3,5-dichloro-8-(4'-nitrophenyl)-4,4-difluoro-4-bora-3a,4a-indacene

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3,5-dichloro-8-(4'-nitrophenyl)-4,4-difluoro-4-bora-3a,4a-indacene
• 英文别名: 3,5-dichloro-8-(4'-nitrophenyl)-4,4-difluoro-4-bora-3α,4α-diaza-s-indacence；3,5-dichloro-8-(4'-nitrophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacence；3,5-dichloro-8-(4’-nitrophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacence；3,5-dichloro-8-(4'-nitrophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene；4,12-Dichloro-2,2-difluoro-8-(4-nitrophenyl)-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene
• 化学式: C₁₅H₈BCl₂F₂N₃O₂
• 分子量: 381.961
• InChiKey: TXGXKYZRBFTMMK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.27
• 重原子数：
  25
• 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：
  53.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3,5-dichloro-8-(4'-nitrophenyl)-4,4-difluoro-4-bora-3a,4a-indacene 在 2-chlorotrityl chloride polystyrene resin 、 铁粉 、 碳酸氢钠 、 溶剂黄146 、 N,N-二异丙基乙胺 作用下， 以 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 25.67h， 生成 3-((2-methylbenzyl)amino)-4,4-difluoro-5-(4-(pentan-2-yl)-1H-1,2,3-triazol-1-yl)-8-(4-(2-hydroxyacetamido)phenyl)-4-bora-3a,4a-diaza-s-indacene
  参考文献：
  名称：

  [EN] MEGASTOKES AMINO-TRIAZOLYL-BODIPY COMPOUNDS AND APPLICATIONS TO LIVE NEURON STAINING AND HUMAN SERUM ALBUMIN FA1 DRUG SITE PROBING
  [FR] COMPOSÉS AMINO-TRIAZOLYL-BODIPY À MÉGADÉPLACEMENT DE STOKES ET APPLICATIONS DE COLORATION DE NEURONES VIVANTS ET SONDAGE DE SITES MÉDICAMENTEUX D'ACIDE GRAS 1 D'ALBUMINE SÉRIQUE HUMAINE

  摘要：

  公开号：

  WO2014104975A9
• 作为产物：
  描述：

  8-(4-nitrophenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene 在 copper(II) choride dihydrate 作用下， 以 乙腈 为溶剂， 反应 6.0h， 以60%的产率得到3,5-dichloro-8-(4'-nitrophenyl)-4,4-difluoro-4-bora-3a,4a-indacene
  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

• 3- and 5-Functionalized BODIPYs via the Liebeskind-Srogl reaction
  作者：Junyan Han、Oswaldo Gonzalez、Angelica Aguilar-Aguilar、Eduardo Peña-Cabrera、Kevin Burgess

  DOI：10.1039/b818390b

  日期：——

  Chemoselective cross-coupling reactions were demonstrated for C–S bonds in the BODIPY dyes 1 and 4, and similar reactions were applied to make the two-dye cassette system 11.

  展现了用于BODIPY染料1和4中C–S键的化学选择性交叉耦合反应，类似反应也应用于制备双染料盒系统11。
• Syntheses and Spectral Properties of Functionalized, Water-Soluble BODIPY Derivatives
  作者：Lingling Li、Junyan Han、Binh Nguyen、Kevin Burgess

  DOI：10.1021/jo702463f

  日期：2008.3.1

  The objective of this work was to form water-soluble 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) derivatives. Sulfonation conditions were developed for several BODIPY dyes to give the monosulfonated products 1a−3a and the disulfonated products 1b−3b. Compounds 1 are functionalized with an aryl iodide for organometallic couplings. Similarly, 2 has an aromatic bromide but also two chlorine atoms

  这项工作的目的是形成水溶性4,4-二氟-4-硼3a，4a-二氮杂s-茚并二烯（BODIPY）衍生物。为几种BODIPY染料开发了磺化条件，得到了单磺化产物1a - 3a和二磺化产物1b - 3b。用芳基碘化物将化合物1官能化以用于有机金属偶联。类似地，2具有芳族溴化物，但也具有两个可通过S N Ar反应取代的氯原子。胺3适合于通过酰化反应与生物分子偶联。重氮化/叠氮化物反应顺序用于转化胺3变成叠氮化物4 ; 后者可以通过点击反应功能化，如4b转化为5所示。化合物5被设计成具有酸官能团以促进活化和与胺偶联。这些材料的光谱数据表明它们是水性环境中的高荧光探针。
• MegaStokes BODIPY-triazoles as environmentally sensitive turn-on fluorescent dyes
  作者：Jun Cheng Er、Mui Kee Tang、Chee Geng Chia、Huimin Liew、Marc Vendrell、Young-Tae Chang

  DOI：10.1039/c3sc22166k

  日期：——

  A novel class of triazole-derivatized BODIPY compounds have been synthesized on solid-phase by employing mild reaction conditions based on the copper-catalyzed azide–alkyne cycloaddition. The resulting BODIPY-triazoles exhibited MegaStokes shifts (up to 160 nm) and remarkable environmentally sensitive quantum yield increments that asserted their potential as turn-on fluorescent sensors. Out of a library of 120 compounds, we identified BDC-9 as a fluorescent chemosensor with high sensitivity and remarkable species-selectivity towards human serum albumin. These results validate MegaStokes BODIPY dyes as new fluorophores for the development of environmentally sensitive fluorescent probes.

  一种新型的三唑衍生BODIPY化合物已通过采用温和反应条件的铜催化叠氮–炔烃环加成反应在固相上合成。得到的BODIPY-三唑表现出巨斯托克位移（高达160纳米）和显著的环境敏感量子产率增益，证明它们作为开启荧光传感器的潜力。在120种化合物库中，我们鉴定出BDC-9作为一种对人血清白蛋白具有高灵敏度和显著物种选择性的荧光化学传感器。这些结果验证了巨斯托克BODIPY染料作为新型荧光探针的环境敏感性荧光团。
• NeuO: a Fluorescent Chemical Probe for Live Neuron Labeling
  作者：Jun Cheng Er、Cheryl Leong、Chai Lean Teoh、Qiang Yuan、Paolomi Merchant、Matthew Dunn、David Sulzer、Dalibor Sames、Akshay Bhinge、Dongyoon Kim、Seong-Min Kim、Myung-Han Yoon、Lawrence W. Stanton、Shawn H. Je、Seong-Wook Yun、Young-Tae Chang

  DOI：10.1002/anie.201408614

  日期：2015.2.16

  To address existing limitations in live neuron imaging, we have developed NeuO, a novel cell‐permeable fluorescent probe with an unprecedented ability to label and image live neurons selectively over other cells in the brain. NeuO enables robust live neuron imaging and isolation in vivo and in vitro across species; its versatility and ease of use sets the basis for its development in a myriad of neuronal

  为了解决活神经元成像中的现有局限性，我们开发了NeuO，这是一种新型的细胞渗透性荧光探针，具有前所未有的能力，可以选择性标记和成像活神经元，而不是大脑中的其他细胞。NeuO可实现跨物种的体内和体外健壮的活神经元成像和分离；它的多功能性和易用性为它在众多神经元靶向应用中的发展奠定了基础。
• Synthesis of 3,5-dichloro-4,4-difluoro-4-bora-3a,4a-diaza-s-indacenes (BODIPYs) via Cu(OTf)2 mediated oxidative nucleophilic substitution of hydrogen by chloride
  作者：Felicity Frank、Laura Manzoli Alice、Philipp Mauker、Abdulrahman A. Alsimaree、Paul Gordon Waddell、Michael Richard Probert、Thomas James Penfold、Julian Gary Knight、Michael John Hall

  DOI：10.1016/j.tet.2020.131113

  日期：2020.4

  3/5-halogenated BODIPYs. Herein we present our development of a 3,5-dihalogenation reaction of unsubstituted BODIPYs, via a double oxidative nucleophilic substitution of hydrogen with chloride. Reaction of a range of meso-aryl, but otherwise unsubstituted, BODIPYs with stoichiometric Cu(OTf)2 in the presence of ethanolamine and tetrabutylammonium chloride gives high isolated yields of the corresponding 3,5-dichlorinated

  通过进行后续的下游C–C或CX键形成步骤，区域选择性卤化通常是形成取代的4,4-二氟-4-硼3a，4a-二氮杂s-茚并四烯（BODIPY）荧光团的关键步骤通过S N Ar或金属催化的交叉偶联反应。古典小号È的2/6-取代或未取代的BODIPYs结果的Ar卤化，排除至3/5-卤代BODIPYs方便地访问。在这里，我们介绍了通过氢与氯化物的双氧化亲核取代，我们未取代的BODIPYs的3,5-二卤代反应的发展。一定范围的内消旋芳基与其他化学计量的Cu（OTf）2反应 在乙醇胺和氯化四丁基铵存在下，分离出相应的3,5-二氯代BODIPYs的产率很高，从而有助于获得这些有价值的合成中间体。