5,6-dibutoxypyrazine-2,3-dicarbonitrile | 729613-46-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5,6-dibutoxypyrazine-2,3-dicarbonitrile
• CAS: 729613-46-1
• 化学式: C₁₄H₁₈N₄O₂
• 分子量: 274.323
• InChiKey: VVGLBKKXZQJJPX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.58
• 重原子数：
  20.0
• 可旋转键数：
  8.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  91.82
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  5,6-dibutoxypyrazine-2,3-dicarbonitrile 在 zinc chloride * 2 quinoline 作用下， 反应 1.0h， 以14%的产率得到2,3,9,10,16,17,23,24-octakis(butoxy)-1,4,8,11,15,18,22,25-(octaaza)phthalocyanine zinc(II)
  参考文献：
  名称：

  The synthesis, photochemical and photophysical properties of zinc aryloxy- and alkyloxy azaphthalocyanines

  摘要：

  Octasubstituted zinc tetrapyrazinoporphyrazines bearing butyloxy, octyloxy, 2,6-diisopropylphenoxy and 4-(hydroxymethyl)phenoxy substituents were synthesized from the corresponding 5,6-disubstituted pyrazine-2,3-dicarbonitriles using Zn(quinoline)(2)Cl-2 in yields varying from 14 to 44%. The reaction procedure proved to be efficient for the synthesis of both alkyloxy- and aryloxy- substituted zinc tetrapyrazinoporphyrazines and did not require strictly anhydrous conditions. Optimal cyclotetramerization conditions were identified for each derivative, in terms of reaction temperature, as overheating cleaved the ether bond leaving a vacant OH group on the macrocycle. The photochemical and photophysical properties of the synthesized compounds were investigated in pyridine. Singlet oxygen quantum yields (Phi(Delta)) ranged from 0.49 to 0.61 and high fluorescence quantum yields (Phi(F)) of similar to 0.30 were observed for non-aggregated compounds. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.dyepig.2010.03.023
• 作为产物：
  描述：

  5,6-二氯-2,3-二氰基吡嗪 、 正丁醇 在 三乙胺 作用下， 反应 3.0h， 生成 5,6-dibutoxypyrazine-2,3-dicarbonitrile
  参考文献：
  名称：

  The synthesis, photochemical and photophysical properties of zinc aryloxy- and alkyloxy azaphthalocyanines

  摘要：

  Octasubstituted zinc tetrapyrazinoporphyrazines bearing butyloxy, octyloxy, 2,6-diisopropylphenoxy and 4-(hydroxymethyl)phenoxy substituents were synthesized from the corresponding 5,6-disubstituted pyrazine-2,3-dicarbonitriles using Zn(quinoline)(2)Cl-2 in yields varying from 14 to 44%. The reaction procedure proved to be efficient for the synthesis of both alkyloxy- and aryloxy- substituted zinc tetrapyrazinoporphyrazines and did not require strictly anhydrous conditions. Optimal cyclotetramerization conditions were identified for each derivative, in terms of reaction temperature, as overheating cleaved the ether bond leaving a vacant OH group on the macrocycle. The photochemical and photophysical properties of the synthesized compounds were investigated in pyridine. Singlet oxygen quantum yields (Phi(Delta)) ranged from 0.49 to 0.61 and high fluorescence quantum yields (Phi(F)) of similar to 0.30 were observed for non-aggregated compounds. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.dyepig.2010.03.023

文献信息

• Peripheral substitution as a tool for tuning electron-accepting properties of phthalocyanine analogs in intramolecular charge transfer
  作者：Antonin Cidlina、Veronika Novakova、Miroslav Miletin、Petr Zimcik

  DOI：10.1039/c5dt00400d

  日期：——

  which is a pathway for excited state relaxation, was studied on the newly synthesized zinc(II) complexes of tetrapyrazinoporphyrazines bearing one fixed donor (i.e., a dialkylamino substituent). The rest of the peripheral substituents on the core was designed with respect to their different electronic effects (OBu, neopentyl, StBu, COOBu). The photophysical (singlet oxygen and fluorescence quantum yields)

  分子内电荷转移（ICT）是激发态弛豫的一种途径，已在新合成的带有一个固定供体（即二烷基氨基取代基）的四吡嗪并卟啉的锌（Ⅱ）配合物上进行了研究。在芯的周边的取代基的其余部分被设计相对于它们的不同的电子效应（OBU，新戊基，S吨卜，COOBu）。测定了该系列的光物理性质（单氧和荧光量子产率）和电化学性质（还原电位），并与不含供体部分的化合物进行了比较。信息和通信技术的效率与两个芯的缺电子字符和哈米特取代基常数相关性良好σ p。对于具有最高电子接受性取代基（COOBu）的芯，观察到最有效的ICT，对于具有最少电子缺陷的芯（被OBu取代），检测到的ICT效率最低。用H 2 SO 4滴定目标化合物的DMSO溶液指出偶氮甲碱桥的碱度在很大程度上受外围取代基特性的影响，而二烷基氨基供体中心几乎不受影响。此外，由于ICT的阻断，施主氮的质子化导致荧光量子产率的部分恢复（提高了90倍）。结果暗示，ICT效率
• Synthesis of Unsymmetrical Alkyloxy/Aryloxy-azaphthalocyanines Based on a Transetherification Reaction
  作者：Veronika Novakova、Miroslav Miletin、Kamil Kopecky、Šárka Franzová、Petr Zimcik

  DOI：10.1002/ejoc.201100689

  日期：2011.10

  found to be suitable for the isolation of unsymmetrical alkyloxy/aryloxy-AzaPcs. Undesired transetherification with alkoxides, which is common with these types of compounds, was considered to be an advantage in this approach, and an unsymmetrical AzaPc was isolated in 10 % yield. An analysis of the transetherification process is also described. Unsymmetrical zinc(II) and magnesium(II) AzaPcs showed excellent

  描述了一种导致在外围带有一个芳氧基和七个丁氧基取代基的不对称氮杂酞菁 (AzaPcs) 的方法。测试了几种环四聚方法，包括金属盐在熔体/溶液中的模板效应和 Linstead 方法，但发现只有一种方法适用于不对称烷氧基/芳氧基-AzaPcs 的分离。与这些类型的化合物常见的与醇盐的不希望的转醚化被认为是这种方法的优势，并且以 10% 的产率分离了不对称的 AzaPc。还描述了转醚化过程的分析。不对称的锌 (II) 和镁 (II) AzaPcs 显示出优异的光谱特性（λmax = 620 nm；ϵ = 1.5–2.2 × 105 dm3mol–1 cm–1）以及有希望的单线态氧（ΦΔ = 0.44 和 0.26，分别）和荧光量子产率（分别为 ΦF = 0.50 和 0.65）。无金属导数（λmax = 603 和 640 nm；ϵ = 0.80 和 1.2 × 105 dm3 mol–1 cm–1）以不同的方式耗散能量，并且
• Structural factors influencing the intramolecular charge transfer and photoinduced electron transfer in tetrapyrazinoporphyrazines
  作者：Veronika Novakova、Petr Hladík、Tereza Filandrová、Ivana Zajícová、Veronika Krepsová、Miroslav Miletin、Juraj Lenčo、Petr Zimcik

  DOI：10.1039/c3cp54731k

  日期：——

  Several structural factors were found to play a critical role in ICT efficiency. The substituent in the ortho position to the donor center significantly influences the ICT, with tert-butylsulfanyl and butoxy substituents inducing the strongest ICTs, whereas chloro, methyl, phenyl, and hydrogen substituents in this position reduce the efficiency. The strength of the donor positively influences the ICT

  合成了一系列具有一个外围连接的氨基取代基（供体）的氮杂酞菁类化合物的一系列不对称四吡嗪并卟啉（TPyzPzs），并确定了它们的光物理性质（荧光量子产率和单线态氧量子产率）。预计合成的TPyzPzs会经历分子内电荷转移（ICT），这是使它们的激发态失活的主要途径。发现一些结构性因素在ICT效率中起着至关重要的作用。在的取代基邻位的位置到供体中心显著影响ICT，与叔-丁基硫烷基和丁氧基取代基可诱导最强的ICT，而该位置的氯，甲基，苯基和氢取代基会降低效率。供体的强度对ICT效率产生积极影响，并且与TPyzPz上用作取代基的胺的氧化势相关性很好，如下所示：正丁胺< N，N-二乙胺<苯胺<吩噻嗪。TPyzPz中的ICT（具有共轭的供体和受体）也被证明比光致电子转移更强，在光电子转移中，供体和受体通过脂族连接基连接。