1,2-dicyano-4,5-p-tolylthiobenzene | 218598-87-9

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 1,2-dicyano-4,5-p-tolylthiobenzene
• 英文别名: 4,5-dithioethertolyl phthalonitrile；1,2-Benzenedicarbonitrile, 4,5-bis[(4-methylphenyl)thio]-；4,5-bis[(4-methylphenyl)sulfanyl]benzene-1,2-dicarbonitrile
• CAS: 218598-87-9
• 化学式: C₂₂H₁₆N₂S₂
• 分子量: 372.514
• InChiKey: HJQPQFYEILJHQP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  26
• 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：
  98.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  4-甲苯硫酚 、 4,5-diiodobenzene-1,2-dicarbonitrile 在 potassium carbonate 作用下， 以 二甲基亚砜 为溶剂， 反应 0.5h， 以81%的产率得到1,2-dicyano-4,5-p-tolylthiobenzene
  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 Optical and Electron Donor Properties by Peripheral Thio–Aryl Substitution of Subphthalocyanine: A New Series of Donor–Acceptor Hybrids for Photoinduced Charge Separation
  作者：Chandra B. KC、Gary N. Lim、Francis D'Souza

  DOI：10.1002/chem.201601345

  日期：2016.9.5

  both in polar and nonpolar solvents conclusively proved electron transfer to be the quenching mechanism in these dyads. The measured rate constants by fitting kinetic data revealed efficient charge separation and charge recombination processes, suggesting that these dyads could be useful materials for the construction of light‐to‐electricity or light‐to‐fuel production devices.

  亚酞菁（SubPc）是普通酞菁家族的独特环还原成员，尽管以其较高的吸收率而闻名，但它在570 nm的最大峰值处吸收较窄，因此限制了其在光能收集应用中的效用。在本研究中，通过SubPc大环的外围硫代-芳基取代，已对光谱特性进行了调制，以将吸收和发射很好地扩展到可见/近红外区域。此外，对于α环取代的衍生物，可以看到SubPc的容易氧化，因此使这些衍生物成为更好的电子给体。接下来，制备含有众所周知的电子受体C 60的供体-受体二元组通过使用1,3-偶极环加成反应可实现与SubPc中心硼原子的连接。使用氧化还原和光谱数据进行的对照实验和自由能计算表明，在这些二元组中观察到的SubPc的荧光猝灭是由于电子转移引起的。因此，在极性和非极性溶剂中进行的瞬态光谱研究最终证明了电子转移是这些二元化合物的猝灭机理。通过拟合动力学数据测得的速率常数揭示了有效的电荷分离和电荷复合过程，表明这些二重体可能是用于构建光电或光燃料生产装置的有用材料。
• Synthesis of near-infrared absorbed metal phthalocyanine with S-aryl groups at non-peripheral positions
  作者：Keiichi Sakamoto、Eiko Ohno-Okumura、Taku Kato、Hisashi Soga

  DOI：10.1142/s1088424610001726

  日期：2010.1

  Phthalocyanines are used as various applications, including as organic charge carriers in photocopiers, laser light absorbers in data storage systems, photoconductors in photovoltaic cells and electrochromic displays, and non-colored transparent film in visible region. The absorption maxima of phthalocyanines are best if moved near the infrared region for these applications. The Q band of phthalocyanines can be moved to bathochromic effects through extension of a π conjugation system such as naphthalocyanines and anthracyanines. Yields of naphthalocyanines and anthracyanines are, however, low. To solve the problem, novel metal phthalocyanines having non-peripheral S-aryl substituent were synthesized. The novel phthalocyanines show a high strain structure and no liquid crystal property. The target compounds were synthesized: 15 phthalocyanines from 2,3-dicyanohydroquinone in 3 steps via 1,2-dicyanobenzene-3,6-bis(trifluorate) and 1,2-dicyanobenzene-3,6-thiophenols. The Q bands of obtained compounds appeared in the near-infrared region. In particular, lead 1,4,8,11,15,18,22,25-octakis(thiophenylmethyl)phthalocyanine shows a Q band at 857 nm. Furthermore, non-colored transparent films in the visible region can be produced.

  酞菁有多种用途，包括复印机中的有机电荷载体、数据存储系统中的激光光吸收器、光伏电池和电致变色显示器中的光电导体以及可见光区域的非彩色透明薄膜。在这些应用中，酞菁的吸收最大值最好接近红外区域。通过扩展 π 共轭体系（如萘花青素和蒽花青素），可将酞菁的 Q 波段转化为浴色效应。然而，萘酞菁和蒽菁的产量很低。为了解决这个问题，我们合成了具有非外周 S-芳基取代基的新型金属酞菁。这些新型酞菁具有高应变结构，且无液晶特性。合成了目标化合物：通过 1,2-二氰基苯-3,6-双(三氟)和 1,2-二氰基苯-3,6-噻吩酚，分三步从 2,3-二氰基对苯二酚合成了 15 个酞菁。所得化合物的 Q 带出现在近红外区域。其中，1,4,8,11,15,18,22,25-八(噻吩甲基)酞菁铅在 857 纳米波长处出现了 Q 带。此外，还可以生产出可见光区域的无色透明薄膜。
• Synthesis of 4-methylthiophenyl silicon phthalocyanines axially substituted with carboxylic acids for MOF materials
  作者：Víctor Sobrino-Bastán、Luis Martín-Gomis、Ángela Sastre-Santos

  DOI：10.1142/s1088424622500961

  日期：2023.1

  Two new peripherally substituted with 4 and 8 electron-donating 4-methylthiophenyl silicon phthalocyanines, [Formula: see text] 1 and [Formula: see text] 2, axially substituted with carboxylic acids have been synthesized using microwave irradiation in a very good yield. The new compounds have been characterized by ¹H-NMR, UV-vis, fluorescence, differential pulse voltammograms, and HR-MALDI-TOF mass spectrometry. An study of the stability of the axial chlorinated SiPcs in the function of the number of thiophenyl substituents indicates than [Formula: see text] 10 degradates faster, to its corresponding unreactive dihydrosilicon phthalocyanine derivative [Formula: see text] 11, than [Formula: see text]. The new SiPcs are excellent candidates as photoactive linkers for the construction of MOF materials.

  利用微波辐照合成了两种新的外围被 4 个和 8 个电子供体取代的 4-甲基噻吩基硅酞菁，[式：见正文]1 和[式：见正文]2，轴向被羧酸取代，收率非常高。新化合物通过 1H-NMR、UV-vis、荧光、微分脉冲伏安图和 HR-MALDI-TOF 质谱进行了表征。对轴向氯化 SiPcs 的稳定性与噻吩取代基数目关系的研究表明，[式：见正文] 10 比[式：见正文]更快降解为相应的无反应二氢硅酞菁衍生物[式：见正文]11。新的 SiPcs 是构建 MOF 材料的光活性连接体的极佳候选材料。
• 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.