4,4-diphenyl-1,3,5,7,8-pentamethyl-2,4-diethyl-4-bora-3a,4a-diaza-s-indacene | 221159-19-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 4,4-diphenyl-1,3,5,7,8-pentamethyl-2,4-diethyl-4-bora-3a,4a-diaza-s-indacene
• 英文别名: 4,4-diphenyl-1,3,5,7,8-pentamethyl-2,6-diethyl-4-bora-3a,4a-diaza-s-indacene；4,4-diphenyl-2,6-diethyl-1,3,5,7,8-pentamethyl-4-bora-3a,4adiaza-s-indacene；2,6-diethyl-4,4-diphenyl-1,3,5,7,8-pentamethyl-4-bora-3a,4a-diaza-s-indacene；5,11-Diethyl-4,6,8,10,12-pentamethyl-2,2-diphenyl-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene；5,11-diethyl-4,6,8,10,12-pentamethyl-2,2-diphenyl-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene
• CAS: 221159-19-9
• 化学式: C₃₀H₃₅BN₂
• 分子量: 434.432
• InChiKey: ITAPMROOTJARTF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.73
• 重原子数：
  33
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  7.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4,4-diphenyl-1,3,5,7,8-pentamethyl-2,4-diethyl-4-bora-3a,4a-diaza-s-indacene 在 copper(II) nitrate trihydrate 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 0.08h， 以62%的产率得到4,4-diphenyl-3-nitro-1,5,7,8-tetramethyl-2,6-diethyl-4-bora-3a,4a-diaza-s-indacene
  参考文献：
  名称：

  Reactions of BODIPY Fluorophore with Cupric Nitrate

  摘要：

  4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) and corresponding 4,4-dimethyl and 4,4-diphenyl analogues were treated with cupric nitrate trihydrate under different conditions. Corresponding 3-nitro-, nitromethyl-, hydroxymethyl BODIPY, and BODIPY 3-carboxyaldehyde were obtained. The UV/vis and fluorescent properties of these BODIPY analogues were determined.

  DOI：

  10.1055/s-0034-1379108
• 作为产物：
  描述：

  2,4-二甲基-3-乙基吡咯 在 碘 、 magnesium 、 乙酰氯 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 3.67h， 生成 4,4-diphenyl-1,3,5,7,8-pentamethyl-2,4-diethyl-4-bora-3a,4a-diaza-s-indacene
  参考文献：
  名称：

  无重原子螺有机​​硼配合物作为三重激发态光敏剂用于单线态氧活化

  摘要：

  在此，我们提出了一种开发基于刚性硼芴支架的高效无重原子单线态氧光敏剂的新策略。硼芴配合物的物理化学性质可以通过配体的选择轻松调整，从而允许探索许多有机硼结构作为有效的1 O 2敏化剂。研究的复合物的单线态氧产生量子产率在 0.55-0.78 的范围内变化。理论计算表明，硼芴部分的引入对于单线态电荷转移态的稳定至关重要，而正交供体-受体分子结构促进了系统间跨越到局部三线态。我们的研究表明，只需 0.05 mol% 的光催化剂负载量，就可以在 20-120 分钟的照射时间内实现对选定有机底物的定量氧化。

  DOI：

  10.1021/acs.joc.1c01254
• 作为试剂：
  描述：

  4-溴-1,2-亚甲二氧基苯 在 2,2'-二吡啶-6,6'-二胺 、 4,4-diphenyl-1,3,5,7,8-pentamethyl-2,4-diethyl-4-bora-3a,4a-diaza-s-indacene 、 Br₂Ni*3H₂O 、 水 、 N,N-二异丙基乙胺 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 24.0h， 以72%的产率得到芝麻酚
  参考文献：
  名称：

  苯酚的合成：芳基卤化物与水的有机光氧化还原/镍双催化羟化反应

  摘要：

  报道了在协同的有机光氧化还原和镍催化下，芳基卤化物与水的高效羟基化反应。在配体上的分子内碱基促进去质子化之后，所得酚的OH基团起源于水。重要的是，芳基溴化物和反应性较低的芳基氯用作有效的底物，以提供具有广泛官能团的酚。不需要强大的无机碱或昂贵的贵金属催化剂，该方法可用于有效制备各种酚，并使多官能药学上相关的芳基卤化物羟基化。

  DOI：

  10.1002/anie.201710698

文献信息

• First Highly Efficient and Photostable<i>E</i>and<i>C</i> Derivatives of 4,4-Difluoro-4-bora-3a,4a-diaza-<i>s</i>-indacene (BODIPY) as Dye Lasers in the Liquid Phase, Thin Films, and Solid-State Rods
  作者：Gonzalo Duran-Sampedro、Ixone Esnal、Antonia R. Agarrabeitia、Jorge Bañuelos Prieto、Luis Cerdán、Inmaculada García-Moreno、Angel Costela、Iñigo Lopez-Arbeloa、María J. Ortiz

  DOI：10.1002/chem.201303579

  日期：2014.2.24

  dyes, both in liquid solution and in the solid phase, with lasing efficiencies under transversal pumping up to 73 % in liquid solution and 53 % in a solid matrix. The new dyes also showed enhanced photostability. In a solid matrix, the derivative of commercial dye PM597 that incorporated cyano groups at the boron center exhibited a very high lasing stability, with the laser emission remaining at the

  的新的库ë -和ç -4,4-二氟-4-硼-3a，4a-二氮杂-小号茚满二烯（BODIPY）衍生物是通过简单的协议从市售BODIPY配合物合成的，并且系统地研究了与B取代基（炔基，氰基，乙烯基，芳基，和烷基）已经进行。用吸电子基团取代氟原子会增强染料的荧光响应，而电子给体基团则会降低荧光效率。结果，这些化合物相对于其母体染料在液相和固相中均表现出增强的激光作用，在横向泵送下的激光效率在液相溶液中高达73％，在固相基质中高达53％。新染料还显示出增强的光稳定性。在固态矩阵中 商业染料PM597的衍生物在硼中心掺入了氰基，表现出非常高的激光稳定性，在10万次重复频率下，在同一位置的100000个泵浦脉冲后，激光发射保持在初始水平。结合了母体染料PM597及其氰基衍生物的有机膜证明了分布反馈激光的发射。将膜沉积在刻有适当周期性结构的石英基板上。这 结合了母体染料PM597及其氰基衍生物的有机膜证
• New fluorescent aryl- or ethynylaryl-boron-substituted indacenes as promising dyes
  作者：Gilles Ulrich、Christine Goze、S?bastien Goeb、Pascal Retailleau、Raymond Ziessel

  DOI：10.1039/b604830g

  日期：——

  A generic design principle based on the use of organometallic (Li or Mg) reagents for the substitution of the fluoro ligands in difluoroboradiazaindacene is described. A library of compounds bearing various substituents (butyl, phenyl, naphthyl, pyrenyl, ethynylnaphthyl, ethynylfluorenyl, ethynylcarbazoyl, ethynylperylenyl, ethynylthiophenyl and ethynylterpyridinyl) has been prepared and characterized. Electrochemical and photochemical measurements show that these novel dyes remain redox-active and strongly luminescent. They offer an interesting perspective for applications in labelling and electroluminescence.

  描述了基于使用有机金属（Li 或 Mg）试剂取代二氟硼二氮茚中的氟配体的通用设计原理。已制备并表征了带有各种取代基（丁基、苯基、萘基、芘基、乙炔基萘基、乙炔基芴基、乙炔基咔唑酰基、乙炔基苝基、乙炔基苯硫基和乙炔基三联吡啶基）的化合物库。电化学和光化学测量表明，这些新型染料仍然具有氧化还原活性和强发光性。它们为标记和电致发光的应用提供了有趣的视角。
• Masking and Demasking Strategies for the BF₂–BODIPYs as a Tool for BODIPY Fluorophores
  作者：Ankush B. More、Soumyaditya Mula、Shrikant Thakare、Nagaiyan Sekar、Alok K. Ray、Subrata Chattopadhyay

  DOI：10.1021/jo502028g

  日期：2014.11.21

  An efficient and chemoselective route for transforming BF(2)BODIPYs to Et2B-BODIPYs (masking) was developed using Et2AlCl. The Et groups can be easily replaced with F atoms using BF3 center dot Et2O in moist CH2Cl2 to regenerate the BF(2)BODIPYs (demasking). The maskingdemasking strategy is very useful for synthesizing functionalized BODIPYs via nucleophilic and reductive reactions. The masking strategy was used to synthesize a BODIPY dimer by McMurry coupling of a formyl Et2BBODIPY, while a new BODIPY with an asymmetrically substituted B-center was synthesized using the demasking strategy.
• Synthesis and Photophysical Properties of Borondipyrromethene Dyes Bearing Aryl Substituents at the Boron Center
  作者：Christine Goze、Gilles Ulrich、Laura J. Mallon、Ben D. Allen、Anthony Harriman、Raymond Ziessel

  DOI：10.1021/ja062405a

  日期：2006.8.1

  Several borondipyrromethene (Bodipy) dyes bearing an aryl nucleus linked directly to the boron center have been prepared under mild conditions. The choice of Grignard or lithio organo-metallic reagents allows the isolation of B(F)(aryl) or B(aryl)(2) derivatives; where aryl refers to phenyl, anisyl, naphthyl, or pyrenyl fragments. A single crystal, X-ray structure determination for the bis-anisyl compound shows that the sp(3) hybridized boron center remains pseudo-tetrahedral and that the B-C bond distances are 1.615 and 1.636 angstrom. All compounds are electrode active but replacement of the fluorine atoms by aryl fragments renders the Bodipy unit more easily oxidized by 100 mV in the B(F)(aryl) and 180 mV in the B(aryl)(2) compounds whereas reduction is made more difficult by a comparable amount. Strong fluorescence is observed from the Bodipy fluorophore present in each of the new dyes, with the radiative rate constant being independent of the nature of the aryl substituent. The fluorescence quantum yields are solvent dependent and, at least in some cases (aryl = anisyl or pyrenyl), nonradiative decay from the first-excited singlet state is strongly activated. There is no indication, however, for population of a charge-transfer state, in which the aryl substituent acts as donor and the Bodipy fragment functions as acceptor, that is strongly coupled to the ground state. Instead, it is conjectured that nonradiative decay involves a conformational change driven by the solvophobic effect. Thus, the rate of nonradiative decay in any given solvent increases with increasing surface accessibility (or molar volume) of the aryl substituent. Intramolecular energy transfer from pyrene or naphthalene residues to Bodipy is quantitative.
• Some observations relating to the stability of the BODIPY fluorophore under acidic and basic conditions
  作者：Lijing Yang、Razvan Simionescu、Alan Lough、Hongbin Yan

  DOI：10.1016/j.dyepig.2011.03.027

  日期：2011.11

  4,4-Difluoro-4-bora-1,3,5,7-tetramethyl-2,6-diethyl-8-methyl-3a,4a-diaza-s-indacene (BODIPY) fluorophore was transformed into its corresponding 4,4-dimethyl, 4,4-dimethoxy and 4,4-diphenyl analogues. The stabilities of these BODIPY fluorophores in acidic (di- and trichloroacetic acid) and basic conditions (aqueous ammonium hydroxide) were investigated using B-11 NMR spectroscopy. (C) 2011 Elsevier Ltd. All rights reserved.