5.7.3'.4'-Tetramethoxy-flav-3-en | 16984-94-4

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 黄酮类化合物
• 英文名称: 5.7.3'.4'-Tetramethoxy-flav-3-en
• 英文别名: 5,7,3',4'-Tetramethoxyflavan-3-ene；2-(3,4-dimethoxyphenyl)-5,7-dimethoxy-2H-chromene
• CAS: 16984-94-4
• 化学式: C₁₉H₂₀O₅
• 分子量: 328.365
• InChiKey: GBQZRVVYZCECRN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5.7.3'.4'-Tetramethoxy-flav-3-en 在 水 、 二甲基二环氧乙烷 、 间苯三酚 作用下， 以 丙酮 、 水 、 二甲基亚砜 为溶剂， 以9 %的产率得到(+)-(2R,3S,4S)-3,4-dihydroxy-5,7,3',4'-tetramethoxyflavan
  参考文献：
  名称：

  Flav-3-ene 的合成和环氧化作为 Flavan-3,4-diols 仿生制备的方法

  摘要：

  由于类黄酮表现出大量的药理特性，如抗氧化、抗炎和抗菌活性，因此人们在这些化合物的医学和治疗应用方面做了大量工作。尽管 flavan-3,4-diols 在许多其他类别的类黄酮的合成中起着核心作用，但仅报道了几种制备这些化合物的方法。在本文中，公开了通过 3 步工艺从容易获得的起始材料制备甲氧基取代的黄烷 3,4-二醇的结果，显示出自然取代模式。还表明，如果在二甲基二氧杂环丙烷 (DMDO) 环氧化过程中添加芳香亲核试剂，则 4-芳基取代的类似物可以从相应的 flav-3-ene 获得。

  DOI：

  10.1055/s-0041-1738441
• 作为产物：
  描述：

  2-羟基-4,6-二甲氧基苯乙酮 在 sodium tetrahydroborate 、 sodium hydride 作用下， 以 正庚烷 、 N,N-二甲基甲酰胺 、 异丙醇 为溶剂， 反应 4.0h， 生成 5.7.3'.4'-Tetramethoxy-flav-3-en
  参考文献：
  名称：

  Flav-3-ene 的合成和环氧化作为 Flavan-3,4-diols 仿生制备的方法

  摘要：

  由于类黄酮表现出大量的药理特性，如抗氧化、抗炎和抗菌活性，因此人们在这些化合物的医学和治疗应用方面做了大量工作。尽管 flavan-3,4-diols 在许多其他类别的类黄酮的合成中起着核心作用，但仅报道了几种制备这些化合物的方法。在本文中，公开了通过 3 步工艺从容易获得的起始材料制备甲氧基取代的黄烷 3,4-二醇的结果，显示出自然取代模式。还表明，如果在二甲基二氧杂环丙烷 (DMDO) 环氧化过程中添加芳香亲核试剂，则 4-芳基取代的类似物可以从相应的 flav-3-ene 获得。

  DOI：

  10.1055/s-0041-1738441

文献信息

• Synthesis of C-3 Coupled Biflavonoids and C-3 Coupled Biflavonoid Analogues
  申请人：Van Der Westhuizen Jan Hendrik

  公开号：US20120289715A1

  公开（公告）日：2012-11-15

  The invention relates to methods for the preparation of an optically inactive and optically active compounds which are selected from the group consisting of C-3 coupled biflavonoids and C-3 coupled biflavonoid analogues from a starting material or intermediate which are respectively selected from the group consisting of optically inactive or optically active flavan-3-ols and optically active flavan-3-ones, the method comprising the steps of (a) providing an optically inactive or active compound having a flavan-3-ol structure or a compound which is a flavan-3-one, (b) if a compound having a flavan-3-ol structure with a hydroxy group on the C-3 carbon is selected as starting material, converting the hydroxy group on the C-3 carbon of the compound having the flavan-3-ol structure to an oxo group to form a flavan-3-one of that compound, (c) providing a compound having a nucleophilic aromatic moiety, which compound is selected from the group of compounds having a nucleophilic aromatic moiety and which have flavonoid base structures and compounds having a nucleophilic aromatic moiety and which do not have a flavonoid base structure, (d) contacting the flavan-3-one provided by step (a) or obtained by step (b) with the compound containing the nucleophilic aromatic moiety in the presence of a Lewis acid; (e) forming a first intermediate compound wherein the oxo group on the C-3 carbon is converted to a hydroxy group by virtue of nucleophilic addition when the compound containing the nucleophilic aromatic moiety is contacted to the C-3 carbon of the flavan-3-one, (f) subjecting the first intermediate compound to dehydration so as to introduce a double bond between the C-3 carbon and C-4 carbon of the intermediate compound with the concomitant removal of the hydroxy group from the C-3 carbon to form an optically active flavene compound which is substituted by the nucleophilic aromatic moiety on the C-3 carbon, (g) optionally subjecting the resultant flavene compound to hydroboration-oxidation hydration thereby removing said double bond between the C-3 carbon and the C-4 carbon with the concomitant introduction of a hydroxy group at the C-4 carbon to form a second intermediate compound, (h) further optionally oxidizing the second intermediate compound of step (g) thereby converting the hydroxy group at the said C-4 carbon to an oxo group, thereby forming a biflavonoid or biflavonoid analogue which is substituted by the selected nucleophilic aromatic moiety on the C-3 carbon, (i) further optionally, and alternatively to step (h), subjecting the resultant flavene compound of step (f) to OsO 4 dihydroxylation thereby removing said double bond between the C-3 carbon and C-4 carbon with the concomitant introduction of a hydroxy group at the C-4 carbon and a hydroxy group at the C-3 carbon to form a third intermediate compound, and (j) subjecting the third intermediate compound to dehydration whereby the hydroxy group at the C-3 carbon is removed and a double bond is introduced between the C-3 carbon and C-4 carbon thereby forming an enol product and allowing such enol product to rearrange spontaneously to form a biflavonoid or biflavonoid analogue having an oxo group at its C-4 carbon and which is substituted by the selected nucleophilic aromatic moiety on its C-3 carbon.

  本发明涉及一种制备选自C-3偶联的双黄酮和C-3偶联的双黄酮类似物的无光学活性和光学活性化合物的方法，其起始材料或中间体分别选自无光学活性或光学活性的黄烷-3-醇和光学活性的黄烷-3-酮，该方法包括以下步骤：(a)提供具有黄烷-3-醇结构的无光学活性或活性化合物或具有黄烷-3-酮结构的化合物；(b)如果选择具有C-3碳上羟基的黄烷-3-醇结构的化合物作为起始材料，则将该化合物的C-3碳上的羟基转化为羰基基团，形成该化合物的黄烷-3-酮；(c)提供一种具有亲核芳香基团的化合物，该化合物选自具有亲核芳香基团的黄酮基结构和不具有黄酮基结构的具有亲核芳香基团的化合物；(d)在路易斯酸的存在下将步骤(a)提供的或步骤(b)获得的黄烷-3-酮与含有亲核芳香基团的化合物接触；(e)形成第一中间体化合物，其中由于亲核加成，C-3碳上的羰基基团转化为羟基基团，当含有亲核芳香基团的化合物与黄烷-3-酮的C-3碳接触时；(f)将第一中间体化合物脱水，以在中间体化合物的C-3碳和C-4碳之间引入双键，并同时去除C-3碳上的羟基基团，形成一种被亲核芳香基团取代的光学活性黄烯化合物；(g)可选地将所得黄烯化合物进行氢硼化-氧化水合反应，从而去除C-3碳和C-4碳之间的双键，并同时在C-4碳引入羟基基团，形成第二中间体化合物；(h)进一步可选地将步骤(g)的第二中间体化合物氧化，将C-4碳上的羟基基团转化为羰基基团，从而形成在C-3碳上被选定的亲核芳香基团取代的双黄酮或双黄酮类似物；(i)进一步可选地，替代步骤(h)，将步骤(f)的所得黄烯化合物进行OsO4二羟基化反应，从而去除C-3碳和C-4碳之间的双键，并同时在C-4碳和C-3碳引入羟基基团，形成第三中间体化合物；(j)将第三中间体化合物脱水，从而去除C-3碳上的羟基基团，并在C-3碳和C-4碳之间引入双键，从而形成烯醇产物，并使该烯醇产物自发地重排，形成在其C-4碳上具有羰基基团且在其C-3碳上被选定的亲核芳香基团取代的双黄酮或双黄酮类似物。
• Synthesis of C-3 coupled biflavonoids and C-3 coupled biflavonoid analogues
  申请人：Van Der Westhuizen Jan Hendrik

  公开号：US09296717B2

  公开（公告）日：2016-03-29

  The preparation of C-3 coupled biflavonoids and C-3 coupled biflavonoid analogs occurs from flavan-3-ones that are contacted with a compound having a nucleophilic aromatic moiety, in the presence of a Lewis acid where an intermediate compound is formed with a C-3 hydroxy group. A flavan-3-ol can be converted to a flavan-3-one as required. The intermediate compound is dehydrated to a flavene with a C-3-C-4 double bond. The flavene compound undergoes hydroboration-oxidation hydration to introduce a C-4 hydroxy group that can be oxidized to an oxo group or can be dihydroxylation to introduce hydroxy groups at the C-4 and C-3 carbons and dehydrated to a biflavonoid or biflavonoid analog having an oxo group at its C-4 carbon and substituted by the selected nucleophilic aromatic moiety on its C-3 carbon.

  制备C-3偶联的双黄酮类化合物和C-3偶联的双黄酮类似物的方法是将黄酮-3-酮与带有亲核芳香基团的化合物接触，在路易斯酸的存在下形成一个带有C-3羟基的中间化合物。需要时，黄酮-3-醇可以转化为黄酮-3-酮。中间化合物被脱水成一个带有C-3-C-4双键的黄素。黄素化合物经过氢硼化-氧化水合反应，引入一个C-4羟基，该羟基可以被氧化成一个酮基，或者可以被二羟基化作用引入羟基在C-4和C-3碳上，然后脱水成一个双黄酮或双黄酮类似物，其C-4碳上带有酮基，C-3碳上被所选的亲核芳香基团取代。
• SYNTHESIS OF C-3 COUPLED BIFLAVONOIDS AND C-3 COUPLED BIFLAVONOID ANALOGUES
  申请人：University Of The Free State

  公开号：EP2467369A1

  公开（公告）日：2012-06-27