bis(difluoroboron) 1,2-bis((1H-pyrrol-2-yl)methylene)hydrazine | 1588489-51-3

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: bis(difluoroboron) 1,2-bis((1H-pyrrol-2-yl)methylene)hydrazine
• 英文别名: 5,5,12,12-tetrafluoro-5H,12H-5λ⁴,6λ⁴,12λ⁴,13λ⁴-pyrrolo[1,2-d]pyrrolo-[1',2':4,51,2,4,3]-triazaborinino[2,1-a][1,2,4,3]triazaborinine；BOPHY；2,2,10,10-Tetrafluoro-3,11-diaza-1,9-diazonia-2,10-diboranuidatetracyclo[7.7.0.03,7.011,15]hexadeca-1(16),4,6,8,12,14-hexaene
• CAS: 1588489-51-3
• 化学式: C₁₀H₈B₂F₄N₄
• 分子量: 281.816
• InChiKey: VEBGVXFIPGAPBX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.24
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  15.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  bis(difluoroboron) 1,2-bis((1H-pyrrol-2-yl)methylene)hydrazine 在 溴 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以62%的产率得到
  参考文献：
  名称：

  多溴BOPHY染料：合成，反应性和性能

  摘要：

  从母体双（二氟硼）-1,2-双（（1 H-吡咯-2-基）亚甲基）肼（BOPHY），肼连接的双吡咯中间体的溴化反应或溴化的2-甲酰基吡咯前体的溴化反应，产率中等至优异。通过区域选择性亲核取代或Suzuki / Stille交叉偶联反应进一步研究了这些多溴化BOPHY染料的反应性，从中获得了一系列5、5,5'-取代的BOPHY与胺，吡咯，噻吩和苯基的混合物。中度至高产37-94％。溴化反应和亲核取代反应以及这些所得的BOPHY染料的区域选择性均通过NMR，HRMS和晶体结构确定。研究了这些生成的BOPHY的光谱性质，它们大多数显示出强吸收性和明亮的荧光，最大波长集中在430和660 nm之间。对于每个结合的溴原子，它们的吸收光谱和发射光谱都发生了红移。溴或取代基的连接位置可调节所得BOPHY染料的光物理性质。

  DOI：

  10.1021/acs.joc.7b02415
• 作为产物：
  描述：

  2-吡咯甲醛 在 溶剂黄146 、 三乙胺 、 肼 作用下， 以 乙醇 、 甲苯 为溶剂， 反应 0.17h， 生成 bis(difluoroboron) 1,2-bis((1H-pyrrol-2-yl)methylene)hydrazine
  参考文献：
  名称：

  Highly Fluorescent BF₂ Complexes of Hydrazine–Schiff Base Linked Bispyrrole

  摘要：

  A series of BF2 complexes of hydrazine-Schiff base linked bispyrrole have been prepared from a simple two-step reaction from commercially available substances and are highly fluorescent in solution, film, and solid states with larger Stokes shift and excellent photostabilities comparable or even super to those of their BODIPY analogues. These resultant fluorescent dyes are highly susceptible to the postfunctionalization, as demonstrated in this work via the Knoevenagel condensation to introducing functionalities or tether groups to the chromophore.

  DOI：

  10.1021/ol501162f

文献信息

• [EN] Highly Fluorescent Pyrrole-BF2 Chromophores<br/>[FR] CHROMOPHORES DE PYRROLE-BF2 HAUTEMENT FLUORESCENTS
  申请人：UNIV AKRON

  公开号：WO2015077427A1

  公开（公告）日：2015-05-28

  Fluorescent chromophores nicknamed BOPHY are provided. The chromophores may be readily synthesized in two steps from readily available reagents via the coupling of a pyrrole aldehyde or ketone with hydrazine, followed by reaction with BF3. The resultant symmetric and dimeric tetracycle is comprised of two BF2 units in six-member chelate rings, appended by pyrrole units on the periphery. The quantum yield of fluorescence for the unmodified compound and the tetramethyl variant are near unity, with values 95 and 92% respectively in CH2Cl2.

  提供了被昵称为BOPHY的荧光色团。这些色团可以通过从易得试剂中的吡咯醛或酮与联氨反应，然后与BF3反应的方式，在两个步骤中轻松合成。所得的对称和二聚四环体由两个BF2单元组成，形成六元螯合环，周围附有吡咯单元。未经修改的化合物和四甲基变体的荧光量子产率几乎为1，分别在CH2Cl2中为95%和92%。
• Microwave-assisted direct synthesis of BODIPY dyes and derivatives
  作者：Ana Da Lama、José Pérez Sestelo、Luis A. Sarandeses、M. Montserrat Martínez

  DOI：10.1039/d2ob01349e

  日期：——

  A microwave-assisted one-pot synthesis of BODIPY dyes from pyrroles and acyl chlorides is reported. This protocol features short reaction times, low temperatures, minimum amount of solvent, scalability, versatility, and good yields of the products. These simple, efficient and sustainable conditions can be also applied to the synthesis of derivatives such as BOPHY, BOAHY and BOPAHY.

  报道了从吡咯和酰氯中微波辅助一锅法合成 BODIPY 染料。该协议具有反应时间短、温度低、溶剂用量最少、可扩展性、多功能性和产品收率高的特点。这些简单、高效和可持续的条件也可以应用于BOPHY、BOAHY和BOPAHY等衍生物的合成。
• A New Highly Fluorescent and Symmetric Pyrrole–BF₂ Chromophore: BOPHY
  作者：Ingrid-Suzy Tamgho、Abed Hasheminasab、James T. Engle、Victor N. Nemykin、Christopher J. Ziegler

  DOI：10.1021/ja502477a

  日期：2014.4.16

  The new fluorescent chromophore BOPHY can be readily synthesized in two steps from commercially available reagents via the coupling of pyrrole-2-carboxaldehyde with hydrazine followed by reaction with BF3. The resultant symmetric and dimeric tetracycle is composed of two BF2 units in six-membered chelate rings appended with pyrrole units on the periphery. The quantum yields of fluorescence for the unmodified compound and the tetramethyl variant are near unity, with values of 95 and 92%, respectively, in CH2Cl2. We have probed the electronic structure of this compound via cyclic voltammetry and density functional theory analysis.
• BOPHYs versus BODIPYs: A comparison of their performance as effective multi-function organic dyes
  作者：R. Sola-Llano、J. Jiménez、E. Avellanal-Zaballa、M. Johnson、T.A. Cabreros、F. Moreno、B.L. Maroto、G. Muller、J. Bañuelos、L. Cerdán、I. García-Moreno、S. de la Moya

  DOI：10.1016/j.dyepig.2019.107662

  日期：2019.11

  The computadonally-aided photophysical and lasing properties of a selected battery of BOPHYs are described and compared to those of related BODIPY counterparts. The present joined theoredcal-experimental study helps to put into context the wealcnesses and strengths of both dye families under different irradiation conditions. The chemical versatility of the BOPHY scaffold has been also comparatively explored to modulate key photonic properties towards the development of red-emitting dyes, chiroptical dyes and singlet oxygen photosensidzers. Thus, BOPHY BINOLation by fluorine substitution with enantiopure BINOLs endows the BOPHY chromophore with chiroptical activity, as supporting by the simulated circular dichroism, decreasing deeply its fluorescent response due to the promotion of fluorescence-quenching intramolecular charge transfer (ICT). Interestingly, the sole alkylation of the BOPHY core strongly modulates the promotion of ICT, allowing the generation of highly bright BINOL-based BOPHY dyes. Moreover, 3,3'-dibromoBINOLating BOPHYs can easily achieve singlet-oxygen photogeneration, owing to spin-orbit coupling mediated by heavy-atom effect feasible in view of the theoretically predicted disposition of the bromines surrounding the chromophore. From this background, we have established the master guidelines to design bright fluorophores and laser dyes, photosensitizers for singlet oxygen production and chiroptical dyes based on BOPHYs. The possibility to finely mix and balance such properties in a given molecular scaffold outstands BOPHYs as promising dyes competing with the well-settled BODIPY dyes.
• 3,8-二吡咯-BODIPY荧光染料的制备方法和 次氯酸根的定性检测方法
  申请人：安徽师范大学

  公开号：CN111187288B

  公开（公告）日：2023-04-28