3,7-二羟基萘-2,6-二甲醛 | 1092649-40-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 中文名称: 3,7-二羟基萘-2,6-二甲醛
• 英文名称: 3,7-dihydroxynaphthalene-2,6-dicarbaldehyde
• 英文别名: 3,7-diformyl-2,6-dihydroxynaphthalene
• CAS: 1092649-40-5
• 化学式: C₁₂H₈O₄
• 分子量: 216.193
• InChiKey: SRTCNFLUZQUMKJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  74.6
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,7-二羟基萘-2,6-二甲醛 、 苄胺 以 甲醇 为溶剂， 以64%的产率得到3,7-Bis(benzyliminomethyl)naphthalene-2,6-diol
  参考文献：
  名称：

  Mutual Interference between Intramolecular Proton Transfer Sites through the Adjoining π-Conjugated System in Schiff Bases of Double-Headed, Fused Salicylaldehydes

  摘要：

  We synthesized two constitutionally isomeric bis(iminomethyl)-2,6-dihydroxynaphthalenes, namely, alpha,alpha-diimines 1 and beta,beta-diimines 2, which can be formally represented as fused salicylaldimines with resonance-assisted hydrogen-bonding sites. Spectroscopic data show that the OH/OH, NH/OH, and NH/NH forms of 1 were in equilibrium in solution and that the proportion of the NH-bearing tautomers increased as the solvent polarity increased. The UV spectra of thin solid films of 1 with various types of hydrogen-bonding networks differed from one another, and the spectral profiles were markedly temperature dependent, whereas the spectra of 1 in the molten state showed quite similar profiles. In contrast, 2 existed predominantly as the OH/OH form irrespective of the solvent polarity or crystal packing. Quantum chemical calculations suggest that the difference between the probabilities of intramolecular proton transfer in 1 and 2 can be explained in terms of the interplay between the resonance-assisted hydrogen-bonding sites and the adjoining pi-conjugated system.

  DOI：

  10.1021/jo401108z
• 作为产物：
  描述：

  2,6-萘二酚 在 盐酸 、 叔丁基锂 、 sodium hydride 作用下， 以 乙醚 、 乙醇 、 水 、 N,N-二甲基甲酰胺 、 正戊烷 为溶剂， 反应 25.33h， 生成 3,7-二羟基萘-2,6-二甲醛
  参考文献：
  名称：

  Designed Synthesis of Porphyrin-based Two-dimensional Covalent Organic Frameworks with Highly Ordered Structures

  摘要：

  卟啉是典型的功能性π系统；合成其高度有序的结构是化学中的一个既定目标。在此，我们报告了一系列基于卟啉的共价有机框架的设计合成，采用了聚缩合的方法，这些框架具有高度有序的结构。基于卟啉的框架表现出高晶体度、高孔隙率，以及在多卟啉片层上扩展的π共轭。

  DOI：

  10.1246/cl.150496

文献信息

• Experimental and Theoretical Studies on Constitutional Isomers of 2,6-Dihydroxynaphthalene Carbaldehydes. Effects of Resonance-Assisted Hydrogen Bonding on the Electronic Absorption Spectra
  作者：Hirohiko Houjou、Takatoshi Motoyama、Seisaku Banno、Isao Yoshikawa、Koji Araki

  DOI：10.1021/jo802345f

  日期：2009.1.16

  characterized a series of mono- and dicarbaldehydes of 2,6-dihydroxynaphthalene that bear potential resonance-assisted hydrogen bonding (RAHB) unit(s). X-ray crystal structures of selected compounds revealed that each salicylaldehyde moiety forms an intramolecular hydrogen bond and that the introduction of formyl groups into either the α- or β-position causes a considerable difference in geometry, which

  我们制备并表征了一系列带有潜在共振辅助氢键（RAHB）单元的2,6-二羟基萘的单和二甲醛。所选化合物的X射线晶体结构表明，每个水杨醛部分均形成分子内氢键，并且将甲酰基引入α-或β-位会导致几何结构上的显着差异，这可从传统的共振方案中得到解释。杂种包括离子态。NMR化学位移分析表明，溶液中的化合物相对于RAHB单元以封闭和开放形式之间的平衡混合物形式存在。从头算计算表明，分子内氢键的形成显着影响萘的各个局部六元环的芳香性。分析了芳香族化合物的变化趋势，并结合了RAHB的额外稳定能。在紫外可见光谱中，与α-甲酰基衍生物相比，β-甲酰基衍生物特别显示出明显的红移。通过TD-DFT计算成功地再现了吸收特征，并且通过RAHB对萘的π系统的电子态的影响来一致地解释了这些数据。最后，我们指出了带有RAHB的分子与催化缩合的芳烃在电子状态上的相似性。分析了芳香族化合物的变化趋势，并结合了RAHB的额外稳定
• Effects of interaction between the chelate rings and π-conjugated systems in fused salphen complexes on UV-Vis-NIR spectra
  作者：Hirohiko Houjou、Keisuke Yagi、Isao Yoshikawa、Toshiki Mutai、Koji Araki

  DOI：10.1002/poc.3635

  日期：2017.6

  a noticeable solvent effect. Time‐dependent density functional theory calculations suggested that the absorption arose from a π → π* transition localized at the naphthalene ring, which was perturbed by the adjoining chelate rings. Effects of the connection topology in the fused salphen complexes are discussed by comparison with those of polycyclic aromatic hydrocarbons.

  由3,7-二甲酰基-2,6-二羟基萘合成并苯并噻吩的双核（Zn 2，Ni 2和NiZn）配合物。将这些配合物的光谱性质与其通过phene型脱嵌的结构异构体的光谱性质进行了比较。并苯型配合物在近红外区域表现出特征吸收带，表现出明显的溶剂作用。随时间变化的密度泛函理论计算表明，吸收是由位于萘环上的π→π*跃迁引起的，该跃迁受到相邻的螯合环的干扰。通过与多环芳烃的比较，讨论了连接拓扑在稠合的马酚配合物中的作用。
• Designed Synthesis of Porphyrin-based Two-dimensional Covalent Organic Frameworks with Highly Ordered Structures
  作者：Xiong Chen、Jia Gao、Donglin Jiang

  DOI：10.1246/cl.150496

  日期：2015.9.5

  Porphyrins are representative functional π-systems; synthesizing their highly ordered structures is an established goal in chemistry. Here, we report the designed synthesis of a series of porphyrin-based covalent organic frameworks with highly ordered structures through polycondensation. The porphyrin-based frameworks exhibited high crystallinity, high porosity, and extended π-conjugation over the polyporphyrin sheets.

  卟啉是典型的功能性π系统；合成其高度有序的结构是化学中的一个既定目标。在此，我们报告了一系列基于卟啉的共价有机框架的设计合成，采用了聚缩合的方法，这些框架具有高度有序的结构。基于卟啉的框架表现出高晶体度、高孔隙率，以及在多卟啉片层上扩展的π共轭。
• Mutual Interference between Intramolecular Proton Transfer Sites through the Adjoining π-Conjugated System in Schiff Bases of Double-Headed, Fused Salicylaldehydes
  作者：Hirohiko Houjou、Hajime Shingai、Keisuke Yagi、Isao Yoshikawa、Koji Araki

  DOI：10.1021/jo401108z

  日期：2013.9.20

  We synthesized two constitutionally isomeric bis(iminomethyl)-2,6-dihydroxynaphthalenes, namely, alpha,alpha-diimines 1 and beta,beta-diimines 2, which can be formally represented as fused salicylaldimines with resonance-assisted hydrogen-bonding sites. Spectroscopic data show that the OH/OH, NH/OH, and NH/NH forms of 1 were in equilibrium in solution and that the proportion of the NH-bearing tautomers increased as the solvent polarity increased. The UV spectra of thin solid films of 1 with various types of hydrogen-bonding networks differed from one another, and the spectral profiles were markedly temperature dependent, whereas the spectra of 1 in the molten state showed quite similar profiles. In contrast, 2 existed predominantly as the OH/OH form irrespective of the solvent polarity or crystal packing. Quantum chemical calculations suggest that the difference between the probabilities of intramolecular proton transfer in 1 and 2 can be explained in terms of the interplay between the resonance-assisted hydrogen-bonding sites and the adjoining pi-conjugated system.