6,8-二溴槲皮素 | 95412-48-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 黄酮类化合物
• 中文名称: 6,8-二溴槲皮素
• 英文名称: 6,8-dibromoquercetin
• 英文别名: Dibromquercetin；6,8-dibromo-2-(3,4-dihydroxyphenyl)-3,5,7-trihydroxychromen-4-one
• CAS: 95412-48-9
• 化学式: C₁₅H₈Br₂O₇
• 分子量: 460.032
• InChiKey: UANVZECKJMLNEN-UHFFFAOYSA-N

物化性质

• 沸点：
  635.4±55.0 °C(Predicted)
• 密度：
  2.296±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  24
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  127
• 氢给体数：
  5
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  6,8-二溴槲皮素 在 sodium sulfite 作用下， 以 水 为溶剂， 反应 18.0h， 以87%的产率得到槲皮素
  参考文献：
  名称：

  在水介质中用亚硫酸钠对苯酚和杂芳族化合物进行还原脱卤和脱卤磺化

  摘要：

  质子互变异构被用作在水介质中使用亚硫酸钠作为唯一试剂的（杂）芳基溴化物和碘化物的还原性脱卤化或（杂）芳基氯和氟化物的脱卤化磺化的工具。该方案不需要金属或相转移催化剂，避免使用有机溶剂作为反应介质。此方法特别适用于容易互变异构的底物（例如2-或4-卤代氨基酚和4-卤代间苯二酚），在温和的反应条件下（≤60°C）会进行脱卤或磺化。由于亚硫酸钠是一种廉价，安全且对环境无害的试剂，因此该方法至少具有三个潜在应用：（i）使用亚硫酸钠作为还原剂对卤素作为保护基进行脱保护；（ii）在温和的反应条件下磺化芳族卤化物，避免使用危险和腐蚀性的试剂/溶剂；（iii）将有毒的卤代芳族化合物转化为危害较小的化合物。

  DOI：

  10.1039/c9gc00467j
• 作为产物：
  描述：

  槲皮素 在 2,3-二溴-3-苯基丙酸 、 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 以50%的产率得到6,8-二溴槲皮素
  参考文献：
  名称：

  黄酮类化合物的温和选择性溴化方法

  摘要：

  开发了一种在碱存在下使用 α,β-二溴氢化肉桂酸以良好收率温和选择性溴化简单芳香族化合物和黄酮类化合物的新方法。该程序能够对氧化或自由基攻击高度敏感的化合物进行选择性单溴化或二溴化。制备了水飞蓟素黄酮木脂素和相关黄酮类化合物的新型溴化衍生物。这些溴化衍生物可在进一步合成中用作有价值的合成中间体。

  DOI：

  10.1021/acs.jnatprod.0c00655

文献信息

• Structure and antioxidant activity of brominated flavonols and flavanones
  作者：Gonçalo C. Justino、Margarida Rodrigues、M. Helena Florêncio、Lurdes Mira

  DOI：10.1002/jms.1630

  日期：2009.10

  Hypobromous acid (HOBr) produced by both eosinophil peroxidase (EPO) and myeloperoxidase (MPO) is a stronger oxidant than HOCl, and is also essential for optimal and efficient microbial killing. Considering the potential cytotoxic effect of HOBr, if it is formed outside the phagosome, it should be useful to scavenge it in order to protect the nearby tissues. In this study the ability of selected flavonoids to protect against HOBr mediated oxidation reactions was performed through a competitive reaction, and the resulting products identified by high performance liquid chromatography (HPLC) and electrospray ionization tandem mass spectrometry(ESI-MS/MS). Several structural features were found to be important to confer high antioxidant activity to flavonoids towards HOBr: the C2C3 double bond and the 3OH group in the C-ring, and the presence of both 5OH and 7OH groups in the A-ring. The MS results showed that flavonoids are dibrominated in the A-ring, suggesting that (except for fisetin) bromination occurs at C6 and C8 positions, through an electrophilic aromatic substitution reaction. The chemical modifications achieved by bromination of flavonoids have changed their biological properties, presenting their brominated derivatives higher antioxidant activity, as radical scavengers, and higher lipophilicity, than the parent flavonoids. Brominated flavonoids may then diffuse easily through membranes increasing the intracellular concentration of the compounds. These locally formed metabolites may also interact with signaling cascades involving cytokines and regulatory transcription factors, thus playing a role in inflammation and in the regulation of immune response. Copyright © 2009 John Wiley & Sons, Ltd.

  由嗜酸性粒细胞过氧化物酶（EPO）和髓过氧化物酶（MPO）产生的次溴酸（HOBr）是一种比次氯酸（HOCl）更强的氧化剂，并且对于最佳和高效的微生物杀灭至关重要。考虑到HOBr可能的细胞毒性效应，如果它在吞噬体外形成，则清除它可以保护附近的组织。在本研究中，选择的黄酮类化合物对抗HOBr介导的氧化反应的保护能力通过竞争反应进行研究，并通过高效液相色谱（HPLC）和电喷雾电离串联质谱（ESI-MS/MS）识别出所产生的产物。发现几个结构特征对赋予黄酮类化合物高抗氧化活性与HOBr相关非常重要：C2=C3双键和C环中的3-OH基团，以及A环中同时存在的5-OH和7-OH基团。质谱结果显示，黄酮类化合物在A环中被二溴化，表明（除了鬼针草素）溴化发生在C6和C8位点，通过电亲电芳香取代反应实现。黄酮类化合物的溴化所带来的化学修饰改变了它们的生物学特性，使得其溴化衍生物在作为自由基清除剂时表现出更高的抗氧化活性和更高的脂溶性，较之于母体黄酮。溴化黄酮可能更容易通过膜扩散，从而提高化合物的细胞内浓度。这些局部形成的代谢物也可能与涉及细胞因子和调节转录因子的信号传导级联反应相互作用，从而在炎症和免疫应答的调节中发挥作用。版权所有 © 2009 John Wiley & Sons, Ltd.
• Synthesis of Brominated Quercetin Derivatives Using Distinct Brominating Systems
  作者：Mei Peng、Fengxian Liu、Xin Feng、Fan Yang、Xiaoping Yang

  DOI：10.14233/ajchem.2014.16175

  日期：——

  6,8-Dibromoquercetin derivatives were obtained through reaction of quercetin with HBr-H2O2. On the other hand, quercetin reacted with bromine to synthesize poly brominated derivatives. The reaction procedures were monitored by either TLC or HPLC or both in some cases. The reaction products were further purified via either recrystallization or silica gel column chromatography. Then the chemical structures were further confirmed by 1H NMR and LC-MS. Two new quercetin brominated derivatives, namely 6,8-dibromoquercetin and 6,8,2,5,6-pentabrominated quercetin were obtained. Two distinct brominated approaches were studied to obtain two different quercetin brominated derivatives, 6,8-dibromoquercetin and 6,8,2,5,6-pentabrominated quercetin with the yields of 80 and 70 %, respectively.

  6,8-二溴槲皮素衍生物是通过槲皮素与HBr-H2O2反应得到的。另一方面，槲皮素与溴反应合成多溴化衍生物。反应过程通过TLC或HPLC或两者在某些情况下进行监测。反应产物通过重结晶或硅胶柱色谱进一步纯化。然后通过1H NMR和LC-MS进一步确认化学结构。得到了两种新的槲皮素溴化衍生物，即6,8-二溴槲皮素和6,8,2,5,6-五溴槲皮素。研究了两种不同的溴化方法，以获得两种不同的槲皮素溴化衍生物，即6,8-二溴槲皮素和6,8,2,5,6-五溴槲皮素，产率分别为80%和70%。
• Identifying therapeutic compounds based on their physical-chemical properties
  申请人：——

  公开号：US20040105817A1

  公开（公告）日：2004-06-03

  The present invention is directed to rapid and efficient methods of identifying therapeutic compounds by allowing only the most favorable molecules initially selected based on their physical-chemical profile falling within a range predefined by the physical-chemical/biological relationship of a previously tested small subset of compounds of same core structure to be assayed; and to the therapeutic compositions identified by said methods.

  本发明旨在通过仅允许最有利的分子最初被选择，这些分子基于它们的物理化学特性落在由之前测试的具有相同核心结构的小型化合物子集的物理化学/生物学关系预定义的范围内进行测定，从而实现快速和高效的识别治疗化合物的方法；以及由该方法确定的治疗组合物。
• Herzig, Monatshefte fur Chemie, 1885, vol. 6, p. 872
  作者：Herzig

  DOI：——

  日期：——
• Solvent-dependent release of bromine from bromoquercetins
  作者：Mario C. Foti、Concetta Rocco

  DOI：10.1016/j.tetlet.2014.05.110

  日期：2014.7

  Quercetin, 6-bromoquercetin (3), and 8-bromoquercetin (4) undergo H/D exchange at 6- and 8-positions, in acetone-d(4) and methanol-d(4), catalyzed by acids and bases. The base-catalyzed process is faster, and in acetone-d(6) the half-lives of H-8 and H-6 are 56.5 and 48.6 h, respectively. A high regioselectivity at the position 8 of quercetin is observed under acid-catalysis in both solvents but in methanol-d(4) regioselectivity is retained even under base-catalysis. On the other hand, 6,8-dibromoquercetin (2), 4 and 6,8-dibromo-2'-hydroxyquercetin (5) manifest the ability of exchanging bromine with hydrogen (or deuterium) under acid-catalysis in acetone and other enolizable ketones (e.g., methyl ethyl ketone, acetylacetone, and isophorone). These bromophenols release bromine from their 8-position only, in a slow bromination process that likely involves their protonated form (arenium ion I) as brominating agent and the enol of the above ketones as Br-acceptor. The arenium ion I of these bromophenols is expected to be a powerful electrophile and its formation is most likely to be rate-determining. (C) 2014 Elsevier Ltd. All rights reserved.