6-(Dicyanomethylene)-3-methylbenzonaphtho<2,3-e><1,4>oxathiin-11-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 6-(Dicyanomethylene)-3-methylbenzonaphtho<2,3-e><1,4>oxathiin-11-one
• 英文别名: 2-(2-Methyl-6-oxobenzo[b]phenoxathiin-11-ylidene)propanedinitrile
• 化学式: C₂₀H₁₀N₂O₂S
• 分子量: 342.378
• InChiKey: YHVLVFIUHMLGFP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  25
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  99.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  4-methyl-2-mercaptophenol 在 吡啶 、 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 54.0h， 生成 6-(Dicyanomethylene)-3-methylbenzonaphtho<2,3-e><1,4>oxathiin-11-one
  参考文献：
  名称：

  Single-Component Donor-Acceptor Organic Semiconductors Derived from TCNQ

  摘要：

  13,13,14,14-Tetracyanobenzo[b]naphtho[2,3-e][1,4]dithiin-6,11-quinodimethane (9a) and 13,13,14,14-tetracyanobenzo[b]naphtho[2,3-e] [1,4]oxathiin-6,11-quinodimethane (10a) and their methyl-substituted derivatives(9b and 10b-d, respectively) have been prepared as single-component donor-acceptor compounds from the corresponding quinones 7 and 8 by using the Lehnert's reagent. UV-vis spectra of the novel compounds reveal the presence of an intramolecular electronic transfer from the donor to the acceptor moiety. Cyclic voltammetry displays, in addition to the oxidation peak, a two-electron reduction wave to the dianion, as confirmed by controlled potential coulometry analysis. The crystallographical study carried out on single crystals of compound 10d shows that molecules are not planar and stack with aromatic interactions between donor and acceptor moieties. In agreement with the crystallographical results, the electrical conductivity measured on a powder sample of 10c exhibits semiconductive behavior. Molecular orbital calculations using the PM3 semiempirical method were performed on both neutral and oxidized/reduced compounds and predict that molecules are severely distorted from planarity. Distortions are compared with crystallographic data and are analyzed in terms of nonbonding interactions and crystal packing. Valence effective Hamiltonian (VEH) nonempirical calculations were used to study the electronic properties and support the intramolecular charge-transfer nature of the lowest-energy absorption band. The evolution of the geometric structure evidences a gain of aromaticity upon oxidation and reduction that just the obtention of stable cations and,anions. The observation of a unique two-electron reduction wave to the dianion is rationalize;by comparing the electronic and structural changes induced by reduction on compound 9a and on the parent TCNQ molecule.

  DOI：

  10.1021/jo00095a042

文献信息

• Single-Component Donor-Acceptor Organic Semiconductors Derived from TCNQ
  作者：Paloma Bando、Nazario Martin、Jose L. Segura、Carlos Seoane、Enrique Orti、Pedro M. Viruela、Rafael Viruela、Armando Albert、Felix H. Cano

  DOI：10.1021/jo00095a042

  日期：1994.8

  13,13,14,14-Tetracyanobenzo[b]naphtho[2,3-e][1,4]dithiin-6,11-quinodimethane (9a) and 13,13,14,14-tetracyanobenzo[b]naphtho[2,3-e] [1,4]oxathiin-6,11-quinodimethane (10a) and their methyl-substituted derivatives(9b and 10b-d, respectively) have been prepared as single-component donor-acceptor compounds from the corresponding quinones 7 and 8 by using the Lehnert's reagent. UV-vis spectra of the novel compounds reveal the presence of an intramolecular electronic transfer from the donor to the acceptor moiety. Cyclic voltammetry displays, in addition to the oxidation peak, a two-electron reduction wave to the dianion, as confirmed by controlled potential coulometry analysis. The crystallographical study carried out on single crystals of compound 10d shows that molecules are not planar and stack with aromatic interactions between donor and acceptor moieties. In agreement with the crystallographical results, the electrical conductivity measured on a powder sample of 10c exhibits semiconductive behavior. Molecular orbital calculations using the PM3 semiempirical method were performed on both neutral and oxidized/reduced compounds and predict that molecules are severely distorted from planarity. Distortions are compared with crystallographic data and are analyzed in terms of nonbonding interactions and crystal packing. Valence effective Hamiltonian (VEH) nonempirical calculations were used to study the electronic properties and support the intramolecular charge-transfer nature of the lowest-energy absorption band. The evolution of the geometric structure evidences a gain of aromaticity upon oxidation and reduction that just the obtention of stable cations and,anions. The observation of a unique two-electron reduction wave to the dianion is rationalize;by comparing the electronic and structural changes induced by reduction on compound 9a and on the parent TCNQ molecule.