2,6-dibromo-4,4-difluoro-8-phenyl-4-bora-3a,4a-diaza-s-indacene | 1350764-65-6

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: 2,6-dibromo-4,4-difluoro-8-phenyl-4-bora-3a,4a-diaza-s-indacene
• 英文别名: 2,8-dibromo-5,5-difluoro-10-phenyl-5H-4λ⁴,5λ⁴-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine；5,11-Dibromo-2,2-difluoro-8-phenyl-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene
• CAS: 1350764-65-6
• 化学式: C₁₅H₉BBr₂F₂N₂
• 分子量: 425.866
• InChiKey: SITPAHNWUBBUCN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.62
• 重原子数：
  22
• 可旋转键数：
  1
• 环数：
  4.0
• 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

• 作为反应物：
  描述：

  2,6-dibromo-4,4-difluoro-8-phenyl-4-bora-3a,4a-diaza-s-indacene 在 硫酸 、 dicyclohexyl(2',4',6'-triisopropyl-[1,1'-biphenyl]-3-yl)phosphine 、 palladium diacetate 、 caesium carbonate 、 溶剂黄146 作用下， 以 1,4-二氧六环 、 氯仿 、 水 为溶剂， 反应 60.08h， 生成
  参考文献：
  名称：

  Synthesis and Properties of Benzothieno[b]-Fused BODIPY Dyes

  摘要：

  Two benzothieno[b]-fused BODIPYs, BT-BODIPY and BBT-BODIPY, in which one parent BODIPY core is fused with one and two benzothieno rings, respectively, were synthesized from BODIPYs substituted with 2-(methylsulfinyl)phenyl at the beta-position. The first H2SO4-induced cyclization and deborylation afforded benzothieno[b]-fused dipyrrin derivatives, which can easily complex with BF3 center dot OEt2 to form the desired benzothieno[b]-fused BODIPYs. It was revealed that the fusion of the benzothieno ring is more effective at extending conjugation than simple attachment of the 2-(methylthio)phenyl substituent, which presumably results from conformational restriction. Compared with the corresponding unstrained SPh-BODIPY and BSPh-BODIPY, which contain one and two 2-(methylthio)phenyl groups at the beta-position, BT-BODIPY and BBT-BODIPY display red shifted absorption, increased absorptivity, and fluorescence efficiency. Furthermore, the ring fusion is also helpful to increase stability of the formed cation in BBT-BODIPY. Thus, BBT-BODIPY exhibits very intriguing properties, such as intense absorption and emission in the red region, very sharp emission spectra, and reversible oxidation and reduction potentials.

  DOI：

  10.1021/acs.joc.5b02531
• 作为产物：
  描述：

  4,4-difluoro-8-phenyl-4-bora-3a,4a-diaza-s-indacene 在 溴 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以93%的产率得到2,6-dibromo-4,4-difluoro-8-phenyl-4-bora-3a,4a-diaza-s-indacene
  参考文献：
  名称：

  硼二吡咯亚甲基（BODIPY）染料的区域选择性逐步溴化反应

  摘要：

  卤代BODIPY是光动力疗法（PDT）的重要合成前体和潜在的敏化剂。使用溴区域选择性地逐步生成单溴到七溴BODIPY的吡咯未取代的BODIPY进行亲电溴化，收率好至极好。这些所得bromoBODIPYs施加用于区域选择性取代和Suzuki偶联反应，以生成BODIPYs 4，5，6，和7产量高到极好。根据NMR和X射线分析结果，逐步溴化首先在2,6-，然后在3,5-，最后在1,7-位发生，而区域选择性取代首先在3,5-发生，然后在发色团的1,7位。研究了这些生成的BODIPY的光谱性质，显示了这些bromoBODIPY作为PDT的敏化剂的潜在应用。

  DOI：

  10.1021/jo201754m

文献信息

• 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。
• Regioselective 2,6-dihalogenation of BODIPYs in 1,1,1,3,3,3-hexafluoro-2-propanol and preparation of novel meso-alkyl polymeric BODIPY dyes
  作者：Liang Wang、Jian-Wei Wang、Ai-jun Cui、Xiao-Xiao Cai、Yan Wan、Qun Chen、Ming-Yang He、Wei Zhang

  DOI：10.1039/c3ra41298a

  日期：——

  Regioselective 2,6-halogenation of BODIPYs in hexafluoro-2-propanol (HFIP) afforded products in less than 5 min. Halogenated BODIPYs were subjected to Pd-catalyzed cross-coupling reactions to form novel meso-alkyl polymeric BODIPY dyes.

  在六氟异丙醇（HFIP）中，对BODIPYs进行区域选择性的2,6-卤化反应，在不到5分钟内获得了产物。卤化的BODIPYs经过Pd催化的交叉偶联反应形成了新型的meso-烷基聚合物BODIPY染料。
• Designing a Red‐Emitting Viscosity‐Sensitive BODIPY Fluorophore for Intracellular Viscosity Imaging
  作者：Karolina Maleckaitė、Jelena Dodonova、Stepas Toliautas、Rugilė Žilėnaitė、Džiugas Jurgutis、Vitalijus Karabanovas、Sigitas Tumkevičius、Aurimas Vyšniauskas

  DOI：10.1002/chem.202102743

  日期：2021.12

  Going into the red: We report a new red-emitting fluorescent viscosity probe suitable for intracellular viscosity imaging of MCF-7 breast cancer cells. This was achieved with the help of DFT calculations that allowed the viscosity sensitivity of the fluorophore to be predicted before synthesis.

  走向红色：我们报告了一种新的发红光的荧光粘度探针，适用于 MCF-7 乳腺癌细胞的细胞内粘度成像。这是在 DFT 计算的帮助下实现的，该计算允许在合成之前预测荧光团的粘度敏感性。
• Engineering a Dual‐Functionalized PolyHIPE Resin for Photobiocatalytic Flow Chemistry
  作者：Emmanouil Broumidis、Francesca Paradisi

  DOI：10.1002/anie.202401912

  日期：——

  A new polyHIPE (high internal phase emulsion) resin served as a solid support system for both a halogenase enzyme and a benzothiadiazole (BTZ) photosensitizer. It was then used in a continuous flow system for the electrophilic bromination of aromatic substrates. This support offers excellent single pass and recirculation yields. It is stable and reusable and allows for straightforward product separation

  新型聚HIPE（高内相乳液）树脂可作为卤化酶和苯并噻二唑（BTZ）光敏剂的固体支撑系统。然后将其用于连续流动系统中，用于芳香族底物的亲电溴化。这种支持提供了出色的单程和再循环产量。它稳定且可重复使用，并且由于其异质性，可以直接进行产品分离。
• Regioselective Stepwise Bromination of Boron Dipyrromethene (BODIPY) Dyes
  作者：Lijuan Jiao、Weidong Pang、Jinyuan Zhou、Yun Wei、Xiaolong Mu、Guifeng Bai、Erhong Hao

  DOI：10.1021/jo201754m

  日期：2011.12.16

  Halogenated BODIPYs are important synthetic precursors and potential sensitizers for photodynamic therapy (PDT). Electrophilic bromination of pyrrolic-unsubstituted BODIPYs using bromine regioselectively generated mono- to heptabromoBODIPYs in a stepwise fashion in good to excellent yields. These resultant bromoBODIPYs were applied for regioselective substitution and Suzuki coupling reaction to generate

  卤代BODIPY是光动力疗法（PDT）的重要合成前体和潜在的敏化剂。使用溴区域选择性地逐步生成单溴到七溴BODIPY的吡咯未取代的BODIPY进行亲电溴化，收率好至极好。这些所得bromoBODIPYs施加用于区域选择性取代和Suzuki偶联反应，以生成BODIPYs 4，5，6，和7产量高到极好。根据NMR和X射线分析结果，逐步溴化首先在2,6-，然后在3,5-，最后在1,7-位发生，而区域选择性取代首先在3,5-发生，然后在发色团的1,7位。研究了这些生成的BODIPY的光谱性质，显示了这些bromoBODIPY作为PDT的敏化剂的潜在应用。