicating enhanced blue-green fluorescence emissions. The λem of these two compounds in different states has been well studied. Besides this, dye1 and dye2 were characterized by single crystal X-ray structural determination. The results show that molecular interactions are formed in the particles, which considerably restrict the intramolecular vibration and rotation.

  具有可旋转N–N单键和氮杂皇冠醚的聚集诱导发光化合物染料2和染料3已被合成。这两种染料在THF中的荧光强度非常弱，而在H2O–THF混合溶液（体积比95%）中变得异常强烈，分别增强了88.9倍和70.7倍，显示出增强的蓝绿色荧光发射。这两种化合物在不同状态下的发射波长已得到充分研究。此外，染料1和染料2通过单晶X射线结构测定进行了表征。结果表明，颗粒中形成了分子间相互作用，大大限制了分子内的振动和旋转。
• Self-assembly involving hydrogen bonds. Spectral properties and structure of supramolecular complexes of bis-aza-18-crown-6-containing dienones with alkanediammonium salts
  作者：Marina V. Fomina、Nikolai A. Kurchavov、Alexandra Ya. Freidzon、Vyacheslav N. Nuriev、Artem I. Vedernikov、Yuri A. Strelenko、Sergey P. Gromov

  DOI：10.1016/j.jphotochem.2020.112801

  日期：2020.11

  Dienones (ketocyanine dyes) containing two aza-18-crown-6 ether residues were synthesized. The complex formation of these dyes with the EtNH3+ and +H3N(CH2)nNH3+ ions (n = 2–10, 12) in MeCN was studied by electronic and 1H NMR spectroscopy, including spectrophotometric and 1H NMR titration. It was found that homoditopic bis-azacrown dienones and alkanediammonium ions with a short polymethylene chain

  合成了包含两个aza-18-crown-6醚残基的二烯酮（酮菁染料）。 通过电子和1 H NMR光谱研究了这些染料与EtNH 3 +和+ H 3 N（CH 2）n NH 3 +离子（n = 2-10，12）的复合形成，包括分光光度法和11 H NMR滴定。发现同位双双氮杂双烯酮和具有短多亚甲基链的烷二铵离子形成1：1、2：2和1：2配合物，而具有长多亚甲基链的烷二铵离子仅形成伪环1：1配合物。确定了所得复合物的稳定性常数（log K 1：1在2.74至5.62 [M –1 ]范围内变化，log K 2：2  = 2.1 [M –1 ]，log K 1：2在范围从2.03到2.96 [M –1 ]）。由于两个NH 3 +的同时结合，最稳定的络合物是由具有长聚亚甲基链的二铵离子形成的基团连接到染料的氮杂皇冠醚残基。超分子配合物的结构通过量子化学计算得到证实。
• Buffering Heavy Metal Ions with Photoactive CrownCast Cages
  作者：Hannah W. Mbatia、Daniel P. Kennedy、Casey E. Camire、Christopher D. Incarvito、Shawn C. Burdette

  DOI：10.1002/ejic.201000673

  日期：2010.11

  photoactive group act as cages for divalent metal ions. The uncaging mechanism of these complexes involves a photoreaction that converts the nitrobenzhydrol, which is para to the aniline nitrogen atom, into the corresponding nitrosobenzophenone. Resonance delocalization of the aniline into the distal carbonyl group of the photoproduct attenuates the ability of the nitrogen atom to interact with the

  历史上，笼状化合物已被用于通过光来研究有机分子的生物活性。然而，R. Tsien 和其他人在过去的三年中开发了使用硝基苄基衍生的笼状复合物来研究 Ca 2+ 信号行为的方法。一系列与 4,5-二甲氧基-2-硝基苄基 (DMNB) 光活性基团整合的阳离子选择性 N-苯基-氮杂大环受体充当二价金属离子的笼子。这些复合物的解笼锁机制涉及将位于苯胺氮原子对位的硝基苯甲醇转化为相应的亚硝基二苯甲酮的光反应。苯胺共振离域进入光产物的远端羰基削弱了氮原子与客体相互作用的能力。CrownCast-1 (3) 利用 13-苯基-1，4,7,10-tetraoxa-13-azacyclopentadecane (A15C5, 2) 受体。CrownCast-1 的结合研究揭示了对 Ca 2+ 的适度选择性；然而，光解时测得的结合亲和力的差异表明 CrownCast-1 更适合笼养 Mg 2+ 。CrownCast-2
• Design of crystal packings of styrylheterocycles and [2+2] photocycloaddition reactions in their single crystals 6. Synthesis and crystal packings of neutral crown-containing and model styrylheterocycles
  作者：L. G. Kuz’mina、A. I. Vedernikov、N. A. Lobova、S. K. Sazonov、S. S. Basok、J. A. K. Howard、S. P. Gromov

  DOI：10.1007/s11172-009-0155-7

  日期：2009.6

  Neutral crown-containing and model styrylheterocycles of the 4-pyridine, 4-quinoline, and 9-acridine series were synthesized under acidic catalysis. The influence of the molecular geometry of these compounds, as well as of related styrylheterocycles of the 2-benzothiazole and benzobisthiazole series, on the formation of a particular crystal packing was investigated based on X-ray diffraction data. An extension of the conjugation system in the molecules can result in the sandwich-herringbone packing motif as the only one of the three packing motifs most typical of this class of compounds. This packing provides the preorganization of the structural units for the [2+2] photocycloaddition reaction. The styrylheterocycle containing the bulky 9-acridine moiety is nonplanar due to strong intramolecular steric interactions. The packing motifs formed by nonplanar molecules do not provide the preorganization of the molecules for the [2+2] photocycloaddition. The introduction of the crown ether moiety into the benzene ring of the styrylheterocycle can decrease the predictability of the packing motif as a result of the inclusion of solvent molecules capable of hydrogen bonding with the heteroatoms of the macrocycle in the crystal structure.

  合成了中性含冠和模型的4-吡啶、4-喹啉和9-咔唑系列的苯乙烯杂环化合物，采用酸催化。基于X射线衍射数据，研究了这些化合物以及相关的2-苯并噻唑和苯并双噻唑系列的苯乙烯杂环的分子几何形状对特定晶体堆积的影响。分子中共轭系统的扩展可能导致三种最典型堆积形式中的唯一一种——夹心鱼骨堆积。这种堆积为[2+2]光环加成反应的结构单元提供了预组织。由于强烈的分子内立体相互作用，含有笨重的9-咔唑单元的苯乙烯杂环呈非平面形态。非平面分子形成的堆积形式不提供分子在[2+2]光环加成反应中的预组织。将冠醚单元引入苯乙烯杂环的苯环中，可能会因能够与宏环的杂原子形成氢键的溶剂分子的参与而降低堆积形式的可预测性。
• Supramolecular Dimerization and [2 + 2] Photocycloaddition Reactions of Crown Ether Styryl Dyes Containing a Tethered Ammonium Group: Structure–Property Relationships
  作者：Evgeny N. Ushakov、Artem I. Vedernikov、Natalia A. Lobova、Svetlana N. Dmitrieva、Lyudmila G. Kuz’mina、Anna A. Moiseeva、Judith A. K. Howard、Michael V. Alfimov、Sergey P. Gromov

  DOI：10.1021/acs.jpca.5b10758

  日期：2015.12.31

  Variable structural parameters for the styryl dyes were the size and structure of macrocyclic moiety, the nature of heteroaromatic residue, and the length of the ammonioalkyl group attached to this residue. Quantum chemical calculations of the pseudocyclic dimers were performed in order to interpret the relationships between the structure of the ammonium dyes and the efficiency of the supramolecular

  分子自组装是控制烯烃的[2 + 2]光环加成反应的有效策略。事实证明，超分子组装体的几何性质对固态和溶液中这种光反应的效率和选择性都具有至关重要的作用，但其他因素的作用仍然知之甚少。研究结构-性质关系的便利的超分子系统是由含有冠醚部分和一个远端铵基的苯乙烯基染料自发形成的假环二聚体。合成了这种新型染料，以研究结构和电子因素对溶液中超分子二聚和[2 + 2]光环加成定量特征的影响。苯乙烯基染料的可变结构参数是大环部分的大小和结构，杂芳族残基的性质以及与该残基连接的氨烷基的长度。为了解释铵染料的结构与超分子光反应效率之间的关系，进行了伪环二聚体的量子化学计算。一种二聚配合物以结晶状态获得并通过X射线衍射研究。所得结果表明，取决于苯环上取代基的供电子能力以及拟环的构象柔韧性，在苯乙烯基部分的电子结构会极大地影响拟环二聚体中的光环加成反应，它决定了烯键的迁移率。几何相似的二聚体结构中的光环加成量子