1,9-diformyl-dipyrromethane | 1299466-62-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 1,9-diformyl-dipyrromethane
• 英文别名: 1,9-formyldipyrromethane；1,9-diformyl-meso-tolyl dipyrromethane；5-[(5-formyl-1H-pyrrol-2-yl)-(4-methylphenyl)methyl]-1H-pyrrole-2-carbaldehyde
• CAS: 1299466-62-8
• 化学式: C₁₈H₁₆N₂O₂
• 分子量: 292.337
• InChiKey: BYCLZDQSEHBFNQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  65.7
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,9-diformyl-dipyrromethane 在 三氟乙酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成
  参考文献：
  名称：

  Sensing Hg(II) in Vitro and in Vivo Using a Benzimidazole Substituted BODIPY

  摘要：

  A multisignaling Hg(II) sensor based on a benzimidazole substituted BODIPY framework was designed, which displays excellent selectively toward Hg(II) in vitro and in vivo. Optical and fluorogenic measurements in solution reveal that the sensor can detect mercury ions at submicromolar concentrations, with high specificity. The detection of Hg(II) is associated with a blue-shift in optical spectra and a simultaneous increase in the fluorescence quantum yield of the sensor, which is attributed to a decrease in charge delocalization and inhibition of photoinduced electron transfer upon binding to Hg(II). Using several spectroscopic measurements, it is shown that the binding mechanism involves two sensor molecules, where lone pairs of the benzimidazole nitrogen coordinate to a single mercury ion. The utility of this BODIPY sensor to detect Hg(II) in vivo was demonstrated by fluorescence imaging and spectroscopy of labeled human breast adenocarcinoma cells. While average emission intensity of the sensor over a large number of cells increases with incubated mercury concentrations, spatially resolved fluorescence spectroscopy performed on individual cells reveals clear spectral blue-shifts from a subensemble of sensors, corroborating the detection of Hg(II). Interestingly, the emission spectra at various submicrometer locations within cells exhibited considerable inhomogeneity in the extent of blue-shift, which demonstrates the potential of this sensor to monitor the local (effective) concentration of mercury ions within various subcellular environments.

  DOI：

  10.1021/ic401365x
• 作为产物：
  描述：

  对甲基苯甲醛 在 三氟乙酸 、 三氯氧磷 作用下， 以 1,2-二氯乙烷 为溶剂， 生成 1,9-diformyl-dipyrromethane
  参考文献：
  名称：

  3,5-Diformylboron Dipyrromethenes as Fluorescent pH Sensors

  摘要：

  A series of boron dipyrromethene (BODIPY) dyes containing two aldehyde functional groups at the 3 and 5 positions have been synthesized in low-to-decent yields in two steps. In the first step, the meso-aryl dipyrromethanes were treated with POCl(3) in N,N-dimethylformamide to afford 1,9-diformylated dipyrromethanes. In the second step, the diformylated dipyrromethanes were first in situ oxidized with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and then reacted with BF(3)center dot OEt(2) to afford 3,5-diformylboron dipyrromethenes. The X-ray structural analysis indicated that the aldehyde groups are involved in intramolecular hydrogen bonding with fluoride atoms, which may be responsible for the stability of the diformylated BODIPY compounds. The presence of two formyl groups significantly alters the electronic properties, which is clearly evident in downfield shifts in the (1)H and (19)F NMR spectra, bathochromic shifts in the absorption and fluorescence spectra, better quantum yields, and increased lifetimes compared to 3,5-unsubstituted BODIPYs. Furthermore, 3,5-diformylboron dipyrromethenes are highly electron-deficient and undergo facile reductions compared to unsubstituted BODIPYs. These compounds exhibit pH-dependent on/off fluorescence and thus act as fluorescent pH sensors.

  DOI：

  10.1021/ic102499h

文献信息

• Photochemical Barcodes
  作者：Sicheng Tang、Yang Zhang、Pravat Dhakal、Laura Ravelo、Cheyenne L. Anderson、Kevin M. Collins、Françisco M. Raymo

  DOI：10.1021/jacs.8b00887

  日期：2018.4.4

  wavelengths and mild illumination sufficient to induce these transformations permit the photochemical barcoding of beads also in living nematodes. Different regions of the same animal can be labeled with distinct barcodes to allow the monitoring of their dynamics for long times with no toxic effects. Thus, our photochemical strategy for the generation of fluorescence barcodes can produce multiple and distinguishable

  围绕可光活化的硼二吡咯亚甲基 (BODIPY) 的独特特性设计了一种在体内编码具有空间控制的荧光信号的光化学策略。两个恶嗪在单个 BODIPY 侧翼的光诱导断开，在两个连续步骤中产生三个发射分子的混合物，聚合物珠内具有解析的荧光。通过调整激活光子的剂量以标记具有不同荧光信号代码的单个粒子，可以精确调节每个珠子中三种荧光团的相对数量和发射强度。足以诱导这些转变的可见波长和温和的光照允许在活的线虫中对珠子进行光化学条形码编码。同一动物的不同区域可以用不同的条形码标记，以便长时间监测它们的动态，而不会产生毒性作用。因此，我们用于生成荧光条码的光化学策略可以在同一生物样本中产生多个可区分的标签，以实现对无法区分的目标的时空跟踪。
• SWALLOWTAIL MOTIFS FOR IMPARTING WATER SOLUBILITY TO PORPHYRINIC COMPOUNDS
  申请人：Borbas K. Eszter

  公开号：US20090297456A1

  公开（公告）日：2009-12-03

  Porphyrinic compounds that contain solubilizing groups are described, along with methods of making and using the same and compositions comprising such compounds. Examples of such compounds include compounds of Formula (I) wherein: Z is a porphyrinic macrocyclic, Alk 1 and Alk 2 are each independently an alkylidene chain; L is a linking group or is absent; R 1 is preferably an ionic group or polar group; R 2 is an ionic group, polar group, bioconjugatable group, or targeting group: R 3 is present or absent and when present is a halo group, bioconjugatable group, or targeting group, n is O or 1 (that is, the CH group is present, or Alk 1 and Alk 2 are bonded directly to a carbon of the porphyrinic macrocycle Z); or a salt thereof.

  本文介绍了含有增溶基团的卟啉化合物，以及制备和使用这些化合物的方法，以及包含这些化合物的组合物。这些化合物的示例包括式（I）的化合物，其中：Z是卟啉大环，Alk1和Alk2分别独立地是烷基链；L是连接基团或不存在；R1优选为离子基团或极性基团；R2是离子基团、极性基团、生物共轭基团或靶向基团；R3存在或不存在，当存在时是卤基团、生物共轭基团或靶向基团，n为O或1（即，CH基团存在，或Alk1和Alk2直接连接到卟啉大环Z的碳原子上）；或其盐。
• Panchromatic Absorbers Tethered for Bioconjugation or Surface Attachment
  作者：Rui Liu、Jie Rong、Zhiyuan Wu、Masahiko Taniguchi、David F. Bocian、Dewey Holten、Jonathan S. Lindsey

  DOI：10.3390/molecules27196501

  日期：——

  The syntheses of two triads are reported. Each triad is composed of two perylene-monoimides linked to a porphyrin via an ethyne unit, which bridges the perylene 9-position and a porphyrin 5- or 15-position. Each triad also contains a single tether composed of an alkynoic acid or an isophthalate unit. Each triad provides panchromatic absorption (350–700 nm) with fluorescence emission in the near-infrared region (733 or 743 nm; fluorescence quantum yield ~0.2). The syntheses rely on the preparation of trans-AB-porphyrins bearing one site for tether attachment (A), an aryl group (B), and two open meso-positions. The AB-porphyrins were prepared by the condensation of a 1,9-diformyldipyrromethane and a dipyrromethane. The installation of the two perylene-monoimide groups was achieved upon the 5,15-dibromination of the porphyrin and the subsequent copper-free Sonogashira coupling, which was accomplished before or after the attachment of the tether. The syntheses provide relatively straightforward access to a panchromatic absorber for use in bioconjugation or surface-attachment processes.

  报告中介绍了两种三聚体的合成。每个三元组都由两个过烯单亚胺组成，通过一个乙炔单元与一个卟啉相连，乙炔单元连接过烯的 9 位和卟啉的 5 位或 15 位。每个三元组还包含一个由炔酸或间苯二甲酸单元组成的单个系链。每个三元组都具有全色吸收（350-700 纳米），并在近红外区域（733 或 743 纳米；荧光量子产率约为 0.2）发出荧光。这些合成依赖于制备反式 AB-卟啉，它们带有一个用于系链连接的位点（A）、一个芳基（B）和两个开放的中间位。AB 型卟啉是由 1,9-二甲基二吡咯甲烷和二吡咯甲烷缩合而成。在卟啉的 5,15-二溴化反应和随后的无铜 Sonogashira 偶联过程中，两个过烯-单亚胺基团被安装上去。这些合成提供了相对直接的全色吸收剂，可用于生物共轭或表面附着过程。
• Synthesis of <i>meso</i>-pyrrole-substituted corroles by condensation of 1,9-diformyldipyrromethanes with pyrrole
  作者：Baris Temelli、Pinar Kapci

  DOI：10.3762/bjoc.18.145

  日期：——

  A copper triflate-mediated approach to access copper complexes of pyrrole-substituted corroles from the reaction of 1,9-diformyldipyrromethanes and an excess amount of pyrrole is presented for the first time. This procedure is a simple and efficient way for the preparation of corroles with a polymerizable substituent on meso-positions.

  首次提出了一种三氟甲磺酸铜介导的方法，从 1,9-二甲酰基二吡咯甲烷和过量吡咯的反应中获得吡咯取代的咯咯的铜络合物。该程序是制备在中间位具有可聚合取代基的corroles的简单而有效的方法。
• US8097609B2
  申请人：——

  公开号：US8097609B2

  公开（公告）日：2012-01-17