6-bromo-2-ferrocenyl-chromen-4-one | 1332699-49-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 6-bromo-2-ferrocenyl-chromen-4-one
• 英文别名: 6-bromido-2-ferrocenylchromen-4-one；(η5-C6H3Br(O)C(O)CHCC5H4)Fe(η5-C5H5)；6-bromo-2-ferrocenyl-4H-chromen-4-one；6-bromo-2-cyclopenta-2,4-dien-1-ylchromen-4-one;cyclopenta-1,3-diene;iron(2+)
• CAS: 1332699-49-6
• 化学式: C₁₉H₁₃BrFeO₂
• 分子量: 409.062
• InChiKey: SBXQENCZXWMJGI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.34
• 重原子数：
  23
• 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：
  26.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  oxone 、 6-bromo-2-ferrocenyl-chromen-4-one 以 二氯甲烷 、 水 、 丙酮 为溶剂， 以76%的产率得到6-bromido-3-hydroxy-2-ferrocenylchromen-4-one
  参考文献：
  名称：

  Synthesis and Structural Characterization of Ferrocenyl-Substituted Aurones, Flavones, and Flavonols

  摘要：

  In the context of our studies on the modification of bioactive molecules with ferrocene, we here report the first examples of ferrocenyl flavonoids, where ferrocene replaces the B ring of the flavonoid skeleton. Ferrocenyl aurones possessing an electron-withdrawing or an electron-donating group in the 5'-position were obtained from 5'-R-2'-hydroxy-3-ferrocenyl chalcones via 1,5 oxidative exocyclization using Hg(OAc)(2) or AgOTf. Treatment of the ferrocenyl aurones with LDA resulted in a ring opening to form ferrocenyl ynones, which could then be selectively recydized to the flavone isomer by treatment with NaOEt. Ferrocenyl flavones were also obtained by isomerization of the aurones with KCN and were hydroxylated in the 3-position to form ferrocenyl flavonols with oxone in a biphasic reaction. In many cases the reactivity of the ferrocenyl compounds was significantly different from that of their organic analogues. This reactivity and regioselectivity can be rationalized by ferrocene's particular ability to destabilize alpha-anions in reaction intermediates. Representative examples of ferrocenyl aurones, ynones, and flavones were characterized by 2D NMR and X-ray crystallography, and the molecules all show a planar arrangement of the organic skeleton with the cyclopentadienyl ring of the ferrocene group. Putative MLCT bands in the visible region are responsible for the variety of highly saturated colors observed.

  DOI：

  10.1021/om200644e
• 作为产物：
  描述：

  1-(5'-bromido-2'-hydroxyphenyl)-3-ferrocenylprop-2-yn-1-one 在 sodium ethanolate 作用下， 以 乙醇 为溶剂， 反应 24.0h， 以65%的产率得到6-bromo-2-ferrocenyl-chromen-4-one
  参考文献：
  名称：

  [EN] FERROCENYL FLAVONOIDS
  [FR] FLAVONOÏDES COMPRENANT UN GROUPE FERROCÉNYLE

  摘要：

  公开号：

  WO2011107572A8

文献信息

• Synthesis of cytotoxic ferrocenyl flavones via a ferricenium-mediated 1,6-oxidative cyclization
  作者：Jean-Philippe Monserrat、Guy G. Chabot、Louis Hamon、Lionel Quentin、Daniel Scherman、Gérard Jaouen、Elizabeth A. Hillard

  DOI：10.1039/c0cc01290d

  日期：——

  The oxidation of the ferrocenyl group of 2′-hydroxyferrocenyl chalcones activates the β-position of the unsaturated ketone to nucleophilic attack to yield the first examples of ferrocenyl flavones. These compounds are significantly more cytotoxic than their organic analogs on B16 melanoma cells, with IC50 values in the low micromolar range.

  2′-hydroxy ferrocenyl chalcones 的二茂铁基团氧化激活了不饱和酮的β位，使其受到亲核攻击，从而产生了首例二茂铁基黄酮。这些化合物对 B16 黑色素瘤细胞的细胞毒性明显高于其有机类似物，IC50 值在低微摩尔范围内。
• Ferrocenyl flavonoid-induced morphological modifications of endothelial cells and cytotoxicity against B16 murine melanoma cells
  作者：Jean-Philippe Monserrat、Keshri Nath Tiwari、Lionel Quentin、Pascal Pigeon、Gérard Jaouen、Anne Vessières、Guy G. Chabot、Elizabeth A. Hillard

  DOI：10.1016/j.jorganchem.2012.12.031

  日期：2013.6

  With the aim of improving the cytotoxic and vascular disrupting activities of flavonoids, several classes of ferrocenyl-modified flavonoids were prepared and tested on cancer and endothelial cells. Three tenmember series of ferrocenyl flavonoids: chalcones ((E)-1-(R-2'-hydroxypheny1)-3-ferrocenylprop-2-en-1-ones), aurones ((Z)-R-2-(ferrocenylidene)benzofuran-3-ones) and flavones (R-2-ferrocenyl-chromen-4-ones) were synthesized by recently reported methods. Three ferrocenyl flavonols (R-3-hydroxy2-ferrocenyl-chromen-4-ones) and four ferrocenyl flavanones (3-ferrocenylmethylidenyl-R-2-phenyl-chroman-4-ones) were also obtained. All compounds were evaluated for their cytotoxic effects on a cancer cell line (B16 murine melanoma) and for their morphological effects on endothelial cells (EAhy 926). Some interesting structure-activity relationships were disclosed: of all the compounds, the halogen-substituted aurones showed the best cytotoxic activity, with IC50 values ranging between 12 and 18 mu M. Ferrocenyl flavonols and ferrocenyl flavanones with substitution in the 3-position (-OH and =C-Fc respectively) were not active against cancer or endothelial cells. Some of the ferrocenyl flavones caused the endothelial cells to adopt a round shape ("rounding up") at submicromolar concentrations, which can be predictive of vascular disrupting activity. The most morphologically active flavones showed only moderate cytotoxicity against cancer cells, indicating that they may primarily act as antivascular agents. (C) 2013 Elsevier B.V. All rights reserved.
• Ferrocenyl-Appended Aurone and Flavone: Which Possesses Higher Inhibitory Effects on DNA Oxidation and Radicals?
  作者：Jia-Feng Chen、Zai-Qun Liu

  DOI：10.1021/tx500405b

  日期：2015.3.16

  The aim of the present work was to compare the antioxidative effect of the ferrocenyl-appended aurone with that of ferrocenyl-appended flavone; therefore, nine aurones together with the flavone-type analogues were synthesized by using chalcone as the reactant. The radical-scavenging property was evaluated by reacting with the 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate) cationic radical (ABTS'), 2,2'-diphenyl-1-picrylhydrazyl radical (DPPH), and galvinoxyl radical, respectively. The cytotoxicity was estimated by inhibiting 2,2'-azobis(2-amidinopropane hydrochloride) (AAPH)-induced oxidation of DNA. It was found that the introduction of the ferrocenyl group remarkably increased the radical-scavenging activities of aurone and flavone. Especially, the ferrocenyl group in flavones can quench radicals even in the absence of the phenolic hydroxyl group, while ferrocenyl-appended aurones can efficiently protect DNA against AAPH-induced oxidation. Therefore, the antioxidative effect was generated by the ferrocenyl group and enhanced by the electron-donating group attaching to the para-position of the ferrocenyl group. Introducing the ferrocenyl group into natural compounds may be a useful strategy for increasing the anticoddative effectiveness.