1,4,8,-11,15,18,22,25-octakis(4-t-butylphenylsulfanyl)phthalocyanine | 101367-23-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: 1,4,8,-11,15,18,22,25-octakis(4-t-butylphenylsulfanyl)phthalocyanine
• 英文别名: 5,8,14,17,23,26,32,35-Octakis[(4-tert-butylphenyl)sulfanyl]-2,11,20,29,37,38,39,40-octazanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1,3,5,7,9,11,13,15,17,19(39),20,22,24,26,28(38),30(37),31,33,35-nonadecaene；5,8,14,17,23,26,32,35-octakis[(4-tert-butylphenyl)sulfanyl]-2,11,20,29,37,38,39,40-octazanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1,3,5,7,9,11,13,15,17,19(39),20,22,24,26,28(38),30(37),31,33,35-nonadecaene
• CAS: 101367-23-1
• 化学式: C₁₁₂H₁₁₄N₈S₈
• 分子量: 1828.72
• InChiKey: QBRJXFYEWBNDJJ-UHFFFAOYSA-N

物化性质

• 密度：
  1.30±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  36.3
• 重原子数：
  128
• 可旋转键数：
  24
• 环数：
  17.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  311
• 氢给体数：
  2
• 氢受体数：
  14

反应信息

• 作为产物：
  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

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。
• Cyclic voltammetry of non-peripheral thioaryl substituted phthalocyanines
  作者：Keiichi Sakamoto、Naoki Furuya、Hisashi Soga、Satoru Yoshino

  DOI：10.1016/j.dyepig.2012.08.025

  日期：2013.2

  Phthalocyanines have become of major interest as functional colorants for dye-sensitized photovoltaic cells. Syntheses of non-peripheral (1,4,8,11,15,18,22,25) thioaryl substituted phthalocyanines have been reported. These phthalocyanines exhibited a Q band in the near-infrared region.In order to develop next generation photovoltaic cells, we have synthesized 1,4,8,11,1538,22,25-octakis(thioaryl)phthalocyanines and estimated their electron transfer ability using cyclic voltammetry. In the cyclic voltammograms, these compounds showed reduction and oxidation potentials, which are attributed to the presence of the sulfur atoms in the thioaryl substituents at the peripheral positions of phthalocyanine.The electron transfer mechanisms of the phthalocyanines having cobalt and zinc as their central metal atoms were attributed to reduction and oxidation of their central metal, while electron transfer in the other metal-free compounds resulted from the highest occupied molecular orbital to the lowest unoccupied molecular orbital electron transitions. (C) 2012 Elsevier Ltd. All rights reserved.
• Routes to some 3,6-disubstituted phthalonitriles and examples of phthalocyanines derived therefrom: An overview
  作者：Martin J. Heeney、Shaya A. Al-Raqa、Aurélien Auger、Paul M. Burnham、Andrew N. Cammidge、Isabelle Chambrier、Michael J. Cook

  DOI：10.1142/s108842461330005x

  日期：2013.8

  3-dicyanohydroquinone concerned its O -alkylation to afford 3,6-dialkoxyphthalonitriles. These are immediate precursors to near-infrared absorbing phthalocyanine derivatives. Triflation of 2,3-dicyanohydroquinone extends the scope of the compound for phthalocyanine synthesis; the bis-triflate derivative is susceptible to S N Ar reactions and readily reacts with thiols to provide 3,6-bis(alkylsulfanyl) and

  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