1,2-dicyano-4,5-p-tolylsulfonylbenzene | 218598-89-1

• 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-p-tolylsulfonylbenzene
• 英文别名: 4,5-Bis-(4-methylphenyl)sulfonylbenzene-1,2-dicarbonitrile
• CAS: 218598-89-1
• 化学式: C₂₂H₁₆N₂O₄S₂
• 分子量: 436.512
• InChiKey: HOWZCQKBNWVDRS-UHFFFAOYSA-N

物化性质

• 沸点：
  701.3±60.0 °C(Predicted)
• 密度：
  1.46±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  30
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.09
• 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：

  三氯化硼 、 1,2-dicyano-4,5-p-tolylsulfonylbenzene 在 1-氯萘 作用下， 以25%的产率得到chloro[2,3,9,10,16,17-hexa-p-tolylsulfonylsubphthalocyaninato]boron(III)
  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
• 作为产物：
  描述：

  1,2-dicyano-4,5-p-tolylthiobenzene 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以99%的产率得到1,2-dicyano-4,5-p-tolylsulfonylbenzene
  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