1,2-dicyano-4,5-bis(octylsulfonyl)benzene | 216771-94-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,2-dicyano-4,5-bis(octylsulfonyl)benzene
• 英文别名: 4,5-bis(octylsulfonyl)phthalonitrile；3,6-di(octylsulfonyl)phthalonitrile；4,5-di(octylsulfonyl)phthalonitrile；4,5-Bis(octylsulfonyl)benzene-1,2-dicarbonitrile
• CAS: 216771-94-7
• 化学式: C₂₄H₃₆N₂O₄S₂
• 分子量: 480.693
• InChiKey: QFBZHMVRDYWNPH-UHFFFAOYSA-N

物化性质

• 沸点：
  683.9±55.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  32
• 可旋转键数：
  16
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  133
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,2-dicyano-4,5-bis(octylsulfonyl)benzene 在 三氯化硼 作用下， 以 对二甲苯 为溶剂， 反应 0.33h， 以64%的产率得到chloro-[2,3,9,10,16,17-hexa(octylsulfonyl)-7,12:14,19-diimino-21,5-nitrilo-5H-tribenzo[c,h,m][1,6,11]triazacyclopentadecinato-(2)-κN²²,κN²³,κN²⁴]-boron(III)
  参考文献：
  名称：

  氯代和苯氧基取代的亚酞菁的高效合成

  摘要：

  描述了一种使用 1 M 三氯化硼在对二甲苯中的溶液合成氯取代的亚酞菁的高效方法，并与其他先前描述的结果进行了比较。优化了苯氧基对轴向氯原子的取代反应。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

  DOI：

  10.1002/ejoc.200300169
• 作为产物：
  描述：

  4,5-dioctylthiobenzene-1,2-dicarbonitrile 在 双氧水 作用下， 以 溶剂黄146 为溶剂， 以84%的产率得到1,2-dicyano-4,5-bis(octylsulfonyl)benzene
  参考文献：
  名称：

  Synthesis and Nonlinear Optical, Photophysical, and Electrochemical Properties of Subphthalocyanines

  摘要：

  Novel boron(III) subphthalocyanines (SubPcs) soluble in organic solvents containing a variety of donor and acceptor substituent groups have been synthesized by boron trihalide-induced cyclotrimerization of adequately substituted derivatives of phthalonitrile in 1-chloronaphthalene. The choice of the substituents on the 1,2-dicyanobenzene derivatives has been made taking into account the high reactivity of the Lewis acid BCl3 toward many functional groups. Considering this limitation. we set out to synthesize phthalodinitriles equipped with iodo, nitro, alkyl- or arylthio, alkyl- or arylsulfonyl groups that are sufficiently stable under the required reaction conditions and also provide an easily accessible set of acceptor/donor substituents. The quadratic and cubic hyperpolarizabilities of these compounds as well as their linear optical and electrochemical properties have been measured by several techniques, including EFISH (at two wavelengths), HRS, and THG, steady-state and time-resolved absorption and fluorescence, laser-induced optoacoustic calorimetry, time-resolved near-infrared emission spectroscopy, and cyclic voltammetry. beta(HRS) has been measured at 1.46 mu m, where the contamination from the multiphoton-induced fluorescence can be ruled out. beta(HRS) reachs high values that markedly depend on substitution. It shows a clear enhancement with the acceptor character of the substituents, the highest values being obtained for the compounds bearing the strongest acceptor groups. They are comparable or even superior to many efficient second-order compounds. A main outcome of these results is that an adequate choice of the substituents offers a promising route for optimization of the quadratic response of the SubPcs. This kind of compounds is less prone to aggregation than their expanded analogues, the phthalocyanines, fluoresces with quantum yields ca. 0.25, lower than those typical for phthalocyanines, and has larger triplet quantum yields. The tripler-state lifetime is in the 100-mu s time range, long enough for efficient oxygen quenching. Indeed, subphthalocyanines sensitize singlet molecular oxygen, O-2((1)Delta(g)), with quantum yields ranging from 0.23 to 0.75. The ground-state oxidation potentials an similar to those of phthalocyanines, while the reduction potentials are clearly more negative; i.e., they are more difficult to reduce. In contrast, electronically excited subphthalocyanines are more easily oxidized than the corresponding phthalocyanines by ca. 500 mV which results in lower photostability, especially in polar solvents.

  DOI：

  10.1021/ja980508q

文献信息

• Tuning Photoinduced Energy- and Electron-Transfer Events in Subphthalocyanine-Phthalocyanine Dyads
  作者：David González-Rodríguez、Christian G. Claessens、Tomas Torres、Shenggao Liu、Luis Echegoyen、Nuria Vila、Santi Nonell

  DOI：10.1002/chem.200400779

  日期：2005.6.20

  subphthalocyanine to the phthalocyanine takes place. On the contrary, stabilization of the radical pair by lowering the redox gap between electron donor and acceptor results in a highly efficient photoinduced electron-transfer process, even in solvents of low polarity such as toluene (Phi(ET) approximately 0.9). These features, together with the extraordinary absorptive cross section that these molecular ensembles

  通过单炔基酞菁与不同的单碘亚酞菁之间的钯催化的交叉偶联反应，已经制备了一系列的亚酞菁-酞菁二价化合物。两个光敏单元之间的电子耦合通过刚性和π共轭的炔基间隔基来确保。另外，通过引入不同的外围取代基来调节亚酞菁部分的电子特性。循环和Osteryoung方波伏安法实验表明，从硫醚或无取代基变为硝基时，该亚基的还原电势可降低约400 mV。结果，可以微调电荷转移状态的能级，以便获得对每个子单元中光激发能的命运的控制。所采用的各种稳态和时间分辨光物理技术表明，当电荷转移态处于高能量状态时，就会发生从激发的亚酞菁到酞菁的定量单重态单重态能量转移机理。相反，通过降低电子供体和受体之间的氧化还原间隙来稳定自由基对，即使在极性低的溶剂（例如甲苯（Phi（ET）约为0.9））中，也可以实现高效的光诱导电子转移过程。这些特征以及这些分子集合体在整个UV / Vis光谱中显示的非凡吸收性截面，使其成为需要宽带光源
• Highly Efficient Synthesis of Chloro- and Phenoxy-Substituted Subphthalocyanines
  作者：Christian G. Claessens、David González-Rodríguez、Belen del Rey、Tomás Torres、Gertraud Mark、Heinz-Peter Schuchmann、Clemens von Sonntag、J. Gavin MacDonald、Ronald S. Nohr

  DOI：10.1002/ejoc.200300169

  日期：2003.7

  A highly efficient method for the synthesis of chloro-substituted subphthalocyanines employing a 1 M boron trichloride solution in p-xylene is described and compared to other previously described results. The substitution reaction of the axial chlorine atom by a phenoxy group has been optimized. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

  描述了一种使用 1 M 三氯化硼在对二甲苯中的溶液合成氯取代的亚酞菁的高效方法，并与其他先前描述的结果进行了比较。优化了苯氧基对轴向氯原子的取代反应。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• Unsymmetrical Phthalocyanines With One TTF unit and Octylthio or Octylsulfonyl Groups: Their Optical and Electrochemical Properties
  作者：Takeshi Kimura、Jasmin Kang、Shidsuko Nakajo

  DOI：10.3987/com-15-s(t)32

  日期：——

  Unsymmetrical phthalocyanines fused with a TTF unit and six octylthio or six octylsulfonyl groups were prepared by the reaction of a mixture of phthalonitrile fused with a TTF unit and 4,5-di(octylthio)- or 4,5-di(octylsulfonyl)phthalonitrile. The optical and electrochemical properties of the products were determined by UV-vis absorption spectra, cyclic voltammetry, and ESR spectra.
• New polythiophenes bearing electron-acceptor phthalocyanine chromophores
  作者：M.Victoria Martı́nez-Dı́az、Sagrario Esperanza、Andrés de la Escosura、Marinella Catellani、Sami Yunus、Silvia Luzzati、Tomás Torres

  DOI：10.1016/j.tetlet.2003.09.096

  日期：2003.11.10

  Two new donor-acceptor copolymers comprising a polythiophene backbone, and bearing phthalocyanine chromophores on the side chains have been prepared. Preliminary photophysical characterization of these materials by FTIR photoinduced absorption indicates that electron transfer from the polythiophene to the phthalocyanine units takes place. (C) 2003 Elsevier Ltd. All rights reserved.
• Synthesis and Nonlinear Optical, Photophysical, and Electrochemical Properties of Subphthalocyanines
  作者：B. del Rey、U. Keller、T. Torres、G. Rojo、F. Agulló-López、S. Nonell、C. Martí、S. Brasselet、I. Ledoux、J. Zyss

  DOI：10.1021/ja980508q

  日期：1998.12.1

  Novel boron(III) subphthalocyanines (SubPcs) soluble in organic solvents containing a variety of donor and acceptor substituent groups have been synthesized by boron trihalide-induced cyclotrimerization of adequately substituted derivatives of phthalonitrile in 1-chloronaphthalene. The choice of the substituents on the 1,2-dicyanobenzene derivatives has been made taking into account the high reactivity of the Lewis acid BCl3 toward many functional groups. Considering this limitation. we set out to synthesize phthalodinitriles equipped with iodo, nitro, alkyl- or arylthio, alkyl- or arylsulfonyl groups that are sufficiently stable under the required reaction conditions and also provide an easily accessible set of acceptor/donor substituents. The quadratic and cubic hyperpolarizabilities of these compounds as well as their linear optical and electrochemical properties have been measured by several techniques, including EFISH (at two wavelengths), HRS, and THG, steady-state and time-resolved absorption and fluorescence, laser-induced optoacoustic calorimetry, time-resolved near-infrared emission spectroscopy, and cyclic voltammetry. beta(HRS) has been measured at 1.46 mu m, where the contamination from the multiphoton-induced fluorescence can be ruled out. beta(HRS) reachs high values that markedly depend on substitution. It shows a clear enhancement with the acceptor character of the substituents, the highest values being obtained for the compounds bearing the strongest acceptor groups. They are comparable or even superior to many efficient second-order compounds. A main outcome of these results is that an adequate choice of the substituents offers a promising route for optimization of the quadratic response of the SubPcs. This kind of compounds is less prone to aggregation than their expanded analogues, the phthalocyanines, fluoresces with quantum yields ca. 0.25, lower than those typical for phthalocyanines, and has larger triplet quantum yields. The tripler-state lifetime is in the 100-mu s time range, long enough for efficient oxygen quenching. Indeed, subphthalocyanines sensitize singlet molecular oxygen, O-2((1)Delta(g)), with quantum yields ranging from 0.23 to 0.75. The ground-state oxidation potentials an similar to those of phthalocyanines, while the reduction potentials are clearly more negative; i.e., they are more difficult to reduce. In contrast, electronically excited subphthalocyanines are more easily oxidized than the corresponding phthalocyanines by ca. 500 mV which results in lower photostability, especially in polar solvents.