4-(chloromethyl)-7-(diethylamino)-2H-chromen-2-on | 1227636-21-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 香豆素及其衍生物
• 英文名称: 4-(chloromethyl)-7-(diethylamino)-2H-chromen-2-on
• 英文别名: 7-diethylamino-4-chloromethyl coumarin；4-chloromethyl-7-N,N-diethylaminocoumarin；4-(chloromethyl)-7-(diethylamino)-2H-chromen-2-one；4-(Chloromethyl)-7-(diethylamino)chromen-2-one；4-(chloromethyl)-7-(diethylamino)chromen-2-one
• CAS: 1227636-21-6
• 化学式: C₁₄H₁₆ClNO₂
• 分子量: 265.74
• InChiKey: IBLIHARAECAWLI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-(chloromethyl)-7-(diethylamino)-2H-chromen-2-on 在 sodium azide 、 palladium on activated charcoal 、 氢气 、 N,N-二异丙基乙胺 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.0h， 生成 N-((7-(diethylamino)-2-oxo-2H-chromen-4-yl)methyl)nicotinamide
  参考文献：
  名称：

  Synthesis, Photophysical, Photochemical, and Computational Studies of Coumarin-Labeled Nicotinamide Derivatives

  摘要：

  The syntheses and photophysical/photochemical properties of two amide-tethered coumarin-labeled nicotinamides are described. Photochemical studies of 6-bromo-7-hydroxycoumarin-4-ylmethylnicotinamide (BHC-nicotinamide) revealed an unexpected solvent effect. This result is rationalized by computational studies of the different protonation states using TD-DFT with the M06L/6-311+G** method with implicit and explicit solvation models. Molecular orbital energies responsible for the lambda(max) excitation show that the functionalization of the coumarin ring results in a strong red-shift from 330 to 370 nm when the pH of solution is increased from 3.06 to 8.07. From this MO analysis, a model for solvent interactions has been proposed. The BHC-nicotinamide proved to be photochemically stable, which is also interpreted in terms of NBO calculations. The results provide a set of principles for the rational design of either photostable labeling reagents or photolabile cage compounds.

  DOI：

  10.1021/jo2025527
• 作为产物：
  描述：

  7-(二乙基氨基)-4-(羟基甲基)-2H-苯并吡喃-2-酮 在 吡啶 、 对甲苯磺酰氯 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以29%的产率得到4-(chloromethyl)-7-(diethylamino)-2H-chromen-2-on
  参考文献：
  名称：

  基于独特的分子内碳-碳螺环化的香豆素笼罩的Rosamine探针

  摘要：

  笼状荧光团：我们报告了基于独特的分子内碳-碳螺环化作用的玫瑰红胺荧光团的第一种笼统策略。与传统的硝基苄基笼式cage吨探针相比，新型的碳-碳螺环笼式探针具有多个显着优势，可用于活细胞的空间控制荧光成像（见图）。

  DOI：

  10.1002/chem.201000015

文献信息

• Coumarin-Caged Rosamine Probes Based on a Unique Intramolecular Carbon-Carbon Spirocyclization
  作者：Weiying Lin、Lingliang Long、Wen Tan、Bingbing Chen、Lin Yuan

  DOI：10.1002/chem.201000015

  日期：2010.4.6

  Caged fluorophore: We report the first caging strategy for rosamine fluorophores based on a unique intramolecular carbon–carbon spirocyclization. The new class of carbon–carbon spirocyclic caged probes exhibit several significant advantages over the traditional nitrobenzyl‐caged xanthene probes and can be employed for spatially controlled fluorescence imaging of living cells (see graphic).

  笼状荧光团：我们报告了基于独特的分子内碳-碳螺环化作用的玫瑰红胺荧光团的第一种笼统策略。与传统的硝基苄基笼式cage吨探针相比，新型的碳-碳螺环笼式探针具有多个显着优势，可用于活细胞的空间控制荧光成像（见图）。
• Visible light-activatable Q-dye molecular beacons for long-term mRNA monitoring in neurons
  作者：Robin Klimek、Paul G. Donlin-Asp、Claudio Polisseni、Vanessa Hanff、Erin M. Schuman、Alexander Heckel

  DOI：10.1039/d1cc05664f

  日期：——

  We present a new class of visible light-activatable Q-dye molecular beacons. They are used to monitor endogenous mRNA in live neurons for up to 14 hours.

  我们提出了一类新型的可见光活化Q染料分子信标。它们用于监测活体神经元中的内源性mRNA长达14小时。
• Synthesis, Photophysical, Photochemical, and Computational Studies of Coumarin-Labeled Nicotinamide Derivatives
  作者：Pauline Bourbon、Qian Peng、Guillermo Ferraudi、Cynthia Stauffacher、Olaf Wiest、Paul Helquist

  DOI：10.1021/jo2025527

  日期：2012.3.16

  The syntheses and photophysical/photochemical properties of two amide-tethered coumarin-labeled nicotinamides are described. Photochemical studies of 6-bromo-7-hydroxycoumarin-4-ylmethylnicotinamide (BHC-nicotinamide) revealed an unexpected solvent effect. This result is rationalized by computational studies of the different protonation states using TD-DFT with the M06L/6-311+G** method with implicit and explicit solvation models. Molecular orbital energies responsible for the lambda(max) excitation show that the functionalization of the coumarin ring results in a strong red-shift from 330 to 370 nm when the pH of solution is increased from 3.06 to 8.07. From this MO analysis, a model for solvent interactions has been proposed. The BHC-nicotinamide proved to be photochemically stable, which is also interpreted in terms of NBO calculations. The results provide a set of principles for the rational design of either photostable labeling reagents or photolabile cage compounds.
• Visible Light Activates Coumarin‐Caged mRNA for Cytoplasmic Cap Methylation in Cells
  作者：Amarnath Bollu、Helena Schepers、Nils Klöcker、Mehmet Erguven、Ann‐Marie Lawrence‐Dörner、Andrea Rentmeister

  DOI：10.1002/chem.202303174

  日期：2024.1.8

  Protein synthesis is important and regulated by various mechanisms in the cell. Translation initiation in eukaryotes starts at the 5′ cap and is the most complex of the three phases of mRNA translation. It requires methylation of the N7 position of the terminal guanosine (m⁷G). The canonical capping occurs in the nucleus, however, cytoplasmic recapping has been discovered. It functions in switching mRNAs between translating and non‐translating states, but the individual steps are difficult to dissect. We targeted cytoplasmic cap methylation as the ultimate step of cytoplasmic recapping. We present an N7G photocaged 5′ cap that can be activated for cytoplasmic methylation by visible light. We report chemical and chemo‐enzymatic synthesis of this 5′ cap with 7‐(diethylamino)‐4‐methyl‐coumarin (DEACM) at the N7G and validate that it is not bound by translation initiation factor 4E (eIF4E). We demonstrate incorporation into mRNA, the release of unmethylated cap analog and enzymatic remethylation to functional cap 0 after irradiation at 450 nm. In cells, irradiation triggers translation of mRNAs with the N7G photocaged 5′ cap via cytoplasmic cap methylation.

  摘要 蛋白质合成在细胞中非常重要，并受到各种机制的调控。真核生物的翻译起始始于 5′帽，是 mRNA 翻译三个阶段中最复杂的一个。它需要末端鸟苷的 N7 位置发生甲基化（m7G）。典型的加帽发生在细胞核中，但也发现了细胞质中的再加帽。它的功能是在翻译和非翻译状态之间切换 mRNA，但其中的各个步骤却很难剖析。我们将细胞质帽甲基化作为细胞质重帽的最终步骤。我们提出了一种可通过可见光激活细胞质甲基化的 N7G 光标记 5′ cap。我们报告了在 N7G 处用 7-（二乙基氨基）-4-甲基香豆素（DEACM）通过化学和化学酶法合成这种 5′帽的过程，并验证了它不会被翻译起始因子 4E （eIF4E）结合。我们证明了在 450 纳米波长的辐照下，未甲基化的帽子类似物掺入到 mRNA 中，并释放出酶再甲基化为功能性帽子 0。在细胞中，辐照通过细胞质帽甲基化触发带有 N7G 光标记 5′ 帽的 mRNA 翻译。