2,6,7-trimethoxy-1,4-anthracenedione

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 2,6,7-trimethoxy-1,4-anthracenedione
• 英文别名: 2,6,7-Trimethoxyanthracene-1,4-dione
• 化学式: C₁₇H₁₄O₅
• 分子量: 298.295
• InChiKey: RGFPNDYAWXHCSJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2,6,7-trimethoxy-1,4-anthracenedione 、 丙二腈 在 吡啶 、 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以63%的产率得到11,11,12,12-Tetracyano-2,6,7-trimethoxy-1,4-anthraquinodimethane
  参考文献：
  名称：

  Synthesis and Characterization of 11,11,12,12-Tetracyano-1,4-anthraquinodimethanes (1,4-TCAQs): Novel Electron Acceptors with Photoinduced Charge-Transfer Properties

  摘要：

  The synthesis of novel substituted 11,11,12,12-tetracyano-1,4-anthraquinodimethanes (1,4-TCAQs) 3 from the corresponding 1,4-anthraquinones 2 by reaction with the Lehnert's reagent is described, thus confirming the validity of this procedure to obtain different substitution patterns on the benzene fused quinone ring. W-vis spectra of the novel compounds show the presence of an intramolecular charge-transfer band in the blue part of the visible region. Depending upon the substitution pattern, the cyclic voltammetry (CV) measurements on 1,4-TCAQs reveal one reduction wave involving two electrons to the dianion or two One-electron reduction waves to the corresponding radical-anion and dianion. Acceptor properties similar to those of TCNQ are expected for 3 when the TCNQ moiety is substituted with chlorine atoms. The molecular and electronic structures of compounds 2 and 3 are investigated using the semiempirical PM3 method and the nonempirical VEH approach, respectively. PM3 calculations predict that 1,4-TCAQs are nonplanar and adopt a butterfly-type structure where the planarity of the lateral naphthalene unit is preserved. VEH calculations show that the naphthalene moiety behaves as an electron donor since the HOMO --> LUMO transition corresponds to an electronic charge transfer from this moiety to the acceptor TCNQ ring, thus supporting the experimental UV-vis results. The evolution of the geometric structure of compounds 3 upon reduction evidences a gain of aromaticity of the TCNQ ring, even if the anions are predicted to remain nonplanar. This absence of planarity justifies the low stability found experimentally for the anions and explains the observation of only one reduction wave involving two-electrons for the most hindered derivatives.

  DOI：

  10.1021/jo00118a025
• 作为产物：
  描述：

  4,5-dimethoxy-phthalaldehyde 、 2-甲氧基对苯二酚 在 sodium carbonate 作用下， 以 various solvent(s) 为溶剂， 以93%的产率得到2,6,7-trimethoxy-1,4-anthracenedione
  参考文献：
  名称：

  Syntheses, electrochemistry and molecular modeling of N,N′-dicyanoquinonediimine (DCNQI) derivatives of substituted 1,4-anthracenediones: precursors for organic metals.

  摘要：

  The title compounds (10) have been obtained from the corresponding 1,4-anthracenedione derivatives (3), prepared by different synthetic routes, by reaction with bis(trimethylsilyl)carbodiimide (BTC). The cyclic voltammetry of these compounds (3 and 10) reveals the presence of two reduction waves to the corresponding anion-radical and dianion. The acceptor ability of compounds 10 can be modulated by the presence of substituents on the DCNQI ring. The syn/anti isomers have been studied by molecular mechanics and the results are in good agreement with the H-1-NMR high resolution spectral data.

  DOI：

  10.1016/s0040-4020(01)80405-1

文献信息

• Syntheses, electrochemistry and molecular modeling of N,N′-dicyanoquinonediimine (DCNQI) derivatives of substituted 1,4-anthracenediones: precursors for organic metals.
  作者：Elena Barranco、Nazario Martín、José L. Segura、Carlos Seoane、Pilar de la Cruz、Fernando Langa、Araceli Gonzalez、José M. Pingarrón

  DOI：10.1016/s0040-4020(01)80405-1

  日期：1993.5

  The title compounds (10) have been obtained from the corresponding 1,4-anthracenedione derivatives (3), prepared by different synthetic routes, by reaction with bis(trimethylsilyl)carbodiimide (BTC). The cyclic voltammetry of these compounds (3 and 10) reveals the presence of two reduction waves to the corresponding anion-radical and dianion. The acceptor ability of compounds 10 can be modulated by the presence of substituents on the DCNQI ring. The syn/anti isomers have been studied by molecular mechanics and the results are in good agreement with the H-1-NMR high resolution spectral data.
• Synthesis and Characterization of 11,11,12,12-Tetracyano-1,4-anthraquinodimethanes (1,4-TCAQs): Novel Electron Acceptors with Photoinduced Charge-Transfer Properties
  作者：Nazario Martin、Jose L. Segura、Carlos Seoane、Pilar de la Cruz、Fernando Langa、Enrique Orti、Pedro M. Viruela、Rafael Viruela

  DOI：10.1021/jo00118a025

  日期：1995.6

  The synthesis of novel substituted 11,11,12,12-tetracyano-1,4-anthraquinodimethanes (1,4-TCAQs) 3 from the corresponding 1,4-anthraquinones 2 by reaction with the Lehnert's reagent is described, thus confirming the validity of this procedure to obtain different substitution patterns on the benzene fused quinone ring. W-vis spectra of the novel compounds show the presence of an intramolecular charge-transfer band in the blue part of the visible region. Depending upon the substitution pattern, the cyclic voltammetry (CV) measurements on 1,4-TCAQs reveal one reduction wave involving two electrons to the dianion or two One-electron reduction waves to the corresponding radical-anion and dianion. Acceptor properties similar to those of TCNQ are expected for 3 when the TCNQ moiety is substituted with chlorine atoms. The molecular and electronic structures of compounds 2 and 3 are investigated using the semiempirical PM3 method and the nonempirical VEH approach, respectively. PM3 calculations predict that 1,4-TCAQs are nonplanar and adopt a butterfly-type structure where the planarity of the lateral naphthalene unit is preserved. VEH calculations show that the naphthalene moiety behaves as an electron donor since the HOMO --> LUMO transition corresponds to an electronic charge transfer from this moiety to the acceptor TCNQ ring, thus supporting the experimental UV-vis results. The evolution of the geometric structure of compounds 3 upon reduction evidences a gain of aromaticity of the TCNQ ring, even if the anions are predicted to remain nonplanar. This absence of planarity justifies the low stability found experimentally for the anions and explains the observation of only one reduction wave involving two-electrons for the most hindered derivatives.