4,4-difluoro-8-(3,4-dimethoxyphenyl)-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene | 1357003-99-6

• 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-(3,4-dimethoxyphenyl)-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene
• 英文别名: 4,4-difluoro-8-(3,4-dimethoxyphenyl)-1,3,5,7-tetramethyl-BODIPY；BODIPY；10-(3,4-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-(3,4-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: 1357003-99-6
• 化学式: C₂₁H₂₃BF₂N₂O₂
• 分子量: 384.234
• InChiKey: YFFLULUVSIMLMY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  4,4-difluoro-8-(3,4-dimethoxyphenyl)-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene 在 四(三苯基膦)钯 、 potassium carbonate 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 24.0h， 生成
  参考文献：
  名称：

  一种基于 BODIPY 的荧光化学传感器，具有 2、6-取代，用于 S2– 的视觉和高选择性检测

  摘要：

  BODIPY 衍生物经常被用作荧光传感器来探测环境和生命系统中的有毒离子，例如硫离子 (S 2− )。虽然在 3、5、8 位的基团上进行了许多结构修饰，但很少有关于为化学传感器研究定制 2,6-取代基的例子。在此，我们设计并合成了一种 2,6-取代的 BODIPY 分子LM-BDP，用作检测水性介质中S 2−的荧光探针。通过密度泛函理论（DFT）计算和单晶X射线衍射分析研究了探针的电子结构和晶体结构。光谱研究在各种条件下进行，表明LM-BDP表现出从粉红色到深红色的显着颜色变化，以及在添加 S 2-后荧光从黄色变为粉红色通道，强度降低。选择性和灵敏度测量表明，LM-BDP只能在不到 100 秒的时间内响应 S 2−，检测限为 0.29 μM。试纸和 RAW 264.7 细胞实验中荧光图像的显着对比表明该探针是检测外源性 S 2−的合适候选者。

  DOI：

  10.1016/j.saa.2023.122741
• 作为产物：
  描述：

  在 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 4.5h， 生成 4,4-difluoro-8-(3,4-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
• An Efficient and Convenient Bromination of BODIPY Derivatives with Copper(II) Bromide
  作者：Jia-Hai Ye、Yan Zhang、Guangpu Wang、Chengmei Huang、Zhengjuan Hu、Whenchao Zhang

  DOI：10.1055/s-0031-1289637

  日期：2012.1

  mono- and dibromination of 1,3,5,7-tetramethyl-substituted BODIPYs were developed by using copper(II) bromide as the bromination reagent under mild reactions, in good to excellent yields. The selectivity of mono- or dibromination depends strongly on the additives of the reactions. copper - bromination - selectivity - fluorescent dyes - 4,4-difluoro-4-bora-3a,4a-diaza-s-indacenes

  以溴化铜（II）为溴化试剂，在温和的反应下，开发了一种高效，简便的单，二溴化1,3,5,7-四甲基取代的BODIPY的方法，收率良好。单溴或二溴的选择性很大程度上取决于反应的添加剂。 铜-溴化-选择性-荧光染料- 4,4-二氟-4-硼-3a，4a-二氮杂-小号-indacenes
• Synthesis and properties of<i>B</i>-cyano-BODIPYs
  作者：Alex L. Nguyen、Maodie Wang、Petia Bobadova-Parvanova、Quynh Do、Zehua Zhou、Frank R. Fronczek、Kevin M. Smith、M. Graça H. Vicente

  DOI：10.1142/s108842461650125x

  日期：2016.12

  A series of boron-functionalized BODIPY dyes with cyano groups were prepared from their corresponding BF₂derivatives using SnCl₄/TMSCN at room temperature for 10 min. Replacement of the fluorines by cyano groups reduces the B–N bond lengths, decreases the charge on boron, and causes characteristic [Formula: see text]B NMR chemical shifts. The 4,4[Formula: see text]-dicyano-BODIPYs show significantly enhanced stability to acidic conditions (excess TFA) and, with one exception, enhanced fluorescence quantum yields. Furthermore, the B(CN)₂-BODIPYs were non-cytotoxic to HEp2 cells, both in the dark and upon exposure to light (1.5 J/cm[Formula: see text], and rapidly accumulated within cells, localizing mainly in the lysosomes, ER and Golgi.

  利用 SnCl4/TMSCN 在室温下 10 分钟，从相应的 BF2 衍生物制备了一系列带有氰基的硼官能化 BODIPY 染料。用氰基取代氟降低了 B-N 键的长度，减少了硼上的电荷，并产生了特征性的[式：见正文]B NMR 化学位移。4,4[式中：见正文]-二氰基-BODIPY 在酸性条件（过量反式脂肪酸）下的稳定性明显增强，而且除了一个例外，荧光量子产率也有所提高。此外，B(CN)2-BODIPYs 对 HEp2 细胞无毒性，无论是在黑暗中还是暴露于光（1.5 J/cm[式：见正文]）下，都能在细胞内迅速积累，主要定位于溶酶体、ER 和高尔基体。
• Synthesis and Reactivity of 4,4-Dialkoxy-BODIPYs: An Experimental and Computational Study
  作者：Alex L. Nguyen、Petia Bobadova-Parvanova、Melissa Hopfinger、Frank R. Fronczek、Kevin M. Smith、M. Graça H. Vicente

  DOI：10.1021/ic502821m

  日期：2015.4.6

  A series of boron-disubstituted O-BODIPYs were synthesized, and their structures and spectroscopic properties were investigated using both computational and experimental methods. Three methods were investigated for the preparation of 4,4-dimethoxy-BODIPYs bearing electron-donating or electron-withdrawing 8-aryl groups: method A employs refluxing in the presence of NaOMe/MeOH, method B uses AlCl3 in refluxing dichloromethane followed by addition of methanol as nucleophile, and method C involves activation of the BODIPYs using TMSOTf in refluxing toluene followed by addition of methanol. The yields obtained depend on the method used and the structure of the starting BODIPYs; for example, 1a and 3a were most efficiently prepared using method C (98 and 70%, respectively), while 2a was best prepared by method A (50%). Methods B and C were employed for the synthesis of seven new 4,4-dialkoxy-BODIPYs. 4,4-Dipropargyloxy-BODIPY 1e reacted under Cu(I)-catalyzed alkyne-azide Huisgen cycloaddition conditions to produce 4,4-bis(1,2,3-triazole)-BODIPY 4 in 78% yield. The substitution of the fluorides for alkoxy groups on the BODIPYs had no significant effect on the absorption and emission wavelengths but altered their fluorescence quantum yields. Among this series of dialkoxy-BODIPYs, the 4,4-dipropargyloxy 1e and its corresponding bis(1,2,3-triazole) 4 show the largest quantum yields in toluene and THF, respectively.
• A new practical and highly efficient iodination of BODIPY derivatives with hypervalent iodine reagent
  作者：Jia-Hai Ye、Zhengjuan Hu、Yixin Wang、Whenchao Zhang、Yan Zhang

  DOI：10.1016/j.tetlet.2012.10.040

  日期：2012.12

  A practical, convenient, and highly efficient mono- and diiodination of 1,3,5,7-tetramethyl BODIPY derivatives was achieved by using IOAc as the iodination reagent which was generated in situ from the mixture of phenyliodine(III) diactate with iodine. The iodinated reactions were performed smoothly to give the mono- or diiodination products in good to excellent yields. (C) 2012 Elsevier Ltd. All rights reserved.