11,11,12,12-Tetracyano-2,6,7-trimethoxy-1,4-anthraquinodimethane

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 11,11,12,12-Tetracyano-2,6,7-trimethoxy-1,4-anthraquinodimethane
• 英文别名: 2-[4-(Dicyanomethylidene)-3,6,7-trimethoxyanthracen-1-ylidene]propanedinitrile
• 化学式: C₂₃H₁₄N₄O₃
• 分子量: 394.389
• InChiKey: PPIXFOGHFJCGDV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  30
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  123
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  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

文献信息

• 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.