4,4-difluoro-8-(3,5-dimethoxyphenyl)-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene | 1189166-56-0

• 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: 4,4-difluoro-8-(3,5-dimethoxyphenyl)-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene
• 英文别名: 10-(3,5-Dimethoxyphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-dipyrrolo[1,2-c:2 inverted exclamation mark,1 inverted exclamation mark-f][1,3,2]diazaborinin-4-ium-5-uide；8-(3,5-dimethoxyphenyl)-2,2-difluoro-4,6,10,12-tetramethyl-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene
• CAS: 1189166-56-0
• 化学式: C₂₁H₂₃BF₂N₂O₂
• 分子量: 384.234
• InChiKey: TYWCYGLULJGRKX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.55
• 重原子数：
  28
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  26.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4,4-difluoro-8-(3,5-dimethoxyphenyl)-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene 在 碘 、 碘酸 作用下， 以 乙醇 为溶剂， 以74.7%的产率得到4,4-difluoro-2,6-di-iodo-8-(3,5-dimethoxyphenyl)-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene
  参考文献：
  名称：

  一系列BODIPY的合成，光动力活性和定量构效关系模型

  摘要：

  这里，我们报告的11个新BODIPYs（合成14 - 24），其特征在于通过在8（芳香环的存在内消旋）的位置和碘原子对吡咯2,6位。这些分子中，连同已被我们（报道12个BODIPYs 1  -  12），代表BODIPYs表示不同的原子或基团作为芳族结构部分的取代基的一个大的面板。已经研究了两个物理化学特征（1 O 2生成速率和亲脂性），它们在光敏剂的结果中起着至关重要的作用。在体外在SKOV3细胞系中，在黑暗中处理细胞24小时，然后用绿色LED装置（通量25.2 J / cm 2）照射2 h，研究了23种PS的光诱导杀伤功效。用MTT试验评估细胞杀伤功效，并将其与内消旋未取代化合物之一进行比较（13）。为了理解取代基的可能作用，建立了基于理论整体分子描述符的预测定量构效关系（QSAR）回归模型。结果清楚地表明，芳环的存在是优异的光动力学响应的基础，而芳环上的电子效应和取代基的位置不影响光动力学功效。

  DOI：

  10.1016/j.jphotobiol.2017.01.012
• 作为产物：
  描述：

  3,5-二甲氧基苯甲醛 在 三氟化硼乙醚 、 三乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 为溶剂， 反应 52.5h， 生成 4,4-difluoro-8-(3,5-dimethoxyphenyl)-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene
  参考文献：
  名称：

  Spectroscopic, computational modeling and cytotoxicity of a series of meso-phenyl and meso-thienyl-BODIPYs

  摘要：

  A series of twenty-two BODIPY compounds were synthesized, containing various meso-phenyl and meso-thienyl groups, and their spectroscopic and structural properties were investigated using both experimental and computational methods. Further functionalization of the BODIPY framework via iodination at the 2,6-pyrrolic positions was explored in order to determine the effect of these heavy atoms on the photophysical and cytotoxicity of the meso-aryl-BODIPYs. BODIPYs bearing meso-thienyl substituents showed the largest red-shifted absorptions and emissions and reduced fluorescence quantum yields. The phototoxicity of the BODIPYs in human carcinoma HEp2 cells depends on both the presence of iodines and the nature of the meso-aryl groups. Six of the eleven 2,6-diiodo-BODIPYs investigated showed at least a sevenfold enhancement in phototoxicity (IC50 = 3.5-28 mu M at 1.5 J/cm(2)) compared with the non-iodinated BODIPYs, while the others showed no cytotoxicity, while their singlet oxygen quantum yields ranged from 0.02 to 0.76. Among the series investigated, BODIPYs 2a and 4a bearing electron-donating meso-dimethoxyphenyl substituents showed the highest phototoxicity and dark/phototoxicity ratio, and are therefore the most promising for application in PDT. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2013.07.017

文献信息

• Heavy-atom-free charge transfer photosensitizers: Tuning the efficiency of BODIPY in singlet oxygen generation via intramolecular electron donor-acceptor interaction
  作者：Wenbin Hu、Yanhe Lin、Xian-Fu Zhang、Mingna Feng、Siwen Zhao、Jing Zhang

  DOI：10.1016/j.dyepig.2019.01.019

  日期：2019.5

  lifetime, excited triplet state formation, and singlet oxygen formation properties are measured. DFT quantum chemical computation is also carried out to explain the experiments. The occurrence of intra-molecular CT is confirmed by UV-Vis absorption, fluorescence properties and quantum chemical computation. The triplet excited state formation is evidenced by laser flash photolysis technique. The quantitative

  在产生单线态氧（以测试的电荷转移（CT）的可调谐性的基于BODIPY光敏剂1 Δ克），十二内消旋已经合成并完全表征了-苯基-BODIPY（供体-受体）型化合物，其中苯基部分分别被0、1、2和3个甲氧基改性以增加其电子给体能力。测量了UV-Vis吸收光谱，荧光发射光谱，荧光量子产率，荧光寿命，激发三重态形成和单重态氧形成性质。还进行了DFT量子化学计算以解释实验。通过UV-Vis吸收，荧光性质和量子化学计算证实了分子内CT的发生。通过激光闪光光解技术证明了三重激发态的形成。通过DPBF（二苯基异苯并呋喃）化学捕集方法证明了光敏单线态氧的定量形成。 这种类型的CT BODIPY光敏剂的显示产生单线态氧良好的可调谐性（1 Δ克）。当供体上的甲氧基数增加时（使CT增强），单线态氧的生成效率从0.070升高到0.30。当溶剂极性增加（CT也增强）时，单线态氧的产生效率也显着提高。单线态氧产生的增加伴
• β-Formyl-BODIPYs from the Vilsmeier−Haack Reaction
  作者：Lijuan Jiao、Changjiang Yu、Jilong Li、Zhaoyun Wang、Min Wu、Erhong Hao

  DOI：10.1021/jo901407h

  日期：2009.10.2

  A series of beta-formyl-BODIPYs 2 were synthesized in high yields from tetramethyl-BODIPYs 1 via the Vilsmeier-Haack reaction and were further functionalized using a Knoevenagel condensation to generate novel BODIPYs 3 and 4.
• Spectroscopic, computational modeling and cytotoxicity of a series of meso-phenyl and meso-thienyl-BODIPYs
  作者：Jaime H. Gibbs、Larry T. Robins、Zehua Zhou、Petia Bobadova-Parvanova、Michael Cottam、Gregory T. McCandless、Frank R. Fronczek、M. Graça H. Vicente

  DOI：10.1016/j.bmc.2013.07.017

  日期：2013.9

  A series of twenty-two BODIPY compounds were synthesized, containing various meso-phenyl and meso-thienyl groups, and their spectroscopic and structural properties were investigated using both experimental and computational methods. Further functionalization of the BODIPY framework via iodination at the 2,6-pyrrolic positions was explored in order to determine the effect of these heavy atoms on the photophysical and cytotoxicity of the meso-aryl-BODIPYs. BODIPYs bearing meso-thienyl substituents showed the largest red-shifted absorptions and emissions and reduced fluorescence quantum yields. The phototoxicity of the BODIPYs in human carcinoma HEp2 cells depends on both the presence of iodines and the nature of the meso-aryl groups. Six of the eleven 2,6-diiodo-BODIPYs investigated showed at least a sevenfold enhancement in phototoxicity (IC50 = 3.5-28 mu M at 1.5 J/cm(2)) compared with the non-iodinated BODIPYs, while the others showed no cytotoxicity, while their singlet oxygen quantum yields ranged from 0.02 to 0.76. Among the series investigated, BODIPYs 2a and 4a bearing electron-donating meso-dimethoxyphenyl substituents showed the highest phototoxicity and dark/phototoxicity ratio, and are therefore the most promising for application in PDT. (C) 2013 Elsevier Ltd. All rights reserved.
• Synthesis, photodynamic activity, and quantitative structure-activity relationship modelling of a series of BODIPYs
  作者：Enrico Caruso、Marzia Gariboldi、Alessandro Sangion、Paola Gramatica、Stefano Banfi

  DOI：10.1016/j.jphotobiol.2017.01.012

  日期：2017.2

  Here we report the synthesis of eleven new BODIPYs (14–24) characterized by the presence of an aromatic ring on the 8 (meso) position and of iodine atoms on the pyrrolic 2,6 positions. These molecules, together with twelve BODIPYs already reported by us (1 − 12), represent a large panel of BODIPYs showing different atoms or groups as substituent of the aromatic moiety. Two physico-chemical features

  这里，我们报告的11个新BODIPYs（合成14 - 24），其特征在于通过在8（芳香环的存在内消旋）的位置和碘原子对吡咯2,6位。这些分子中，连同已被我们（报道12个BODIPYs 1  -  12），代表BODIPYs表示不同的原子或基团作为芳族结构部分的取代基的一个大的面板。已经研究了两个物理化学特征（1 O 2生成速率和亲脂性），它们在光敏剂的结果中起着至关重要的作用。在体外在SKOV3细胞系中，在黑暗中处理细胞24小时，然后用绿色LED装置（通量25.2 J / cm 2）照射2 h，研究了23种PS的光诱导杀伤功效。用MTT试验评估细胞杀伤功效，并将其与内消旋未取代化合物之一进行比较（13）。为了理解取代基的可能作用，建立了基于理论整体分子描述符的预测定量构效关系（QSAR）回归模型。结果清楚地表明，芳环的存在是优异的光动力学响应的基础，而芳环上的电子效应和取代基的位置不影响光动力学功效。