3,6-二癸基酞腈 | 119931-48-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 3,6-二癸基酞腈
• 英文名称: 3,6-bis(decyl)phthalonitrile
• 英文别名: 3,6-didecylphthalonitrile；3,6-didecylbenzene-1,2-dicarbonitrile
• CAS: 119931-48-5
• 化学式: C₂₈H₄₄N₂
• 分子量: 408.671
• InChiKey: DSZGQEHPKNNPFU-UHFFFAOYSA-N

物化性质

• 熔点：
  70 °C
• 沸点：
  530.6±38.0 °C(Predicted)
• 密度：
  0.93±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  11.6
• 重原子数：
  30
• 可旋转键数：
  18
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  47.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,6-二癸基酞腈 在 戊醇 、 lithium 、 溶剂黄146 作用下， 以 戊醇 为溶剂， 反应 16.5h， 生成 1,4,8,11,15,22,25-octadecylphthalocyanine
  参考文献：
  名称：

  Synthesis and electrochemical characterisation of some long chain 1,4,8,11,15,18,22,25-octa-alkylated metal-free and zinc phthalocyanines possessing discotic liquid crystalline properties

  摘要：

  一系列长链（C10、C12、C15 和 C18）3,6-二烷基邻苯二甲酰亚胺经 4 个步骤由噻吩制备而成，并转化为标题酞菁的无金属锌衍生物。使用 1H NMR、MALDI-TOF ms 和溶液相电子（UV-VIS）光谱对对称大环进行了表征。在二氯甲烷或 1,2-二氯乙烷中，拥有较短烷基取代基的无金属大环的四个环基氧化还原过程的电位范围为-1.8 至 1.2 V vs. Ag/Ag+。随着 8 个烷基取代基链长的增加，可逆性变差。锌配合物的氧化还原过程不像无金属酞菁那样明确。所有化合物都表现出盘状热向性液晶行为，研究采用了偏光光学显微镜和差示扫描量热法（DSC）。最多可检测到三种不同的介相。与不含金属的化合物相比，锌衍生物在更高的温度下显示出液晶特性。无金属酞菁和带有 C12 链的锌酞菁的结晶到盘状液晶介相转变温度最低。在玻璃上浇铸的薄膜（厚度约为 1000 埃）的变温紫外-可见光谱中，获得了结晶、介相和各向同性液相化合物的光谱。各向同性液态薄膜的光谱与同一化合物溶液的光谱相似。

  DOI：

  10.1039/b006123i
• 作为产物：
  描述：

  3,6-二羟基邻苯二甲腈 在 2,6-二甲基吡啶 、 bis(triphenylphosphine)nickel(II) chloride 、 正丁基锂 、 三苯基膦 、 lithium chloride 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 31.0h， 生成 3,6-二癸基酞腈
  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

• 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。
• Efficient singlet oxygen generation by triptycene substituted A3B type zinc(II) phthalocyanine photosensitizers
  作者：Bandar R. Al-Sohaimi、Mehmet Pişkin、Bader S. Ghanem、Shaya Y. Al-Raqa、Mahmut Durmuş

  DOI：10.1016/j.tetlet.2015.12.004

  日期：2016.1

  time. Their photophysical and photochemical properties were investigated as solutions in toluene and obtained values were compared with unsubstituted zinc(II) phthalocyanine for determination of substitution effect. Both newly synthesized phthalocyanines showed high singlet oxygen generation making them good candidates as photosensitizers for photocatalytic reactions.

  阿3 B型不对称8,11,15,18,22,25十六烷基- 2,3-（9,10-二辛基-6,7-二甲氧基-2,3- dioxytriptycene）（11）和8,11， 15,18,22,25十六烷基- 2,3-（9,10-十一烷基-6,7-二甲氧基-2,3- dioxytriptycene）（12）锌（II）酞菁被首次合成。以甲苯溶液的形式研究了它们的光物理和光化学性质，并将所得值与未取代的酞菁锌（II）进行了比较，以确定取代效果。两种新合成的酞菁均显示出高的单线态氧生成，使其成为光催化反应的光敏剂的良好候选者。
• Phthalocyanine Analogues: Unexpectedly Facile Access to Non‐Peripherally Substituted Octaalkyl Tetrabenzotriazaporphyrins, Tetrabenzodiazaporphyrins, Tetrabenzomonoazaporphyrins and Tetrabenzoporphyrins
  作者：Andrew N. Cammidge、Isabelle Chambrier、Michael J. Cook、David L. Hughes、Muhibur Rahman、Lydia Sosa‐Vargas

  DOI：10.1002/chem.201002176

  日期：2011.3.7

  by reaction with benzyl and long‐chain alkyl Grignard reagents unexpectedly gave only the parent macrocycle unsubstituted at the meso position. The synthetic protocols are by far the most straightforward and convenient means to access these interesting, but scarcely studied, classes of material. The new series of substituted macrocyclic compounds, obtained as the metal‐free and magnesium‐ and copper(II)‐metallated

  已经实现了酞菁/苯并卟啉杂化结构的受控合成。我们报告了一种简单的方法，该方法通过用不同量的格氏试剂处理3,6-二烷基邻苯二甲腈来获得四苯并三氮杂卟啉（TBTAP），四苯并二氮杂卟啉（TBDAP），四苯并单氮杂卟啉（TBMAP）和四苯并卟啉（TBP）大环的非周边八烷基取代衍生物甲基溴。该范围的大环产物不是通过先前报道的格氏试剂与4-取代的邻苯二甲腈的相应反应或MeMgBr与4,5-二烷基邻苯二甲腈的反应而获得的。尝试形成介观通过用苄基和长链烷基格氏试剂反应从3,6-二烷基邻苯二甲腈取代TBTAP意外得到仅在未取代的母体大环内消旋位置。到目前为止，合成协议是访问这些有趣但很少研究的材料类别的最直接，最方便的方法。以无金属以及镁和铜（II）的金属化衍生物形式获得的一系列新的取代的大环化合物，其紫外/可见光谱的趋势与小林在其他地方所预测的一致。新家族的特征允许进一步的趋势被确定为中观氮原子被次甲基
• Synthesis and electrochemical characterisation of some long chain 1,4,8,11,15,18,22,25-octa-alkylated metal-free and zinc phthalocyanines possessing discotic liquid crystalline properties
  作者：Jannie C. Swarts、Ernie H. G. Langner、Nina Krokeide-Hove、Michael J. Cook

  DOI：10.1039/b006123i

  日期：——

  A series of long chain (C10, C12, C15 and C18) 3,6-dialkylated phthalonitriles, prepared in 4 steps from thiophene, have been converted into the title phthalocyanines as metal-free and zinc derivatives. The symmetric macrocycles were characterised using 1H NMR, MALDI-TOF ms and solution phase electronic (UV-VIS) spectroscopy. Four ring-based redox processes for the metal-free macrocycles possessing shorter alkyl substituents could be identified in the potential range −1.8 to 1.2 V vs. Ag/Ag+ in dichloromethane or 1,2-dichloroethane. Reversibility became poorer with an increase in chain length of the eight alkyl substituents. The redox processes of the zinc complexes were not as well defined as those of the metal-free phthalocyanines. All compounds exhibited discotic thermotropic liquid crystal behaviour, which was studied using polarised optical microscopy and differential scanning calorimetry (DSC). Up to three different mesophases were detected. The zinc derivatives showed liquid crystalline behaviour at much higher temperatures than the metal-free compounds. The metal-free and zinc phthalocyanines with C12 chains had the lowest crystalline to discotic liquid crystalline mesophase transition temperatures. Variable temperature UV-VIS spectra of thin films (ca. 1000 Å thick) of the title compounds cast on glass were obtained for the compounds in the crystalline, meso- and isotropic liquid phase. The spectrum of a thin film of the isotropic liquid resembled the spectrum obtained from a solution of the same compound.

  一系列长链（C10、C12、C15 和 C18）3,6-二烷基邻苯二甲酰亚胺经 4 个步骤由噻吩制备而成，并转化为标题酞菁的无金属锌衍生物。使用 1H NMR、MALDI-TOF ms 和溶液相电子（UV-VIS）光谱对对称大环进行了表征。在二氯甲烷或 1,2-二氯乙烷中，拥有较短烷基取代基的无金属大环的四个环基氧化还原过程的电位范围为-1.8 至 1.2 V vs. Ag/Ag+。随着 8 个烷基取代基链长的增加，可逆性变差。锌配合物的氧化还原过程不像无金属酞菁那样明确。所有化合物都表现出盘状热向性液晶行为，研究采用了偏光光学显微镜和差示扫描量热法（DSC）。最多可检测到三种不同的介相。与不含金属的化合物相比，锌衍生物在更高的温度下显示出液晶特性。无金属酞菁和带有 C12 链的锌酞菁的结晶到盘状液晶介相转变温度最低。在玻璃上浇铸的薄膜（厚度约为 1000 埃）的变温紫外-可见光谱中，获得了结晶、介相和各向同性液相化合物的光谱。各向同性液态薄膜的光谱与同一化合物溶液的光谱相似。
• 1,4,8,11,15,18-Hexa-alkyl-22,25-bis(carboxypropyl)phthalocyanines: materials designed for deposition as Langmuir–Blodgett films
  作者：Michael J. Cook、Mervyn F. Daniel、Kenneth J. Harrison、Neil B. McKeown、Andrew J. Thomson

  DOI：10.1039/c39870001148

  日期：——

  Examples of the title compounds form stable monolayers on a water surface and are transferred onto hydrophobic silica as Langmuir–Blodgett films, which are highly ordered as judged by polarised absorption spectroscopy.

  标题化合物的例子在水表面形成稳定的单层，并以Langmuir-Blodgett膜的形式转移到疏水性二氧化硅上，通过偏振吸收光谱法可以确定其高度有序。