2-(3,5-dimethoxy-4-hydroxyphenyl)-8-hydroxy-5-methyl-3-O-β-D-glucopyranosyloxypyrano[4,3,2-de]-1-benzopyrilium

• 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: 2-(3,5-dimethoxy-4-hydroxyphenyl)-8-hydroxy-5-methyl-3-O-β-D-glucopyranosyloxypyrano[4,3,2-de]-1-benzopyrilium
• 英文别名: methyl pyranomalvidin-3-O-glucoside；methylpyranomalvidin-3-glucoside；pyranomalvidin
• 化学式: C₂₆H₂₇O₁₂
• 分子量: 531.493
• InChiKey: QDPWYLHHTYIKLU-BKBOFEOXSA-O

计算性质

• 辛醇/水分配系数(LogP)：
  1.74
• 重原子数：
  38.0
• 可旋转键数：
  6.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  178.83
• 氢给体数：
  6.0
• 氢受体数：
  11.0

反应信息

• 作为反应物：
  描述：

  2-(3,5-dimethoxy-4-hydroxyphenyl)-8-hydroxy-5-methyl-3-O-β-D-glucopyranosyloxypyrano[4,3,2-de]-1-benzopyrilium 生成 syringetin 3-O-glucoside
  参考文献：
  名称：

  Chemical Behavior of Methylpyranomalvidin-3-O-glucoside in Aqueous Solution Studied by NMR and UV−Visible Spectroscopy

  摘要：

  In the present work, the proton-transfer reactions of the methylpyranomalvidin-3-O-glucoside pigment in water with different pH values was studied by NMR and UV-visible spectroscopies. The results showed four equilibrium forms: the methylpyranomalvidin-3-O-glucoside cation, the neutral quinoidal base, the respective anionic quinoidal base, and a dianionic base unprotonated at the methyl group. According to the NMR data, it seems that for methylpyranomalvidin-3-O-glucoside besides the acid base equilibrium between the pyranoflavylium cation and the neutral quinoidal base, a new species is formed at pD 4.88-6.10. This is corroborated by the appearance of a new set of signals in the NMR spectrum that may be assigned to the formation of hemiketal/cis-chalcone species to a small extent. The two ionization constants (pK(a1) and pK(a2)) obtained by both methods (NMR and UV-visible) for methylpyranomalvidin-3-O-glucoside are in agreement (pK(a1) = 5.17 +/- 0.03; pK(a2) = 8.85 +/- 0.08; and pK(a1) = 4.57 +/- 0.07; pK(a2) = 8.23 +/- 0.04 obtained by NMR and UV-visible spectroscopies, respectively). Moreover, the fully dianionic unprotonated form (at the methyl group) of the methylpyranomalvidin-3-O-glucoside is converted slowly into a new structure that displays a yellow color at basic pH. On the basis of the results obtained through LC-MS and NMR, the proposed structure was found to correspond to the flavonol syringetin-3-glucoside.

  DOI：

  10.1021/jp110593c
• 作为产物：
  描述：

  氯化锦葵色素-3-β-葡糖苷 、 乙酰乙酸锂 以 水 为溶剂， 反应 240.0h， 生成 2-(3,5-dimethoxy-4-hydroxyphenyl)-8-hydroxy-5-methyl-3-O-β-D-glucopyranosyloxypyrano[4,3,2-de]-1-benzopyrilium
  参考文献：
  名称：

  Chemical Behavior of Methylpyranomalvidin-3-O-glucoside in Aqueous Solution Studied by NMR and UV−Visible Spectroscopy

  摘要：

  In the present work, the proton-transfer reactions of the methylpyranomalvidin-3-O-glucoside pigment in water with different pH values was studied by NMR and UV-visible spectroscopies. The results showed four equilibrium forms: the methylpyranomalvidin-3-O-glucoside cation, the neutral quinoidal base, the respective anionic quinoidal base, and a dianionic base unprotonated at the methyl group. According to the NMR data, it seems that for methylpyranomalvidin-3-O-glucoside besides the acid base equilibrium between the pyranoflavylium cation and the neutral quinoidal base, a new species is formed at pD 4.88-6.10. This is corroborated by the appearance of a new set of signals in the NMR spectrum that may be assigned to the formation of hemiketal/cis-chalcone species to a small extent. The two ionization constants (pK(a1) and pK(a2)) obtained by both methods (NMR and UV-visible) for methylpyranomalvidin-3-O-glucoside are in agreement (pK(a1) = 5.17 +/- 0.03; pK(a2) = 8.85 +/- 0.08; and pK(a1) = 4.57 +/- 0.07; pK(a2) = 8.23 +/- 0.04 obtained by NMR and UV-visible spectroscopies, respectively). Moreover, the fully dianionic unprotonated form (at the methyl group) of the methylpyranomalvidin-3-O-glucoside is converted slowly into a new structure that displays a yellow color at basic pH. On the basis of the results obtained through LC-MS and NMR, the proposed structure was found to correspond to the flavonol syringetin-3-glucoside.

  DOI：

  10.1021/jp110593c

文献信息

• Isolation and Structural Characterization of New Anthocyanin-Derived Yellow Pigments in Aged Red Wines
  作者：Jingren He、Celestino Santos-Buelga、Artur M. S. Silva、Nuno Mateus、Victor de Freitas

  DOI：10.1021/jf062325q

  日期：2006.12.1

  structures of these pigments correspond to methyl-linked pyranomalvidin 3-glucoside and its respective coumaroyl glucoside derivative. They were shown to arise from the reaction between acetoacetic acid and genuine grape anthocyanins. Isolation and NMR identification using 1D and 2D NMR techniques are reported for the first time for this new family of anthocyanin-derived yellow pigments occurring in red

  通过TSK Toyopearl HW-40（s）凝胶色谱法从陈年的Port红酒中检测并分离出两种具有独特光谱特征的黄色颜料，并通过紫外可见分光光度法，1H NMR和13C NMR以及质谱（LC）对其进行了表征。 -ESI / MS）。这些颜料的UV-vis光谱显示在478 nm处有最大吸收，这与原始葡萄花色苷和其他吡喃花青素的吸收相比显着变色，在酸性溶液中显示出更多的黄色调。这些颜料的结构对应于甲基连接的吡喃马维丁3-葡糖苷及其各自的香豆酰基葡糖苷衍生物。已显示它们是由乙酰乙酸与纯正的葡萄花色苷之间的反应产生的。
• Unusual anthocyanin reaction with acetone leading to pyranoanthocyanin formation
  作者：Yinrong Lu、L.Yeap Foo

  DOI：10.1016/s0040-4039(00)02246-2

  日期：2001.2

  Anthocyanins undergo unusual facile reactions with acetone to give rise to pyranoanthocyanins, thus showing that the new class of pigments isolated from blackcurrant seeds were a result of solvent participation. This oxidative addition was extended to the successful synthesis of pyranomalvidin or 2-(3,5-dimethoxy-4-hydroxyphenyl)-8-hydroxy-5-methyl-3-O-β-d-glucopyranosyloxypyrano[4,3,2-de]-1-benzopyrylium

  花色素苷与丙酮发生异常的易反应，生成吡喃花色素苷，因此表明从黑加仑子种子中分离出的新型颜料是溶剂参与的结果。这种氧化加成作用扩展到成功合成了吡喃马维丁或2-（3,5-二甲氧基-4-羟基苯基）-8-羟基-5-甲基-3- O -β-d-吡喃葡萄糖基氧基吡喃并[4,3,2-主要葡萄花色苷麦维京素3- O-葡萄糖苷与丙酮的反应生成de ] -1-苯并吡啶鎓。通过2D NMR充分表征了吡喃马维菌素，吡喃花色素B和吡喃德啡肽B的化学结构。
• Pyranoanthocyanin Dimers: A New Family of Turquoise Blue Anthocyanin-Derived Pigments Found in Port Wine
  作者：Joana Oliveira、Joana Azevedo、Artur M. S. Silva、Natércia Teixeira、Luis Cruz、Nuno Mateus、Victor de Freitas

  DOI：10.1021/jf9044414

  日期：2010.4.28

  found to occur in aged Port wines and respective sediments (lees). The data obtained revealed two new families of compounds with unique spectroscopic characteristics, displaying a wavelength of the maximum absorption at high wavelength in the visible spectrum at ∼730 and ∼680 nm. The structure of these pigments was elucidated by liquid chromatography/diode array detector−mass spectrometry (LC/DAD−MS) and

  在目前的工作中，已发现几种具有相似光谱特征的化合物出现在陈年的波特酒和各自的沉积物（酒糟）中。获得的数据揭示了两个具有独特光谱特征的化合物新家族，它们在〜730和〜680 nm的可见光谱中显示了在高波长下最大吸收的波长。通过液相色谱/二极管阵列检测器质谱（LC / DAD-MS）和核磁共振（NMR）阐明了这些色素的结构，并建立了它们在葡萄酒中的形成途径。它们的结构由通过亚甲基桥连接在一起的两个吡喃花色素苷部分组成。这个新的化合物家族在酸性条件下显示出诱人且稀有的绿松石蓝色，并且从未在文献中进行报道。
• Synthesis and Structural Characterization of Amino-Based Pyranoanthocyanins with Extended Electronic Delocalization
  作者：Joana Oliveira、Paula Araújo、Ana Fernandes、Nuno Mateus、Victor de Freitas

  DOI：10.1055/s-0035-1562471

  日期：——

  pyranoanthocyanin amino derivatives with extended electronic delocalization were obtained from the reaction of methyl­pyranomalvidin-3- O -glucoside with two amino-derived cinnamaldehydes, 4-(dimethylamino)- and 4-(diethylamino)-cinnamaldehyde. Structural characterization revealed the presence of a butadienylidene linkage connecting the pyranoanthocyanin and the cinnamyl moieties. The unexpected red color presented

  两个新的吡喃花青素氨基衍生物具有扩展的电子离域作用是从甲基吡喃麦芽糖苷-3-O-葡萄糖苷与两种氨基衍生的肉桂醛、4-(二甲氨基)-和 4-(二乙氨基)-肉桂醛的反应中获得的。结构表征表明存在连接吡喃花青素和肉桂基部分的丁二烯基键。新分子呈现出意外的红色是由于 ESI-MS 证实在酸性 pH 下存在双阳离子形式的颜料。
• Synthesis of a new bluish pigment from the reaction of a methylpyranoanthocyanin with sinapaldehyde
  作者：Joana Oliveira、Nuno Mateus、Victor de Freitas

  DOI：10.1016/j.tetlet.2011.02.079

  日期：2011.4

  The synthesis of a new pigment with a bluish color was obtained from the reaction of methylpyranomalvidin-3-glucoside with sinapaldehyde and its formation mechanism seems to involve a charge-transfer reaction pathway. The structure of this compound was fully characterized by LC/DAD-MS and NMR. Its equilibrium forms present in water at different pH values and the respective ionization constants were

  通过甲基吡喃醛清蛋白-3-葡萄糖苷与芥子醛的反应获得了带蓝色的新颜料，其形成机理似乎涉及电荷转移反应途径。该化合物的结构通过LC / DAD-MS和NMR充分表征。它的平衡形式存在于不同pH值的水中，并且各自的电离常数通过紫外可见光谱法测定。结果表明存在三个仅在吡喃花青素部分的7-OH和4'-OH位置以及丁香酚部分的4'''-OH处发生去质子反应的平衡（p K a1  = 3.64±0.01； p K a2  = 8.02±0.01； p K a3  = 11.19±0.01）。