3-nitro-6-methoxycoumarin | 88184-85-4

• 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: 3-nitro-6-methoxycoumarin
• 英文别名: 6-methoxy-3-nitrocoumarin；2H-1-Benzopyran-2-one, 6-methoxy-3-nitro-；6-methoxy-3-nitrochromen-2-one
• CAS: 88184-85-4
• 化学式: C₁₀H₇NO₅
• 分子量: 221.169
• InChiKey: KPUDEBDVRHIZLR-UHFFFAOYSA-N

物化性质

• 熔点：
  195-196 °C
• 沸点：
  407.9±45.0 °C(Predicted)
• 密度：
  1.46±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  81.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-nitro-6-methoxycoumarin 在 三溴化硼 、 碳酸氢钠 作用下， 以 5,5-dimethyl-1,3-cyclohexadiene 、 二氯甲烷 为溶剂， 反应 32.0h， 生成
  参考文献：
  名称：

  通过Glob反应构建五环lamellarin骨架：在Lamellarins H和D的全合成中的应用

  摘要：

  据报道，在密封管中通过3-硝基香豆素和罂粟碱的碱促进的Grob型偶联有效地构建了苯基取代的香豆素-吡咯-异喹啉-稠合的五环。该反应进一步应用于三个线性步骤中的层状蛋白H和八个线性步骤中的层状蛋白D的总合成，总产率分别为31％和14％。

  DOI：

  10.1021/acs.joc.7b01061
• 作为产物：
  描述：

  2-羟基-5-甲氧基苯甲醛 、 硝基乙酸甲酯 在 二乙胺盐酸盐 作用下， 以 甲苯 为溶剂， 反应 48.0h， 以79%的产率得到3-nitro-6-methoxycoumarin
  参考文献：
  名称：

  A Convenient One-Flask Synthesis of 3-Nitrocoumarins

  摘要：

  DOI：

  10.1055/s-1983-30534

文献信息

• Improvement of Fluorescence Characteristics of Coumarins: Syntheses and Fluorescence Properties of 6-Methoxycoumarin and Benzocoumarin Derivatives as Novel Fluorophores Emitting in the Longer Wavelength Region and Their Application to Analytical Reagents
  作者：Chiyomi Murata、Toshinobu Masuda、Yasuko Kamochi、Kenichiro Todoroki、Hideyuki Yoshida、Hitoshi Nohta、Masatoshi Yamaguchi、Akira Takadate

  DOI：10.1248/cpb.53.750

  日期：——

  To improve the fluorescence characteristics, especially emission wavelength, of coumarins, various 3-substituted-6-methoxycoumarin derivatives were synthesized, and then benzocoumarin derivatives were also synthesized in expectation of the shift to the longer wavelength region by the extension of the conjugated system. Their fluorescence properties were investigated spectrophotometrically in acetonitrile and evaluated from the viewpoint of the intramolecular charge transfer (ICT) between push- and pull-substituents in the ground and the excited states. Among them, benzocoumarin derivatives especially fluoresced in the longer wavelength around 540 nm with remarkably large Stokes shifts beyond 10000 cm−1. Using such fluorophores, some novel fluorescence derivatization reagents for carboxylic acids, alcohols, phenols, and amines were preliminarily prepared as an example, and their derivatized products were also found to fluoresce in the longer wavelength region with large Stokes shifts.

  为了改善香豆素的荧光特性，特别是发射波长，合成了多种3取代-6-甲氧基香豆素衍生物，随后又合成了苯香豆素衍生物，期待通过延长共轭体系实现向长波长区域的转移。采用光谱法在乙腈中研究了它们的荧光特性，并从基态和激发态中推送和拉动取代基之间的分子内电荷转移（ICT）角度进行了评估。在这些衍生物中，苯香豆素衍生物特别在540 nm附近的长波长范围内具有显著的荧光，斯托克斯位移超过10000 cm−1。利用这些荧光基团，初步制备了一些新型的荧光衍生化试剂用于羧酸、醇、酚和胺，发现其衍生化产物在长波长区域也具有显著的荧光和较大的斯托克斯位移。
• Looking for New Targets: Simple Coumarins as Antibacterial Agents
  作者：Maria Joao Matos、Saleta Vazquez-Rodriguez、Lourdes Santana、Eugenio Uriarte、Cristina Fuentes-Edfuf、Ysabel Santos、Angeles Munoz-Crego

  DOI：10.2174/1573406411208061140

  日期：2012.9.1

  The dramatic worldwide increase of dangerous infections by resistant and multi-resistant microbes makes the search of new molecules and new chemical entities an important topic in Medicinal Chemistry. As the ideal drug candidate has not been attained, an intensive search for new and innovative antimicrobials is still needed. A small series of 3- amino/nitrocoumarins without substitutions or substituted by methyl or methoxy groups at different positions were synthesized and evaluated for their antibacterial and antifungal activities against clinical isolates of Staphylococcus aureus, Escherichia coli and Candida albicans strains. Some of these structurally simple molecules exhibited antibacterial activity. The preliminary SAR study showed that the antibacterial activity against E. coli and S. aureus was dependent on the kind and position of the substitution pattern at the coumarin moiety.

  全球范围内由耐药和多重耐药微生物引起的危险感染急剧增加，使得 寻找新分子和新化学实体是药物化学的重要课题。作为理想的候选药物 虽然尚未实现，但仍需要深入寻找新的创新抗菌药物。小编整理了3- 合成了未取代或在不同位置被甲基或甲氧基取代的氨基/硝基香豆素 并评估其对金黄色葡萄球菌临床分离株的抗菌和抗真菌活性， 大肠杆菌和白色念珠菌菌株。其中一些结构简单的分子表现出抗菌活性。 初步SAR研究表明，对大肠杆菌和金黄色葡萄球菌的抗菌活性取决于 香豆素部分的取代模式的种类和位置。
• Copper(I) phosphoramidite catalyzed asymmetric conjugate addition of dialkylzinc reagents of α,β-unsaturated nitroacetates; an enantioselective route to β-aryl-nitroalkanes
  作者：Jos P.G. Versleijen、Albert M. van Leusen、Ben L. Feringa

  DOI：10.1016/s0040-4039(99)01118-1

  日期：1999.7

  The asymmetric copper(I) phosphoramidite catalyzed conjugate addition of dialkylzinc reagents to E,Z-mixtures of α,β-unsaturated nitroacetates provided the 1,4-adducts in excellent yields but with low e.e.'s. High enantioselectivities (e.e.'s up to 92%) were obtained with structurally rigid 3-nitrocoumarins, leading to a new route to optically active β-aryl-nitroalkanes.

  不对称铜（I）亚磷酰胺催化将二烷基锌试剂共轭加成到α，β-不饱和硝基乙酸酯的E，Z混合物中，从而以优异的收率提供1,4加合物，但ee较低。使用结构刚性的3-硝基香豆素可实现高对映选择性（ee高达92％），从而开辟了一种新的制备旋光性β-芳基-硝基烷烃的途径。
• Lewis acid-controlled divergent condensation of 1,1-bis(methylthio)-2‑nitroethylene and salicylaldehydes for the synthesis of 3-nitrocoumarins and 4H-chromenes
  作者：Li Han、Xiaocao Quan、Xusheng Shao、Xiaoyong Xu、Zhong Li

  DOI：10.1016/j.tetlet.2022.154080

  日期：2023.3

  An efficient Lewis acid-controlled divergent synthesis of 3-nitrocoumarins and 4H-chromenes under mild conditions has been developed. The corresponding 3-nitrocoumarin products were obtained in moderate to excellent yields through FeCl3-catalyzed annulation of 1,1-bis (methylthio)-2‑nitroethylene with various salicylaldehydes, while 4H-chromene products were afforded by using BF3·OEt2 as catalyst with

  已开发出一种在温和条件下有效的路易斯酸控制发散合成 3-硝基香豆素和 4 H-色烯的方法。FeCl 3催化1,1-双(甲硫基)-2-硝基乙烯与各种水杨醛环化得到相应的3-硝基香豆素产物，收率中等，而4 H-色烯产物通过BF 3 ·OEt得到2作为具有相同起始原料的催化剂。
• Photoredox-Catalyzed Redox-Neutral Decarboxylative C–H Acylations of Coumarins with α-Keto Acid
  作者：Bin Sun、Yingying Wang、Jiayin Wang、Maojie Chen、Zhicheng Zhong、Jiayang Wang、Can Jin

  DOI：10.1021/acs.orglett.3c00632

  日期：——

  A novel and green photocatalytic strategy for the synthesis of C-4-acylated coumarins with α-keto acids and 3-nitrocoumarin has been developed. This operationally simple protocol works under mild reaction conditions, providing convenient access to 4-acyl coumarin derivatives. The control experimental results showed that the nitro radical produced by the cleavage of the C–N bond acts as an electron

  开发了一种新型绿色光催化策略，用于用 α-酮酸和 3-硝基香豆素合成 C-4-酰化香豆素。这个操作简单的协议在温和的反应条件下工作，提供了方便地获取 4-酰基香豆素衍生物。对照实验结果表明，C-N键断裂产生的硝基自由基作为电子受体完成光催化循环，实现氧化还原中性反应。