4,4-difluoro-3,5-dimethyl-8-(4-piperidinophenyl)-4-bora-3a,4a-diaza-s-indacene | 865479-47-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 4,4-difluoro-3,5-dimethyl-8-(4-piperidinophenyl)-4-bora-3a,4a-diaza-s-indacene
• 英文别名: 5,5-difluoro-3,7-dimethyl-10-(4-(piperidin-1-yl)phenyl)-5H-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinin-4-ium-5-uide
• CAS: 865479-47-6
• 化学式: C₂₂H₂₄BF₂N₃
• 分子量: 379.26
• InChiKey: WABJVVDBPMRGSX-UHFFFAOYSA-N

计算性质

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

反应信息

• 作为产物：
  描述：

  2-吡咯甲醛 在 hydrazine hydrate 、 四甲基乙二胺 、 3,4-bis((3,5-bis(trifluoromethyl)phenyl)amino)cyclobut-3-ene-1,2-dione 、 氢气 、 palladium diacetate 、 sodium hydroxide 、 正丁基二(1-金刚烷基)膦 作用下， 以 甲苯 为溶剂， 20.0~160.0 ℃ 、1.0 MPa 条件下， 反应 28.5h， 生成 4,4-difluoro-3,5-dimethyl-8-(4-piperidinophenyl)-4-bora-3a,4a-diaza-s-indacene
  参考文献：
  名称：

  羰基化作为新串联反应的关键步骤——通往 BODIPY 的途径

  摘要：

  在此，提出了 BODIPY 的高效五步反应序列。 55 种衍生物的合成总产率高达 78%，这表明我们能够扩大易于获得的 BODIPY 的范围，同时证明我们开发的方法的普遍适用性和优势。

  DOI：

  10.1002/chem.202303752

文献信息

• Modifying the meso-phenyl with electron donating amino groups strongly enhances BODIPY's ability as good singlet oxygen photosensitizer
  作者：Wenbin Hu、Xian-Fu Zhang、Xulin Lu、Shuai Lan、Dandan Tian、Tingting Li、Liangxia Wang、Siwen Zhao、Mingna Feng、Jing Zhang

  DOI：10.1016/j.dyepig.2017.10.018

  日期：2018.2

  correlated with singlet oxygen formation efficiency. The results are explained by PCT (photoinduced charge transfer) mechanism. The presence of the methyl groups at 1 and 7 positions disables the rotation of the phenyl ring, and therefore, the corresponding BODIPY 1a, 2a, and 3a were characterized by significant higher singlet oxygen generation efficiency and fluorescence quantum yield than that of BODIPY

  我们合成了三种1,3,5,7-四甲基-BODIPY（1a，2a，3a）和三种3,5-二甲基-BODIPY（1b，2b，3b）光敏剂，其中内消旋位置被不同的对位修饰-氨基苯基。通过紫外可见吸收光谱，荧光发射光谱方法研究了BODIPYs的单线态氧的产生和光物理性质。发现这些BODIPY衍生物是环境敏感的和荧光光敏剂，其在中等极性环境中显示出产生单线态氧的高效率，而在极性和非极性溶剂中几乎没有光活性。同时，它们在非极性溶剂中具有高荧光性，但在极性溶剂中的发射性低得多，ICT发射发生在中等极性溶剂中，并且与单线态氧的形成效率相关。该结果通过PCT（光致电荷转移）机理来解释。在1和7位上甲基的存在会导致苯环无法旋转，因此，与BODIPY 1b， 2b和3b相比， 1a， 2a和3a的单线态氧产生效率和荧光量子产率明显高。
• Photophysical Properties of Borondipyrromethene Analogues in Solution
  作者：Wenwu Qin、Mukulesh Baruah、Mark Van der Auweraer、Frans C. De Schryver、Noël Boens

  DOI：10.1021/jp052626n

  日期：2005.8.1

  The photophysical properties of seven new 8-(p-substituted)phenyl analogues of 4,4-difluoro-3,5-dimethyl-8-(aryl)-4-bora-3a,4a-diaza-s-indacene (derivatives of the well-known fluorophore BODIPY) in several solvents have been studied by means of absorption and steady-state and time-resolved fluorimetry. For each compound, the fluorescence quantum yield and lifetime are lower in solvents with higher polarity owing to an increase in the rate of nonradiative deactivation. Increasing the electron withdrawing strength of the p-substituent on the phenyl group in position 8 also leads to lower fluorescence quantum yields and lifetimes. When the p-substituent on the phenyl group in position 8 is a tertiary amine [8-(4-piperidinophenyl), 8-(4-N,N-dimethylaminophenyl), and 8-(4-morpholinophenyl)], the low quantum yields of these compounds in more polar solvents can be rationalized by the inversion of the energy levels of an apolar, highly fluorescent and a polar, nonfluorescent excited state, where charge transfer from the tertiary amine to the BODIPY unit occurs. These amine analogues can be protonated at low pH in aqueous solution. Fluorescence titrations yielded pK(a) values of their conjugate ammonium salts which are in agreement with the electron donating tendency of the amine group: piperidino (4.15) > dimethylamino (2.37) > morpholino (1.47), with the pK(a) values in parentheses. The rate constant of radiative deactivation (k(f)) is the same for all compounds in all solvents studied (k(f) = 1.4 x 10(8) s(-1)).
• Carbonylation as a Key Step in New Tandem Reactions – A Route to BODIPYs
  作者：Lukas Miller、Alba Impelmann、Felix Bauer、Bernhard Breit

  DOI：10.1002/chem.202303752

  日期：2024.2.12

  Herein, a highly efficient five-step reaction sequence for BODIPYs is presented. The synthesis of 55 derivatives with overall yields of up to 78 % showed that we were able to expand the range of readily accessible BODIPYs while demonstrating the general applicability and advantages of our developed method.

  在此，提出了 BODIPY 的高效五步反应序列。 55 种衍生物的合成总产率高达 78%，这表明我们能够扩大易于获得的 BODIPY 的范围，同时证明我们开发的方法的普遍适用性和优势。