8-vinyl-1,3,5,7-tetramethylpyrromethene Fluoroborate | 1625689-07-7

• 英文名称: 8-vinyl-1,3,5,7-tetramethylpyrromethene Fluoroborate
• CAS: 1625689-07-7
• 化学式: C₁₅H₁₇BF₂N₂
• 分子量: 274.121
• InChiKey: XCSUFRRWEKRZHB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  8-vinyl-1,3,5,7-tetramethylpyrromethene Fluoroborate 在 N-氯代丁二酰亚胺 作用下， 以 四氢呋喃 为溶剂， 以51%的产率得到
  参考文献：
  名称：

  Substituted meso-vinyl-BODIPY as thiol-selective fluorogenic probes for sensing unfolded proteins in the endoplasmic reticulum

  摘要：

  基于BODIPY结构的巯基选择性探针被开发用于检测小分子巯基和未折叠蛋白。探针的良好细胞器特异性使其在活细胞中报告内质网应激下蛋白质展开的实用性。

  DOI：

  10.1039/d0cc08160d
• 作为产物：
  描述：

  [[(3,5-二甲基-1H-吡咯-2-基)(3,5-二甲基-2H-吡咯-2-亚基)甲基]甲烷](二氟硼烷) 在 potassium hydroxide 作用下， 以 二氯甲烷 、 水 、 丙酮 、 乙腈 为溶剂， 反应 74.0h， 生成 8-vinyl-1,3,5,7-tetramethylpyrromethene Fluoroborate
  参考文献：
  名称：

  Substituted meso-vinyl-BODIPY as thiol-selective fluorogenic probes for sensing unfolded proteins in the endoplasmic reticulum

  摘要：

  基于BODIPY结构的巯基选择性探针被开发用于检测小分子巯基和未折叠蛋白。探针的良好细胞器特异性使其在活细胞中报告内质网应激下蛋白质展开的实用性。

  DOI：

  10.1039/d0cc08160d

文献信息

• Synthesis and Transformations of 5-Chloro-2,2′-Dipyrrins and Their Boron Complexes, 8-Chloro-BODIPYs
  作者：Haijun Wang、M. Graça H. Vicente、Frank R. Fronczek、Kevin M. Smith

  DOI：10.1002/chem.201304310

  日期：2014.4.22

  reacted with methoxide or ethoxide ions to produce monopyrrole esters, presumably via a 5,5‐dialkoxy‐dipyrromethane intermediate. In contrast, 8‐chloro‐BODIPYs underwent a variety of nucleophilic substitutions of the chloro group in the presence of alkoxide ions, Grignard reagents, and thiols. In the presence of excess alkoxide or Grignard reagent, at room temperature or above, substitution at the boron

  对称二吡咯酮1 a , b通过与硫光气反应，然后在碱性条件下氧化水解，由相应的无α吡咯分两步合成。二吡咯酮分别与光气或 Meerwein 盐反应生成相应的 5-氯-二吡啉盐或 5-乙氧基-二吡啉。双吡喃的硼络合以高产率提供了相应的 8 功能化 BODIPY（硼二吡咯亚甲基）。5-氯-二吡啉盐与甲醇盐或乙醇盐离子反应生成单吡咯酯，推测是通过 5,5-二烷氧基-二吡咯甲烷中间体。相比之下，8-氯-BODIPY 在醇盐离子、格氏试剂和硫醇的存在下经历了氯基团的各种亲核取代。在过量醇盐或格氏试剂存在下，在室温或更高温度下，硼中心的替代也发生了。8-氯-BODIPY 是一种特别有用的试剂，用于以非常高的产率制备 8-芳基-、8-烷基-和 8-乙烯基取代的 BODIPY，使用 Pd0催化的 Stille 交叉偶联反应。展示了 11 个 BODIPY 和两个吡咯的 X 射线结构，并讨论了合成的 BODIPY
• When Push Comes to Shove: Unravelling the Mechanism and Scope of Nonemissive <i>meso</i>-Unsaturated BODIPY Dyes
  作者：Richard Lincoln、Lana E. Greene、Cheryl Bain、Juan O. Flores-Rizo、D. Scott Bohle、Gonzalo Cosa

  DOI：10.1021/acs.jpcb.5b02080

  日期：2015.4.2

  We report herein spectroscopy and computational results that illustrate an efficient intramolecular deactivation pathway for meso-unsaturated boron-dipyrromethene (BODIPY) dyes in their singlet excited state. Our results show that the mechanism hinges on the structural flexibility imparted by the boron atom and on the energetic stabilization conferred by extending the conjugation into the meso substituent, which is otherwise unconjugated in the ground state. Following photoexcitation, rotation along the dihedral angle of the meso-unsaturated group results in its conjugation at the expense of shifting one pyrrole moiety in dipyrrin out of the plane. Internal conversion to an energetically hot, ground-state species efficiently competes with emission. The mechanism applies to meso-vinyl, -formyl, and -iminyl moieties. The presence of methyl groups at positions C1 and C7 exacerbates the energetic penalty toward conjugation of the meso groups leading to a small energy gap between relaxed excited state and ground state and undetected emission quantum yields. Importantly, methyls at C1 and C7 prevent nonradiative deactivation in meso-aryl moieties, illustrating that when push comes to shove, the energetic (kinetic) barrier toward reaching conjugation is too large for aryl moieties but low enough for smaller groups to effectively compete with radiative transitions. Wisely chosen meso-unsaturated BODIPY dyes may serve as richly sensitive platforms for the preparation of novel fluorogenic substrates to monitor chemical reactions or to probe the rigidity of their surrounding environment.