5-Bromo-2,2-difluoro-8-(2,4,6-trimethylphenyl)-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene | 1301766-05-1

• 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: 5-Bromo-2,2-difluoro-8-(2,4,6-trimethylphenyl)-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene
• CAS: 1301766-05-1
• 化学式: C₁₈H₁₆BBrF₂N₂
• 分子量: 389.05
• InChiKey: YCTRXZNZLVHTIH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.82
• 重原子数：
  24
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  5-Bromo-2,2-difluoro-8-(2,4,6-trimethylphenyl)-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 caesium carbonate 、 联硼酸频那醇酯 、 2-二环己基磷-2,4,6-三异丙基联苯 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 48.0h， 以81%的产率得到5-[2,2-Difluoro-8-(2,4,6-trimethylphenyl)-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaen-5-yl]-2,2-difluoro-8-(2,4,6-trimethylphenyl)-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene
  参考文献：
  名称：

  Synthesis of Directly Connected BODIPY Oligomers through Suzuki–Miyaura Coupling

  摘要：

  Treatment of a meso-arylboron dipyrrin (BODIPY) with NBS provides mono- and dibromlnated BODIPYs at the 2- and 6-positions In excellent yields with high regioselectivity. Brominated products can be employed as a nice building block for the synthesis of a variety of BODIPY derivatives through Suzuki-Miyaura coupling. Because of a lack of substituents at the 1,3,5,7-positions, a directly beta-beta-linked BODIPY dimer exhibits a completely coplanar conformation of BODIPY units, offering effective pi-conjugation.

  DOI：

  10.1021/ol200799u
• 作为产物：
  描述：

  8-(2,4,6-三甲苯基)-4,4-DIFLUOROBORADIAZAINDACENE 在 copper(ll) bromide 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以72%的产率得到5-Bromo-2,2-difluoro-8-(2,4,6-trimethylphenyl)-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene
  参考文献：
  名称：

  Highly Regioselective α-Chlorination of the BODIPY Chromophore with Copper(II) Chloride

  摘要：

  A general and efficient method for a-chlorination of 4,4'-difluoro-4-bora-3a,4a-diaza-s-indacenes (BODIPYs) has been developed using CuCl2 as chlorination reagent. The reaction is characterized by complete 3/5-positions of BODIPY regioselectivity. This unusual highly regioselective alpha-halogenation of BODIPY is in sharp contrast to previously reported halogenation methods which preferred to occur first at the 2,6-positions of BODIPY. This approach provides a straightforward, facile, and economical route to 3- and/or 5-chloroBODIPYs with various meso-groups (H, alkyl, and aryl) and their derivatives.

  DOI：

  10.1021/acs.orglett.5b02383

文献信息

• Significant Enhancement of Absorption and Luminescence Dissymmetry Factors in the Far‐Red Region: A Zinc(II) Homoleptic Helicate Formed by a Pair of Achiral Dipyrromethene Ligands
  作者：Hiroaki Ito、Hayato Sakai、Yoshinori Okayasu、Junpei Yuasa、Tadashi Mori、Taku Hasobe

  DOI：10.1002/chem.201804171

  日期：2018.11.13

  A homoleptic zinc(II) helicate organized by a pair of achiral dipyrromethene ligands through zinc(II) coordination was synthesized to evaluate the chiroptical properties. This zinc complex showed strong exciton‐coupled chiroptical responses from the helical configuration with a large absorption dissymmetry factor |gabs| (up to 0.20). More importantly, intense polarized luminescence in the far‐red region

  合成了由一对非手性二吡咯亚甲基配体通过锌（II）配位组织的均化锌（II）螺旋结构，以评估手性。这种锌络合物显示出强烈的激子耦合的螺旋响应，其螺旋构型具有较大的吸收不对称因子。g abs | （最大为0.20）。更重要的是，在远红外区域（700-850纳米）与荧光量子产率强烈偏振发光Φ FL观察到这个helicate与不对称因子0.23 | 摹LUM | 值为0.022，这是不含稀土和贵金属的小分子中的最大值。这些空前大的g值得到了理论计算的支持。
• 一类不对称苯并氟硼二吡咯荧光染料及其制 法
  申请人：南京大学

  公开号：CN109233325B

  公开（公告）日：2021-03-19

  本发明涉及一类不对称苯并氟硼二吡咯荧光染料，它具有如下结构：本发明的一类不对称苯并氟硼二吡咯荧光染料优点是在光谱显著红移的同时保持高强度发光。并且合成简单，通过直接修饰溴代BODIPY前体，一锅法与不同的二炔烃反应得到一系列新颖的单边[a]位苯并BODIPY。
• Systematic Control of Structural and Photophysical Properties of π‐Extended Mono‐ and Bis‐BODIPY Derivatives
  作者：Hiroaki Ito、Hayato Sakai、Yasutaka Suzuki、Jun Kawamata、Taku Hasobe

  DOI：10.1002/chem.201904282

  日期：2020.1.2

  two terminal nonplanar units of BODIPYs. The oxidation and reduction potentials agree with the estimated energies obtained through DFT calculations. The localized HOMO and LUMO states suggested the intramolecular charge-transfer characteristics in these BODIPY derivatives. The absorption spectra of these compounds extended up to the near-IR region. Strong redshifted trends of fluorescence spectra were

  一系列π扩展的单-和双-BODIPY（BODIPY =硼-二吡咯亚甲基）衍生物，即苯并[a]菲-稠合的BODIPY（Phena-MOno-BDP），苯并[a]蒽-稠合的BODIPY（Ant-设计并合成了二苯并[a，h]蒽（DBA）桥联的双-BODIPY（Ant-Bis-BDP），以检查它们的结构，电化学和光物理性质。单晶X射线晶体学分析表明，与非平面Phena-MOno-BDP相比，Ant-MOno-BDP具有平面构型，而Ant-Bis-BDP具有DBA中心的平面构型和两个末端非平面单元。身体 氧化和还原电势与通过DFT计算获得的估计能量一致。本地化的HOMO和LUMO状态表明了这些BODIPY衍生物的分子内电荷转移特性。这些化合物的吸收光谱一直延伸到近红外区域。从李珀特-马塔加（Lippert-Mataga）图估计的偶极矩差异支持了在Ant-Bis-BDP中随着溶剂极性增加而出现的强烈荧
• Highly regioselective palladium-catalyzed domino reaction for post-functionalization of BODIPY
  作者：Sisi Wang、Zhaoli Wang、Hu Gao、Liang Jiang、Hui Liu、Fan Wu、Yue Zhao、Kin Shing Chan、Zhen Shen

  DOI：10.1039/d0cc08163a

  日期：——

  naphthyl-BODIPYs have been synthesized through a facile one-pot palladium-catalyzed domino reaction of BODIPY precursors (2-bromo-BODIPYs) with diarylethynes, via “cis, cis” and “trans, cis” addition transition states with alkynes, respectively. This reaction exhibits unprecedentedly complete cyclization regioselectivity to the a-position of the BODIPY over the b-one, and the resulting products can be effectively

  通过BODIPY前体（2-溴-BODIPYs）与二芳基乙炔的简单的一锅钯催化多米诺反应，通过“顺式，顺式”合成了一系列的苯并[ a ]稠合的BODIPY和相应的异构萘基-BODIPY。和“反式，顺式”分别与炔烃的加成过渡态。该反应对BODIPY的b位上的BODIPY的a位表现出前所未有的完全环化区域选择性，并且可以通过在二芳基乙炔上选择取代基来有效调节所得产物。
• Synthesis and Photophysical Properties of Naphtho[b]- and Indeno[b]-fused BODIPYs
  作者：Baogeng Wu、Zhikuan Zhou、Lei Chen、Aihua Yuan

  DOI：10.1016/j.dyepig.2020.108676

  日期：2020.12

  Electron donating methoxy group facilitate both the 6-endo and 5-exo cyclization procedure to produce naphtho[b]- and indeno[b]-fused BODIPYs in one pot reaction. Naphtho[b]-fused BODIPY exhibits redshifted absorption and emission (591 nm/621 nm) with higher quantum yield (0.56 in DCM), while indeno[b]-fused BODIPY shows very low quantum yield (0.01 in DCM) with shorter absorption and emission wavelength

  报道了一种新的合成方法，该方法通过PtCl 2催化的被外围苯乙炔取代的BODIPYs的环异构化反应来构建[ b ]融合的BODIPY衍生物。供电子甲氧基便于将6-内切和5-外型环化方法，以产生萘并[ b ] -茚并[ b ]在一锅反应-融合BODIPYs。萘并[ b ]融合的BODIPY表现出红移的吸收和发射（591 nm / 621 nm），具有更高的量子产率（在DCM中为0.56），而茚并[ b融合的BODIPY的量子产率非常低（在DCM中为0.01），具有较短的吸收和发射波长（571 nm / 600 nm）和较强的吸收强度。量子化学计算表明，环戊二烯基环在茚并[ b ]稠合的BODIPY中具有抗芳香性，这是其光化学性质较差的原因。