3,5-diphenyl-8-(2,6-dichlorophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene | 1395897-66-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 3,5-diphenyl-8-(2,6-dichlorophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene
• 英文别名: 8-(2,6-Dichlorophenyl)-2,2-difluoro-4,12-diphenyl-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene
• CAS: 1395897-66-1
• 化学式: C₂₇H₁₇BCl₂F₂N₂
• 分子量: 489.159
• InChiKey: LZSUKICQHLGDHV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.53
• 重原子数：
  34
• 可旋转键数：
  3
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  7.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  溴苯 、 10-(2,6-dichlorophenyl)-5,5-difluoro-5H-4λ⁴,5λ⁴-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine 在 tricyclohexylphosphine tetrafluoroborate 、 palladium diacetate 、 potassium carbonate 、 三甲基乙酸 作用下， 以 邻二甲苯 为溶剂， 反应 96.0h， 以39%的产率得到3,5-diphenyl-8-(2,6-dichlorophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene
  参考文献：
  名称：

  Direct palladium-catalysed C–H arylation of BODIPY dyes at the 3- and 3,5-positions

  摘要：

  开发了一种通过钯催化的 C–H 芳基化一步合成 3- 和 3,5-芳基化 BODIPY 染料的新方法，并对其适用范围进行了研究。

  DOI：

  10.1039/c2cc34549h

文献信息

• Visible-Light Excitation of BODIPYs Enables Self-Promoted Radical Arylation at Their 3,5-Positions with Diazonium Salts
  作者：Dandan Wang、Cheng Cheng、Qinghua Wu、Jun Wang、Zhengxin Kang、Xing Guo、Hao Wu、Erhong Hao、Lijuan Jiao

  DOI：10.1021/acs.orglett.9b01722

  日期：2019.7.5

  A metal- and additive-free photochemical strategy for the direct arylation of boron dipyrromethene dyes (BODIPYs) at their 3,5-positions is reported. The operationally simple approach occurs under illumination by visible light in the absence of any external photoredox catalyst. The chemistry is driven by the singlet excited state (1PS*) of BODIPYs upon visible-light absorption while successively triggering

  报道了无金属和无添加剂的光化学策略，用于在其3,5-位上直接芳构化硼二吡咯亚甲基染料（BODIPYs）。在没有任何外部光氧化还原催化剂的情况下，在可见光照射下发生操作简单的方法。化学反应是由可见光吸收时BODIPY的单重激发态（1 PS *）驱动的，同时又触发了由芳基重氮盐形成芳基的过程。此外，还首次合成了一种新型的具有近红外吸收的吲哚融合的BODIPY。
• Radical CH Arylation of the BODIPY Core with Aryldiazonium Salts: Synthesis of Highly Fluorescent Red-Shifted Dyes
  作者：Bram Verbelen、Stijn Boodts、Johan Hofkens、Noël Boens、Wim Dehaen

  DOI：10.1002/anie.201410853

  日期：2015.4.7

  describe herein the first radical CH arylation of BODIPY dyes. This novel, general, one‐step synthetic procedure uses ferrocene to generate aryl radical species from aryldiazonium salts and allows the straightforward synthesis of brightly fluorescent (Φ>0.85) 3,5‐diarylated and 3‐monoarylated boron dipyrrins in up to 86 % yield for a broad range of aryl substituents. In this way, new and complex dyes

  我们在本文中描述了BODIPY染料的第一个自由基CH芳基化。这种新颖，通用的一步合成方法使用二茂铁从芳基重氮盐生成芳基自由基物种，并允许以高达86％的产率直接合成明亮的荧光（Φ > 0.85）3,5-二芳基化和3-一芳基化硼联吡啶广泛的芳基取代基。这样，可以轻松制备具有红移光谱的新型复杂染料。
• Radical CH Alkylation of BODIPY Dyes Using Potassium Trifluoroborates or Boronic Acids
  作者：Bram Verbelen、Lucas Cunha Dias Rezende、Stijn Boodts、Jeroen Jacobs、Luc Van Meervelt、Johan Hofkens、Wim Dehaen

  DOI：10.1002/chem.201500938

  日期：2015.9.1

  synthetic procedure for the radical CH alkylation of BODIPY dyes has been developed. This new reaction generates alkyl radicals through the oxidation of boronic acids or potassium trifluoroborates and allows the synthesis of mono‐, di‐, tri‐, and tetraalkylated fluorophores in a good to excellent yield for a broad range of organoboron compounds. Using this protocol, multiple bulky alkyl groups can be introduced

  对于基团C A的一步合成方法者H已被开发BODIPY染料的烷基化。这种新的反应通过硼酸或三氟硼酸钾的氧化生成烷基自由基，并允许合成单，二，三和四烷基化的荧光团，对各种有机硼化合物的收率都非常好。使用此协议，可以将多个庞大的烷基引入BODIPY核中，从而创建固态发光BODIPY染料。
• UV—vis spectroscopy of the coupling products of the palladium-catalyzed C—H arylation of the BODIPY core
  作者：Lina Wang、Bram Verbelen、Claire Tonnelé、David Beljonne、Roberto Lazzaroni、Volker Leen、Wim Dehaen、Noël Boens

  DOI：10.1039/c3pp25385f

  日期：2013.5

  The steady-state, UV—vis electronic absorption and fluorescence emission properties of a large set of 3-aryl and 3,5-diaryl substituted difluoroboron dipyrromethene dyes obtained via direct, palladiumcatalyzed C—H (het)arylation of the BODIPY core are reported. The spectra display the narrow absorption and fluorescence emission bands and the generally quite small Stokes shifts characteristic of classic difluoroboron dipyrrins. As a function of the solvent, the spectral maxima are located within a very narrow wavelength range and are slightly red-shifted with increasing solvent polarizability, which is shown to be the crucial parameter influencing the wavelength position of the maxima. The extended π-conjugation in the 3,5-diaryl products always leads to bathochromically shifted absorption and emission spectra compared to those of the 3-aryl analogues. The derivative with a 3-mesityl substituent has blue-shifted spectra in comparison to its 3-phenyl substituted analogue, reflecting the diminished π-conjugation in the former due to steric strain. The nature of the meso-aryl has only a small effect on the spectral positions but affects the fluorescence quantum yield Φ. The majority of the dyes have high Φ (>0.85), except the compounds with meso-phenyl and meso-(p-nitrophenyl) substituents. Quantumchemical calculations were performed to evaluate the differences in spectroscopic properties upon substitution of the BODIPY core and to compare them with the corresponding experimental results.

  报告了通过直接钯催化 BODIPY 核的 CH（杂）芳基化获得的大量 3-芳基和 3,5-二芳基取代的二氟硼二吡咯亚甲基染料的稳态、紫外可见电子吸收和荧光发射特性。光谱显示出经典二氟硼二吡林的窄吸收带和荧光发射带以及通常相当小的斯托克斯位移特征。作为溶剂的函数，光谱最大值位于非常窄的波长范围内，并且随着溶剂极化率的增加而轻微红移，这被证明是影响最大值波长位置的关键参数。与 3-芳基类似物相比，3,5-二芳基产物中扩展的 π-共轭总是导致吸收和发射光谱红移。与 3-苯基取代的类似物相比，具有 3-异丙基取代基的衍生物具有蓝移光谱，反映了前者由于空间应变而减少了 π 共轭。内消旋芳基的性质对光谱位置只有很小的影响，但会影响荧光量子产率Φ。除具有内消旋苯基和内消旋（对硝基苯基）取代基的化合物外，大多数染料具有高Φ（>0.85）。通过量子化学计算来评估取代 BODIPY 核后光谱特性的差异，并将其与相应的实验结果进行比较。
• Direct palladium-catalysed C–H arylation of BODIPY dyes at the 3- and 3,5-positions
  作者：Bram Verbelen、Volker Leen、Lina Wang、Noël Boens、Wim Dehaen

  DOI：10.1039/c2cc34549h

  日期：——

  A new one-step synthetic method towards 3- and 3,5-arylated BODIPY dyes via palladium-catalysed C–H arylation has been developed and its scope has been investigated.

  开发了一种通过钯催化的 C–H 芳基化一步合成 3- 和 3,5-芳基化 BODIPY 染料的新方法，并对其适用范围进行了研究。