2-Cyano-3-(4-cyanophenyl)prop-2-enethioamide

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-Cyano-3-(4-cyanophenyl)prop-2-enethioamide
• 化学式: C₁₁H₇N₃S
• mdl: MFCD02025384
• 分子量: 213.263
• InChiKey: UBRXJZYRGLBYEC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  106
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-Cyano-3-(4-cyanophenyl)prop-2-enethioamide 在 bis-triphenylphosphine-palladium(II) chloride 、 N-溴代丁二酰亚胺(NBS) 、 potassium carbonate 作用下， 以 乙二醇二甲醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 生成
  参考文献：
  名称：

  3-Aryl-2-(thiazol-2-yl)acrylonitriles assembled with aryl/hetaryl rings: Design of the optical properties and application prospects

  摘要：

  New fluorescent thiazoles were designed and synthesized based on a 3-aryl-2-(thiazol-2-yl)acrylonitrile core. Three synthetic approaches were developed to introduce specific combinations of substituents at the 2-, 4- and 5-thiazole positions. The obtained thiazolyl-2-acrylonitriles exhibited a wide range of fluorescent colours (from green to red), long wavelength maxima and intensity depending on the combination of the substituents located at rings A, B and C. The expanded photophysical investigation established the best substituent combinations to increase their emission. Absorption and emission were studied in solvents with different polarities, as well as in DMSO-water and dioxane-water mixtures. The thiazoles showed multifunctional properties and exhibited good emission in the solid phase and in suspension (aggregation induced enhancement emission/AIEE effect). Photophysical investigations revealed a large Stokes shift, significant positive solvatochmmism, and the tunability of the colour and intensity. Sharp strengthening of the emission intensity of the thiazoles was observed upon stimulation with some acid (H2SO4 and BF3 center dot OEt2) in solvents and in the solid phase (HCl). State-of-the-art quantum mechanical calculations were performed to interpret the experimental findings. Biological experiments revealed the good penetration of the thiazoles into living cells and the accumulation both in lysosomes and, to a lesser extent, near membranes.

  DOI：

  10.1016/j.dyepig.2020.108836

文献信息

• Design and synthesis of disubstituted and trisubstituted thiazoles as multifunctional fluorophores with large Stokes shifts
  作者：Polina O. Suntsova、Alexander K. Eltyshev、Tatiana A. Pospelova、Pavel A. Slepukhin、Enrico Benassi、Nataliya P. Belskaya

  DOI：10.1016/j.dyepig.2019.02.051

  日期：2019.7

  long-wavelength emission, large Stokes shifts and good quantum yields. Additionally, the thiazole-2-acrylonitrile fluorophores demonstrate a multifunctional character with significant fluorescence properties (i.e., quantum yields and a large Stokes shift in both the liquid and solid states). The influences of different factors, including the solvent polarity, on the fluorescence properties of the synthesized

  合成了一系列基于噻唑核的荧光团，显示出对结构变化和微环境都非常敏感。取代基的电子性质，空间效应和在分子中的位置的简单修饰，可通过表现出长波长发射，大斯托克斯位移和良好的量子产率来调节所研究化合物的光物理性质及其对环境的敏感性。此外，噻唑-2-丙烯腈荧光团显示出具有显着荧光特性（即，在液态和固态下的量子产率和较大的斯托克斯位移）的多功能特征。详细讨论了溶剂极性等不同因素对合成化合物荧光性质的影响。量子力学方法被用来理解潜在的转变并解释实验结果。这项工作为设计具有较大斯托克斯位移的新型传感器提供了进一步的信息。
• Photocaging of Carboxylic Function Bearing Biomolecules by New Thiazole Derived Fluorophore
  作者：Aleksey A. Gagarin、Artem S. Minin、Vadim A. Shevyrin、Irena P. Kostova、Enrico Benassi、Nataliya P. Belskaya

  DOI：10.1002/chem.202302079

  日期：2023.10.23

  The design and synthesis of a new fluorophore containing an arylidene thiazole scaffold resulted in a compound with good photophysical characteristics. Furthermore, the thiazole C5‐methyl group was easily modified into specific functional groups (CH₂Br and CH₂OH) for the formation of a series of photocourier molecules containing model compounds (benzoic acids), as well as prodrugs, including salicylic acid, caffeic acid, and chlorambucil via a “benzyl” linker. Spectral characteristics (¹H, ¹³C NMR, and high‐resolution mass spectra) corresponded to the proposed structures. The photocourier molecules demonstrated absorption with high values of coefficient of molar extinction, exhibited contrasting green emission, and showed good dark stability. The mechanism of the photorelease was investigated through spectral analysis, HPLC‐HRMS, and supported by TD‐DFT calculations. The photoheterolysis and elimination of carboxylic acids were proved to occur in the excited state, yielding a carbocation as an intermediate moiety. The fluorophore structure provided stability to the carbocation through the delocalization of the positive charge via resonance structures. Viability assessment of Vero cells using the MTT‐test confirmed the weak cytotoxicity of prodrugs without irradiation and it increase upon UV‐light.

  摘要 通过设计和合成含有芳基噻唑支架的新型荧光团，得到了一种具有良好光物理特性的化合物。此外，噻唑的 C5-甲基基团很容易被修饰成特定的官能团（CH2Br 和 CH2OH），从而通过 "苄基 "连接物形成一系列含有模型化合物（苯甲酸）的光电载体分子以及原药，包括水杨酸、咖啡酸和氯霉素。光谱特征（1H、13C NMR 和高分辨率质谱）与提出的结构相符。光电载体分子的吸收具有较高的摩尔消光系数值，显示出对比鲜明的绿色发射，并具有良好的暗稳定性。通过光谱分析、HPLC-HRMS 和 TD-DFT 计算，研究了光释放的机理。研究证明，羧酸的光解和消除发生在激发态，并产生一个碳代化合物作为中间分子。荧光团结构通过共振结构使正电荷分散，从而为碳位化合物提供了稳定性。使用 MTT 测试法对 Vero 细胞进行的活力评估证实，原药在未经照射的情况下细胞毒性较弱，而在紫外线照射下细胞毒性会增强。