黄芩素-7-甲醚 | 29550-13-8

• 物质功能分类: 有机原料 - 醚类化合物及其衍生物
• 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: 黄芩素-7-甲醚
• 中文别名: 5,6-二羟基-7-甲氧基黄酮；黄岑素-7-甲醚
• 英文名称: 5,6-dihydroxy-7-methoxyflavone
• 英文别名: negletein；baicalein-7-methyl ether；5,6-dihydroxy-7-methoxy-2-phenyl-4H-chromen-4-one；7-O-methylbaicalein；7-methoxybaicalein；5,6-dihydroxy-7-methoxy-2-phenylchromen-4-one
• CAS: 29550-13-8
• 化学式: C₁₆H₁₂O₅
• 分子量: 284.268
• InChiKey: ZTHLHHDJRXJGRX-UHFFFAOYSA-N

物化性质

• 熔点：
  218-220°C
• 沸点：
  541.1±50.0 °C(Predicted)
• 密度：
  1.420±0.06 g/cm3(Predicted)
• 溶解度：
  溶于二甲基亚砜
• LogP：
  3.220 (est)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  76
• 氢给体数：
  2
• 氢受体数：
  5

安全信息

• 危险类别码：
  R36/37/38
• 海关编码：
  2914509090
• 安全说明：
  S26,S36
• 危险性防范说明：
  P261,P280,P302+P352,P304+P340,P305+P351+P338,P362+P364
• 危险性描述：
  H315,H319,H335
• 储存条件：
  | 2-8℃ |

制备方法与用途

生物活性

Negletein 是一种神经保护剂，能增强神经生长因子的作用并诱导 PC12 细胞中的神经突向外生长。Negletein 还表现出抗炎活性，通过抑制 TNF-α 和 IL-1β 的表达，其 IC50 值分别为 16.4 μM 和 10.8 μM。

靶点

目标分子	IC50 值（单位：nM）
TNF-α	16.4 nM
IL-1β	10.8 nM

反应信息

• 作为反应物：
  描述：

  黄芩素-7-甲醚 在 水 、 氢溴酸 、 甲基三辛基氯化铵 作用下， 反应 8.0h， 以80%的产率得到黄芩素
  参考文献：
  名称：

  Efficient Method for Demethylation of Aryl Methyl Ether Using Aliquat-336

  摘要：

  A rapid method for selective cleavage of aryl methylethers can be achieved in the presence of a protic acid and a catalytic amount of phase-transfer catalyst (Aliquat-336). Aliquat-336 accelerates the rate of reaction and affords the corresponding phenols in excellent to good yields on a wide variety of substrates. [Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications (R) for the following free supplemental resource(s): Full experimental and spectral details.]

  DOI：

  10.1080/00397911.2013.772201
• 作为产物：
  描述：

  黄芩苷 在 sodium tetrahydroborate 、 硫酸 作用下， 生成 黄芩素-7-甲醚
  参考文献：
  名称：

  A convenient and efficient approach to synthesize negletein from baicalin

  摘要：

  A simple two-step/one-pot and highly efficient strategy for the synthesis of negletein from naturally abundant and inexpensive baicalin has been developed. In this one-pot sequence, esterification of baicalin catalyzed by concentrated H2SO4 in methanol followed by the treatment with excess NaBH4 afforded negletein in moderate yield. This method provides an additional approach for the synthesis of negletein. (C) 2016 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2016.03.085

文献信息

• [EN] PROCESS FOR SYNTHESIS OF OROXYLIN A<br/>[FR] PROCÉDÉ DE SYNTHÈSE D'OROXYLINE A
  申请人：MAJEED MUHAMMED

  公开号：WO2020032913A1

  公开（公告）日：2020-02-13

  Disclosed is a novel, simple, scalable and environment friendly process for the synthesis of Oroxylin A from Baicalin. Baicalm is esterified to obtain a methyl ester which is further selectively methylated to provide Oroxylin A gluciironide methyl ester which on de- glycosylation results in the formation of Oroxylin A.

  揭示了一种新颖、简单、可扩展且环境友好的过程，用于从黄芩苷合成黄芩素A。将黄芩苷酯化以获得甲酯，进一步选择性地甲基化以提供黄芩素A葡糖苷甲酯，脱糖后形成黄芩素A。
• A new domino oxidation—rearrangement of 2,3-dihydrowogonin to negletein
  作者：Cornelia Spoerlein-Guettler、Wolfgang Milius、Johannes Obenauf、Rainer Schobert

  DOI：10.1016/j.tetlet.2016.02.093

  日期：2016.4

  We report an expeditious, iodine-catalysed oxidation of 2,3-dihydrowogonin to negletein which comprises a Wessely–Moser rearrangement (WMR), associated not with an O-demethylation, as usual, but with an oxygen to oxygen methyl shift. In contrast, DDQ in 1,4-dioxane oxidised 2,3-dihydrowogonin to wogonin without rearrangements.

  我们报道了碘的快速催化氧化作用，将2,3-二氢牛精蛋白氧化为神经节蛋白，该蛋白包括Wessely-Moser重排（WMR），与通常的O-去甲基化无关，而是氧到氧的甲基转移。相反，在1，4-二恶烷中的DDQ将2，3-二氢沃戈宁氧化成沃戈宁而没有重排。
• An unambiguous and practical synthesis of Oroxylin A: a commonly misidentified flavone
  作者：Hosahalli P. Hemantha、Rajendran Ramanujam、Muhammed Majeed、Kalyanam Nagabhushanam

  DOI：10.1080/14786419.2019.1650359

  日期：2021.5.3

  published routes claiming the synthesis of Oroxylin A (1) have in fact led to a regioisomer Negletein that was misinterpreted as Oroxylin A. In the present work, we describe a novel, straight-forward and scalable semi-synthetic approach for rapid access to the title compound, the structure of which is unambiguously secured by NMR and X-ray crystallographic analysis of a derivative. This work also encompasses

  摘要 木蝴蝶A，中的提取物的主要类黄酮木蝴蝶以及黄芩具有有用的药用功效。许多声称合成Oroxylin A（1）的已公开路线实际上导致了区域异构体Negletein被误解为OroxylinA。在本工作中，我们描述了一种新颖，直接且可扩展的半合成方法，可快速进行合成。获得标题化合物，其结构通过衍生物的NMR和X射线晶体学分析明确确定。这项工作还涵盖了Oroxylin A即OAGME（2）的糖基化衍生物的合成，该衍生物具有明显的药理学重要性。
• Process for synthesis of Oroxylin A
  申请人：Majeed Muhammed

  公开号：US10407401B1

  公开（公告）日：2019-09-10

  Disclosed is a novel, simple, scalable and environment friendly process for the synthesis of Oroxylin A from Baicalin. Baicalin is esterified to obtain a methyl ester which is further selectively methylated to provide Oroxylin A glucuronide methyl ester which on de-glycosylation results in the formation of Oroxylin A.

  揭示了一种新颖、简单、可扩展且环境友好的过程，用于从黄芩苷合成黄芩素A。将黄芩苷酯化以获得甲酯，进一步选择性地进行甲基化以提供甲酯化的黄芩素A葡萄糖苷，脱糖后形成黄芩素A。
• Crystal structures of the flavonoid Oroxylin A and the regioisomers Negletein and Wogonin
  作者：Ruel Valerio Robles De Grano、Elena V. Vashchenko、Madiha Nisar、Herman H.-Y. Sung、Valerii V. Vashchenko、Ian D. Williams

  DOI：10.1107/s2053229620005550

  日期：2020.5.1

  The flavonoid Oroxylin A (6-methoxychrysin or 5,7-dihydroxy-6-methoxy-2-phenyl-4H-chromen-4-one, C₁₆H₁₂O₅) and its regioisomers are of increasing interest for a variety of bioactive functions and their pharmaceutical formulation is of importance. Previous difficulties in the separation and misidentification of Oroxylin A from its regioisomers Wogonin (8-methoxychrysin or 5,7-dihydroxy-8-methoxy-2-phenyl-4H-chromen-4-one) and Negletein (5,6-dihydroxy-7-methoxyflavone or 5,6-dihydroxy-7-methoxy-2-phenyl-4H-chromen-4-one) render its full structural and powder X-ray characterization highly desirable. The low-temperature (100 K) crystal structures of Oroxylin A, Negletein and Wogonin sesquihydrate are reported for the first time. Wogonin crystallizes in two related but distinct hydrated forms. These have very similar powder diffractograms, indicating that such issues need to be addressed for its pharmaceutical formulation.

  黄酮类化合物 Oroxylin A（6-甲氧基金丝桃素或 5,7-二羟基-6-甲氧基-2-苯基-4H-苯并吡喃-4-酮，C16H12O5）及其 Regioisomers 因具有多种生物活性功能而越来越受到关注，其药物配方也非常重要。以前在将 Oroxylin A 从其 Regioisomers Wogonin（8-甲氧基 Chrysin 或 5,7-二羟基-8-甲氧基-2-苯基-4H-苯并吡喃-4-酮）和 Negletein（5,6-二羟基-7-甲氧基黄酮或 5,6-二羟基-7-甲氧基-2-苯基-4H-苯并吡喃-4-酮）中分离和错误鉴别方面存在困难，因此非常需要对其进行全面的结构和粉末 X 射线表征。本研究首次报道了 Oroxylin A、Negletein 和 Wogonin sesquihydrate 的低温（100 K）晶体结构。Wogonin 以两种相关但不同的水合形式结晶。它们的粉末衍射图非常相似，这表明其药物制剂需要解决这些问题。