Benzonaphtho<2,3-e><1,4>oxathiin-6,11-quinone | 153036-89-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: Benzonaphtho<2,3-e><1,4>oxathiin-6,11-quinone
• 英文别名: Benzo[b]phenoxathiine-6,11-dione
• CAS: 153036-89-6
• 化学式: C₁₆H₈O₃S
• 分子量: 280.304
• InChiKey: ZOTVXWJIASCDPZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  68.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  二(三甲基硅基)碳酰二亚胺 、 Benzonaphtho<2,3-e><1,4>oxathiin-6,11-quinone 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以83%的产率得到N,N'-dicyanobenzonaphtho<2,3-e><1,4>oxathiin-6,11-quinonediimine
  参考文献：
  名称：

  光诱导分子内电子转移的含硫供体-受体DCNQI衍生物的合成，表征和理论研究。

  摘要：

  供体-受体化合物N，N'-二氰基苯并[b，naphtho [2,3-e] [1,4] dithiin-6,11-奎宁二胺（9a）和N，N'-二氰基苯并[b]萘[2]制备了3-（3-e）[1,4]草苷-6,11-奎宁二胺（10a）及其甲基取代的衍生物（分别为9b和10b-d），并通过两种方法对它们的结构和电子性质进行了表征实验技术和量子化学计算。（1）H-NMR光谱证明溶液中存在顺/反异构体。实验和理论数据均表明，N-CN基团的优选构型对应于9的同分异构体和10的反异构体。对9b进行的X射线分析表明，分子不是平面的，而是堆积在垂直堆栈中显示相邻分子的供体和受体部分之间有重叠。与X射线数据一致，理论计算预测，对于9和10而言，受体DCNQI部分都会折叠并采用蝶形结构，供体部分会沿着穿过杂原子的线弯曲。从头算起6-31G的水平，平面结构与蝶形结构之间的能量差经计算<3 kcal / mol。UV

  DOI：

  10.1021/jo952274o
• 作为产物：
  描述：

  2,3-二氯-1,4-萘醌 、 2-羟基苯硫酚 在 吡啶 作用下， 以82%的产率得到Benzonaphtho<2,3-e><1,4>oxathiin-6,11-quinone
  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.
• Synthesis, Characterization, and Theoretical Study of Sulfur-Containing Donor−Acceptor DCNQI Derivatives with Photoinduced Intramolecular Electron Transfer
  作者：Nazario Martín、José L. Segura、Carlos Seoane、Enrique Ortí、Pedro M. Viruela、Rafael Viruela、Armando Albert、Félix H. Cano、José Vidal-Gancedo、Concepció Rovira、Jaume Veciana

  DOI：10.1021/jo952274o

  日期：1996.1.1

  11-quinonediimine (10a) and their methyl-substituted derivatives (9b and 10b-d, respectively) have been prepared, and their structural and electronic properties have been characterized by both experimental techniques and quantum-chemical calculations. The (1)H-NMR spectra evidence the existence of a syn/anti isomerism in solution. Both experimental and theoretical data suggest that the preferred configuration

  供体-受体化合物N，N'-二氰基苯并[b，naphtho [2,3-e] [1,4] dithiin-6,11-奎宁二胺（9a）和N，N'-二氰基苯并[b]萘[2]制备了3-（3-e）[1,4]草苷-6,11-奎宁二胺（10a）及其甲基取代的衍生物（分别为9b和10b-d），并通过两种方法对它们的结构和电子性质进行了表征实验技术和量子化学计算。（1）H-NMR光谱证明溶液中存在顺/反异构体。实验和理论数据均表明，N-CN基团的优选构型对应于9的同分异构体和10的反异构体。对9b进行的X射线分析表明，分子不是平面的，而是堆积在垂直堆栈中显示相邻分子的供体和受体部分之间有重叠。与X射线数据一致，理论计算预测，对于9和10而言，受体DCNQI部分都会折叠并采用蝶形结构，供体部分会沿着穿过杂原子的线弯曲。从头算起6-31G的水平，平面结构与蝶形结构之间的能量差经计算<3 kcal / mol。UV