3,6-bis[(tert-butylphenyl)sulfanyl]phthalonitrile | 1130308-49-4

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 3,6-bis[(tert-butylphenyl)sulfanyl]phthalonitrile
• 英文别名: 3,6-bis[(4-tert-butylphenyl)thio]phthalonitrile；3,6-bis(4-tert-butylthiophenyl)phthalonitrile；4,5-bis(4-tert-butylphenylthio)phthalonitrile；3,6-bis(tert-butyl thiophenyl)phthalonitrile；3,6-bis(thiophenyl-tert-butyl)phthalonitrile；3,6-Bis[(4-tert-butylphenyl)sulfanyl]benzene-1,2-dicarbonitrile；3,6-bis[(4-tert-butylphenyl)sulfanyl]benzene-1,2-dicarbonitrile
• CAS: 1130308-49-4
• 化学式: C₂₈H₂₈N₂S₂
• 分子量: 456.676
• InChiKey: BPRAHAIZGOMVSU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.8
• 重原子数：
  32
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 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：

  3,6-bis[(tert-butylphenyl)sulfanyl]phthalonitrile 在 cerium(III) chloride 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 戊醇 为溶剂， 反应 5.0h， 以10%的产率得到1,4,8,-11,15,18,22,25-octakis(4-t-butylphenylsulfanyl)phthalocyanine
  参考文献：
  名称：

  一些 3,6-二取代邻苯二甲腈的路线和从中衍生的酞菁实例：概述

  摘要：

  本文回顾了一些合成途径，这些途径提供了 3,6-二取代酞腈，这是合成 1,4,8,11,15,18,22,25-八取代酞菁衍生物的前体。评价了使用 Diels-Alder 反应合成 3,6-二烷基、3,6-二烷氧基甲基、3,6-二烯基和 3,6-二苯基邻苯二甲腈的早期路线。然而，审查的重点集中在 2,3-二氰基氢醌作为获得 3,6-二取代邻苯二甲腈的起始原料的范围和应用。使用 2,3-二氰基氢醌的最早例子涉及其 O-烷基化以提供 3,6-二烷氧基邻苯二甲腈。这些是近红外吸收酞菁衍生物的直接前体。2,3-二氰基氢醌的三氟甲磺酸化扩展了该化合物用于合成酞菁的范围；ñAr 反应并容易与硫醇反应生成 3,6-双（烷基硫烷基）和 3,6-双（芳基硫烷基）邻苯二甲腈。3,6-双（苯基硒基）邻苯二甲腈最近也从相同的前体中获得。从中获得的酞菁衍生物通常表现出强烈的红移 Q 波段吸收，该吸收对中心金属离子特别敏感。2

  DOI：

  10.1142/s108842461330005x
• 作为产物：
  描述：

  3,6-二羟基邻苯二甲腈 在 吡啶 、 potassium carbonate 作用下， 以 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 48.0h， 生成 3,6-bis[(tert-butylphenyl)sulfanyl]phthalonitrile
  参考文献：
  名称：

  Synthesis of arylsulfanyl-subphthalocyanines and their ring expansion reaction

  摘要：

  对于染料敏化太阳能电池而言，酞菁需要对 700 至 850 纳米之间的远红光有很强的吸收能力，因为它们具有很高的电子传递效率。然而，酞菁对基底板缺乏亲和力，因此无法用作染料敏化太阳能电池的光敏剂。因此，我们使用亚酞菁作为前体，利用扩环技术制备出不对称的 3:1 型酞菁，以增加与基底板的亲和力。由于亚酞菁具有芳基硫酰基作为前体，因此不对称酞菁有望与基底板具有良好的亲和性。对合成非周边芳基硫酰亚酞菁的光谱特性和电子转移能力进行了估算。除了试制之外，还利用相应的亚酞菁合成了不对称的 3:1 型酞菁--六[（4-甲基苯基）硫]酞菁。

  DOI：

  10.1142/s1088424615500194

文献信息

• 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。
• Syntheses of near infrared absorbed phthalocyanines to utilize photosensitizers
  作者：Keiichi Sakamoto、Satoru Yoshino、Makoto Takemoto、Naoki Furuya

  DOI：10.1142/s1088424613500326

  日期：2013.8

  Phthalocyanines have become of major interest as functional colorants for various applications. In order to use various applications especially photosensitizers, the absorption maxima called Q-band of phthalocyanines are required to be shifted to the near infrared region. Substituted phthalocyanine analog alkylbenzopiridoporphyrazins, especially zinc bis(1,4-didecylbenzo)-bis(3,4-pyrido)porphyrazine, and toroidal-shaped phthalocyanines having aminoamine dendric side chains such as toroidal zinc poly(aminoamine)phthalocyanine dendrons were synthesized. Phthalocyanines of two types reportedly use photosensitizers for photodynamic therapy of cancer. The respective efficacies of photodynamic therapy of cancer for zinc bis(1,4-didecylbenzo)-bis(3,4-pyrido)porphyrazine and its regioisomers were estimated using laser-flash photolysis. The capability of using photodynamic therapy for toroidal zinc poly(aminoamine)phthalocyanine dendrons was assessed using a cancer cell culture. Both phthalocyanines were suitable for the use as a photosensitizer as photodynamic therapy of cancer. Then, non-peripheral thioaryl substituted phthalocyanines, 1,4,8,11,15,18,22,25-octakis(thioaryl)phthalocyanines, such as 1,4,8,11,15,18,22,25-octakis(thiophenylmethyl)phthalocyanines, 1,4,8,11,15,18,22,25-octakis(thiophenylmethoxy)phthalocyanines, and 1,4,8,11,15,18,22,25-octakis(thiophenyl tert-butyl)phthalocyanines were also synthesized in order to develop next- generation photovoltaic cells and/or dye-sensitized solar cells. Non-peripheral substituted 1,4,8,11,15,18,22,25-octakis(thioaryl)phthalocyanines exhibited a Q-band in the near infrared region. Electrochemical measurements were performed on the above-mentioned 1,4,8,11,15,18,22,25-octakis(thioaryl)phthalocyanines described above to examine their electron transfer abilities and electrochemical mechanisms. The compounds 1,4,8,11,15,18,22,25-octakis(thioaryl)phthalocyanines are anticipated to be appropriate materials for use in the next generation of photovoltaic cells.

  酞菁作为功能着色剂，在各种应用领域都引起了极大的兴趣。为了实现各种应用，尤其是光敏剂的应用，需要将酞菁的最大吸收波段（Q 波段）转移到近红外区域。我们合成了取代的酞菁类似物烷基苯并吡啶卟嗪，特别是双(1,4-二癸基苯并)-双(3,4-吡啶)卟嗪锌，以及具有氨基树枝状侧链的环状酞菁，如环状多(氨基胺)酞菁树枝状锌。据报道，这两种类型的酞菁可作为光敏剂用于癌症的光动力疗法。利用激光闪烁光解法估算了双(1,4-二癸基苯并)-双(3,4-吡啶并)卟吩锌及其区域异构体各自的癌症光动力疗法疗效。利用癌细胞培养物评估了环状锌聚(氨基胺)酞菁树枝体使用光动力疗法的能力。这两种酞菁都适合用作光敏剂，对癌症进行光动力治疗。还合成了 1,4,8,11,15,18,22,25-八(噻吩甲氧基)酞菁和 1,4,8,11,15,18,22,25-八(噻吩叔丁基)酞菁，以开发新一代光伏电池和/或染料敏化太阳能电池。非周边取代的 1,4,8,11,15,18,22,25-八(硫代芳基)酞菁在近红外区域显示出 Q 波段。对上述 1,4,8,11,15,18,22,25-辛二基（硫芳基）酞菁进行了电化学测量，以研究它们的电子转移能力和电化学机制。预计 1,4,8,11,15,18,22,25-辛二基（硫芳基）酞菁化合物将成为下一代光伏电池的合适材料。
• Design, Synthesis, and Properties of Phthalocyanine Complexes with Main-Group Elements Showing Main Absorption and Fluorescence beyond 1000 nm
  作者：Taniyuki Furuyama、Koh Satoh、Tomofumi Kushiya、Nagao Kobayashi

  DOI：10.1021/ja411016f

  日期：2014.1.15

  that all of the central group 15 elements, peripheral group 16 elements, and their positions are necessary to shift the Q-band beyond 1000 nm, indicating that the substitution effects of group 15 and 16 elements act synergistically. The Pcs having Q-bands beyond 1000 nm in this study also had stability under aerobic conditions comparative to that of CuPc, which is presently being widely used in consumer

  我们全面描述了新开发的酞菁 (Pcs) 的独特性质，其中包含在近红外区域吸收和发射的主族元素。第 16 族（S、Se 和 Te）元素和第 15 族（P、As 和 Sb）元素用作外围和中心（核心）取代基。随着第 16 族元素引入游离碱 Pc，观察到 Q 带的红移，这是由于第 16 族元素的给电子能力，特别是在 α 位置。α-ArS-、ArSe- 和 ArTe 连接的游离碱 Pcs 的 X 射线晶体学分析也成功进行，并阐明了结构和光学性质之间的关系。当第 15 族元素离子被引入 Pc 环的中心时，所得的 Pcs 显示出超过 1000 nm（在 CH2Cl2 中高达 1056 nm）的单个 Q 带峰。特别是，[(ArS)8PcP(OMe)2](+) 和 [(ArS)8PcAs(OMe)2](+) 在 960-1400 nm 区域表现出明显的荧光，具有中等的量子产率。15 族元素的原子半径对于决定
• Near-infrared absorbing unsymmetrical Zn(II) phthalocyanine for dye-sensitized solar cells
  作者：Varun Kumar Singh、Paolo Salvatori、Anna Amat、Saurabh Agrawal、Filippo De Angelis、Md.K. Nazeeruddin、Narra Vamsi Krishna、Lingamallu Giribabu

  DOI：10.1016/j.ica.2013.07.052

  日期：2013.10

  Unsymmetrical Zn phthalocyanine consisting of six S-aryl groups at α-positions and a carboxy anchoring group at β-position has been designed and synthesized for dye-sensitized solar cells (DSCs) applications. The unsymmetrical phthalocyanine has been characterized by elemental, MALDI-MS, IR, 1H NMR, UV–Vis, fluorescence (steady-state & lifetime) and electrochemical (including spectroelectrochemical)

  已经设计并合成了由α位上的六个S-芳基和β位上的羧基锚定基组成的不对称Zn酞菁，用于染料敏化太阳能电池（DSC）应用。非对称酞菁的特征在于元素，MALDI-MS，IR，1H NMR，UV-Vis，荧光（稳态和寿命）和电化学（包括光谱电化学）方法。由于存在S-芳基，非对称酞菁的Q带吸收最大值发生了红移，这与电化学和原位光谱电化学研究一致，使HOMO含量不稳定。氧化还原过程被分配给基于大环的电子转移过程，不对称酞菁的LUMO位于TiO2导带之上，并且HOMO远低于I- / I3-氧化还原电解质的电势。实验结果得到DFT / TD-DFT研究的支持。使用I / I3-氧化还原电解质系统在DSC中测试了新的不对称酞菁。
• Optical, electrochemical, third-order nonlinear optical, and excited state dynamics studies of thio-zinc phthalocyanine
  作者：Debasis Swain、Varun K. Singh、Narra V. Krishna、L. Giribabu、S. Venugopal Rao

  DOI：10.1142/s1088424614500035

  日期：2014.4

  Zinc phthalocyanine with S-aryl groups at α-positions have been synthesized and its optical, emission, electrochemical and third-order nonlinear optical properties were investigated. Both the Soret and Q-bands were red-shifted and obeyed Beer–Lambert's law. Electrochemical properties indicated that both oxidation and reduction processes were ring centered. Emission spectra were recorded in different solvents and the fluorescence yields obtained were in the range of 0.02 while time-resolved fluorescence data revealed lifetimes of typically few ns. Excited state dynamics in this novel thio-zinc phthalocyanine molecule has been investigated using femtosecond (fs) degenerate pump-probe spectroscopy. Nonlinear optical properties of this molecule have been examined using the Z-scan technique with picosecond (ps) and fs pulses. Both open and closed aperture Z-scan curves were recorded with ~2 ps/~150 fs laser pulses at a wavelength of 800 nm and nonlinear optical coefficients were extracted from both the studies. Degenerate pump-probe data performed at 600 nm suggested a single long lifetime of ~300 ps, possibly originating from the non-radiative decay of S₁ state.

  研究人员合成了在α-位上带有 S-芳基的锌酞菁，并对其光学、发射、电化学和三阶非线性光学特性进行了研究。索雷特波段和 Q 波段都发生了红移，并服从比尔-朗伯定律。电化学特性表明，氧化和还原过程均以环为中心。在不同溶剂中记录了发射光谱，获得的荧光产率在 0.02 之间，而时间分辨荧光数据显示其寿命通常为几毫微秒。利用飞秒（fs）变性泵浦探针光谱法研究了这种新型硫代锌酞菁分子的激发态动力学。利用皮秒（ps）和fs 脉冲的 Z 扫描技术研究了这种分子的非线性光学特性。利用波长为 800 纳米的 ~2 ps/~150 fs 激光脉冲记录了开孔和闭孔 Z 扫描曲线，并从这两项研究中提取了非线性光学系数。在 600 纳米波长下进行的去极化泵浦探针数据表明，S1 状态的非辐射衰变可能导致约 300 ps 的单个长寿命。