4,4-difluoro-8-(4-tert-butylphenyl)-4-bora-3a,4a-diaza-s-indacene | 870753-27-8

• 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-(4-tert-butylphenyl)-4-bora-3a,4a-diaza-s-indacene
• 英文别名: 8-(p-tert-butylphenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene；N,N'-difluoroboryl-5-(4-tert-butylphenyl)dipyrrin；10-[4-(tert-Butyl)phenyl]-5,5-difluoro-5H-dipyrrolo[1,2-c:2 inverted exclamation mark,1 inverted exclamation mark-f][1,3,2]diazaborinin-4-ium-5-uide；8-(4-tert-butylphenyl)-2,2-difluoro-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene
• CAS: 870753-27-8
• 化学式: C₁₉H₁₉BF₂N₂
• 分子量: 324.181
• InChiKey: AMMVJPMOUOYXEA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.43
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  7.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4,4-difluoro-8-(4-tert-butylphenyl)-4-bora-3a,4a-diaza-s-indacene 、 二苯基乙炔 在 bis(benzonitrile)palladium(II) chloride 、 特戊酸银 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 12.0h， 以76%的产率得到C₄₇H₃₇BF₂N₂
  参考文献：
  名称：

  Pd-Catalyzed Direct C–H Functionalization/Annulation of BODIPYs with Alkynes to Access Unsymmetrical Benzo[b]-Fused BODIPYs: Discovery of Lysosome-Targeted Turn-On Fluorescent Probes

  摘要：

  A highly efficient palladium-catalyzed direct C-H functionalization/annulation of BODIPYs with alkynes has been developed for the first time to construct a series of unsymmetrical benzo[b]-fused BODIPYs from readily available starting materials. These unsymmetrical benzo[b]-fused BODIPYs exhibit remarkably red-shifted emissions and larger Stokes shifts than classical BODIPY dyes. Cell imaging experiments and cytotoxicity assays demonstrate that BODIPYs 4c and 4d have specific lysosome-labeling capacities, turn-on fluorescence emissions in cells, and low cytotoxicity.

  DOI：

  10.1021/acs.joc.8b01239
• 作为产物：
  描述：

  对叔丁基苯甲醛 在 三氟乙酸 、 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 0.25h， 生成 4,4-difluoro-8-(4-tert-butylphenyl)-4-bora-3a,4a-diaza-s-indacene
  参考文献：
  名称：

  溴化BODIPY的合成，结构，光物理，电化学性质和抗菌活性†

  摘要：

  合成并表征了一系列单溴和二溴BODIPY（1-5），以研究染料对抗菌活性的性能。在BODIPY核心的2位和2,6-位进行区域选择性溴化反应，定量收率。内消旋-（4-羟苯基）BODIPY（5）的溴化反应出乎意料的二溴衍生物，其中溴基团安装在苯环的3,5-位而不是BODIPY核的2,6-位，由紫外线可见，荧光和1证实并支持1 H NMR光谱分析，电化学研究以及还通过单晶X射线晶体学。对于在BODIPY核心处安装的每个溴基团，我们观察到CH 2 Cl 2的吸收光谱中的红移约为16nm，发射光谱中的偏移为20-29nm 。母体和二溴衍生物的一阶还原电位之间的微小差异（5和5b）表明在溴的部分上没有发生二溴化反应。涉及C⋯H，F⋯H，H⋯H和Br⋯H的分子间相互作用是稳定分子晶体堆积的关键因素。研究了这些染料的抗菌特性，溴化衍生物显示出比其相应的母体BODIPY更好的抗菌效果，尤其是不寻常的二溴衍生物5b。

  DOI：

  10.1039/c6ra12258b

文献信息

• Structural Control of the Photodynamics of Boron−Dipyrrin Complexes
  作者：Hooi Ling Kee、Christine Kirmaier、Lianhe Yu、Patchanita Thamyongkit、W. Justin Youngblood、Matthew E. Calder、Lavoisier Ramos、Bruce C. Noll、David F. Bocian、W. Robert Scheidt、Robert R. Birge、Jonathan S. Lindsey、Dewey Holten

  DOI：10.1021/jp0525078

  日期：2005.11.1

  Boron-dipyrrin chromophores containing a 5-aryl group with or without internal steric hindrance toward aryl rotation have been synthesized and then characterized via X-ray diffraction, static and time-resolved optical spectroscopy, and theory. Compounds with a 5-phenyl or 5-(4-tert-butylphenyl) group show low fluorescence yields (similar to 0.06) and short excited-singlet-state lifetimes (similar to 500 ps), and decay primarily (> 90%) by nonradiative internal conversion to the ground state. In contrast, sterically hindered analogues having an o-tolyl or mesityl group at the 5-position exhibit high fluorescence yields (similar to 0.9) and long excited-state lifetimes (similar to 6 ns). The X-ray structures indicate that the phenyl or 4-tert-butylphenyl ring lies at an angle of similar to 60 degrees with respect to the dipyrrin framework whereas the angle is similar to 80 degrees for mesityl or o-tolyl groups. The calculated potential energy surface for the phenyl-substituted complex indicates that the excited state has a second, lower energy minimum in which the nonhindered aryl ring rotates closer to the mean plane of the dipyrrin, which itself undergoes some distortion. This relaxed, distorted excited-state conformation has low radiative probability as well as a reduced energy gap from the ground state supporting a favorable vibrational overlap factor for nonradiative deactivation. Such a distorted conformation is energetically inaccessible in a complex bearing the sterically hindered o-tolyl or mesityl group at the 5-position, leading to a high radiative probability involving conformations at or near the initial Franck-Condon form of the excited state. These combined results demonstrate the critical role of aryl-ring rotation in governing the excited-state dynamics of this class of widely used dyes.
• COMPOUND AND OPTICAL FILM COMPRISING SAME
  申请人：LG CHEM, LTD.

  公开号：US20230287008A1

  公开（公告）日：2023-09-14

  The present specification relates to a compound represented by Chemical Formula 1, a composition for forming an optical film and an optical film including the same, and a display device including the optical film.
• Pd-Catalyzed Direct C–H Functionalization/Annulation of BODIPYs with Alkynes to Access Unsymmetrical Benzo[<i>b</i>]-Fused BODIPYs: Discovery of Lysosome-Targeted Turn-On Fluorescent Probes
  作者：Xiuguang Yang、Linfeng Jiang、Mufan Yang、Huaxing Zhang、Jingbo Lan、Fulin Zhou、Xingyu Chen、Di Wu、Jingsong You

  DOI：10.1021/acs.joc.8b01239

  日期：2018.8.17

  A highly efficient palladium-catalyzed direct C-H functionalization/annulation of BODIPYs with alkynes has been developed for the first time to construct a series of unsymmetrical benzo[b]-fused BODIPYs from readily available starting materials. These unsymmetrical benzo[b]-fused BODIPYs exhibit remarkably red-shifted emissions and larger Stokes shifts than classical BODIPY dyes. Cell imaging experiments and cytotoxicity assays demonstrate that BODIPYs 4c and 4d have specific lysosome-labeling capacities, turn-on fluorescence emissions in cells, and low cytotoxicity.
• Synthesis, structure, photophysical, electrochemical properties and antibacterial activity of brominated BODIPYs
  作者：Dijo Prasannan、Darpan Raghav、Subramaniam Sujatha、Haritha Hareendrakrishna kumar、Krishnan Rathinasamy、Chellaiah Arunkumar

  DOI：10.1039/c6ra12258b

  日期：——

  reveal that dibromination does not occur on the pyrrolic moiety. The intermolecular interactions involving C⋯H, F⋯H, H⋯H, and Br⋯H are the key factors in stabilizing the molecular crystal packing. The antibacterial properties of these dyes were investigated and the brominated derivatives showed better antibacterial effects than their corresponding parent BODIPYs, particularly the unusual dibromo derivative

  合成并表征了一系列单溴和二溴BODIPY（1-5），以研究染料对抗菌活性的性能。在BODIPY核心的2位和2,6-位进行区域选择性溴化反应，定量收率。内消旋-（4-羟苯基）BODIPY（5）的溴化反应出乎意料的二溴衍生物，其中溴基团安装在苯环的3,5-位而不是BODIPY核的2,6-位，由紫外线可见，荧光和1证实并支持1 H NMR光谱分析，电化学研究以及还通过单晶X射线晶体学。对于在BODIPY核心处安装的每个溴基团，我们观察到CH 2 Cl 2的吸收光谱中的红移约为16nm，发射光谱中的偏移为20-29nm 。母体和二溴衍生物的一阶还原电位之间的微小差异（5和5b）表明在溴的部分上没有发生二溴化反应。涉及C⋯H，F⋯H，H⋯H和Br⋯H的分子间相互作用是稳定分子晶体堆积的关键因素。研究了这些染料的抗菌特性，溴化衍生物显示出比其相应的母体BODIPY更好的抗菌效果，尤其是不寻常的二溴衍生物5b。