5,5',6,6'-tetrahydroxy-2,2'-biindolyl | 98192-27-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 5,5',6,6'-tetrahydroxy-2,2'-biindolyl
• 英文别名: 5,6,5',6'-tetrahydroxy-2,2'-biindolyl；5,5',6,6'-tetrahydroxy-2,2'biindolyl；2-(5,6-dihydroxy-1H-indol-2-yl)-1H-indole-5,6-diol
• CAS: 98192-27-9
• 化学式: C₁₆H₁₂N₂O₄
• 分子量: 296.282
• InChiKey: JOKGEXDXSDUJIL-UHFFFAOYSA-N

物化性质

• 沸点：
  768.7±55.0 °C(Predicted)
• 密度：
  1.709±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  22
• 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：
  113
• 氢给体数：
  6
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5,5',6,6'-tetrahydroxy-2,2'-biindolyl 在 双氧水 、 potassium carbonate 作用下， 生成 2,3,5-三羧酸吡咯
  参考文献：
  名称：

  Oxidative degradation of melanins to pyrrole acids: A model study

  摘要：

  The origin of pyrrole-2,3,5-tricarboxylic acid (PTCA), the most characteristic degradation product of melanins, was investigated by use of synthetic pigments prepared from the major biosynthetic precursors, 5,6-dihydroxyindole (DHI) and 5,6-dihydroxyindole-2-carboxylic acid (DHICA). Under the reported conditions, i.e. acidic permanganate, oxidative degradation of DHI- and DHICA-melanins afforded PTCA in 0.15 and 3.0% w/w yield, respectively. A significant improvement of PTCA yields up to 7% was obtained using alkaline hydrogen peroxide as the oxidising agent. Under these conditions pyrrole-2,3-dicarboxylic acid (PDCA) was also obtained in significant yields. Investigation of the oxidative degradation of some model indole oligomers (1-4) provided unambiguous evidence that PTCA may originate from 2-linked DHI-units in the pigment polymer as well as from DHICA-derived units, whereas PDCA arises from DHI-units not substituted at 2-position. Monitoring of the oxidation of dimer 1 to PTCA showed the intermediate formation of DHICA. Accordingly, a mechanistic route is proposed for the degradation of 2-substituted DHI-units in melanin polymer to PTCA which also accounts for the observed yields of formation of the pyrrole acid from the model oligomers.

  DOI：

  10.1016/0040-4020(95)00259-b
• 作为产物：
  描述：

  leucomelanochrome A acetate 在 sodium phosphate 、 potassium bromide 作用下， 以 甲醇 为溶剂， 反应 0.02h， 生成 5,5',6,6'-tetrahydroxy-2,2'-biindolyl
  参考文献：
  名称：

  从 5,6-二羟基吲哚二聚体到真黑素聚合物的短寿命醌类物质：综合化学、脉冲辐射分解和量子力学研究

  摘要：

  已经研究了由 5,6-二羟基吲哚 (1) 的三个二聚体氧化形成的瞬态物种，这是天然生物聚合物真黑色素的主要组成部分。5,5',6,6'-四羟基-2,4'-二吲哚基 (3) 和 5,5',6,6'-四羟基-2,7'-二吲哚基 (4) 的脉冲辐解氧化导致半醌吸收大约 450 nm，它以二级动力学（分别为 2k=2.8x10(9) 和 1.4x10(9) M-1 s-1）衰减，得到相应的醌（500-550 nm）。另一方面，5,5',6, 6'-四羟基-2,2'-二吲哚基 (2) 提供了一种半醌 (lamdamax=480 nm)，其歧化速率相当 (2k=3x10(9) M -1 s-1) 得到相对稳定的醌 (lamdamax=570 nm)。邻醌、醌亚胺的量子力学研究 2-4 的醌甲基化物结构表明氧化的 2-4 主要以 2-取代的扩展醌甲基化物互变异构体形式存在。最后，首次分离出 3 的氧化产物，并将其配制成羟基化衍生物

  DOI：

  10.1021/ja0650246

文献信息

• 2,2′-Biindolyl revisited. Synthesis and reactions
  作者：Jan Bergman、Eva Koch、Benjamin Pelcman

  DOI：10.1016/0040-4020(95)00223-u

  日期：1995.5

  An improved synthesis of 2,2′-biindolyl (1) is described. Derivatives of 1 with a variety of substituents in the 3,3′-positions, such as the 3,3′-diformyl derivative 19 have been synthesized. Potential syntheses of indolocarbazole alkaloids from such derivatives are outlined.

  描述了2,2'-联吲哚基（1）的改进的合成。已经合成了在3，3'-位置具有多个取代基的1的衍生物，例如3，3'-二甲酰基衍生物19。概述了由此类衍生物潜在合成吲哚并咔唑生物碱的方法。
• A reinvestigation of the structure of melanochrome
  作者：Alessandra Napolitano、Maria Grazia Corradini、Giuseppe Prota

  DOI：10.1016/s0040-4039(00)94917-7

  日期：1985.1
• Oxidative degradation of melanins to pyrrole acids: A model study
  作者：Alessandra Napolitano、Alessandro Pezzella、M.Rosaria Vincensi、Giuseppe Prota

  DOI：10.1016/0040-4020(95)00259-b

  日期：1995.5

  The origin of pyrrole-2,3,5-tricarboxylic acid (PTCA), the most characteristic degradation product of melanins, was investigated by use of synthetic pigments prepared from the major biosynthetic precursors, 5,6-dihydroxyindole (DHI) and 5,6-dihydroxyindole-2-carboxylic acid (DHICA). Under the reported conditions, i.e. acidic permanganate, oxidative degradation of DHI- and DHICA-melanins afforded PTCA in 0.15 and 3.0% w/w yield, respectively. A significant improvement of PTCA yields up to 7% was obtained using alkaline hydrogen peroxide as the oxidising agent. Under these conditions pyrrole-2,3-dicarboxylic acid (PDCA) was also obtained in significant yields. Investigation of the oxidative degradation of some model indole oligomers (1-4) provided unambiguous evidence that PTCA may originate from 2-linked DHI-units in the pigment polymer as well as from DHICA-derived units, whereas PDCA arises from DHI-units not substituted at 2-position. Monitoring of the oxidation of dimer 1 to PTCA showed the intermediate formation of DHICA. Accordingly, a mechanistic route is proposed for the degradation of 2-substituted DHI-units in melanin polymer to PTCA which also accounts for the observed yields of formation of the pyrrole acid from the model oligomers.
• Short-Lived Quinonoid Species from 5,6-Dihydroxyindole Dimers en Route to Eumelanin Polymers:  Integrated Chemical, Pulse Radiolytic, and Quantum Mechanical Investigation
  作者：Alessandro Pezzella、Lucia Panzella、Orlando Crescenzi、Alessandra Napolitano、Suppiah Navaratman、Ruth Edge、Edward J. Land、Vincenzo Barone、Marco d'Ischia

  DOI：10.1021/ja0650246

  日期：2006.12.1

  The transient species formed by oxidation of three dimers of 5,6-dihydroxyindole (1), a major building block of the natural biopolymer eumelanin, have been investigated. Pulse radiolytic oxidation of 5,5',6,6'-tetrahydroxy-2,4'-biindolyl (3) and 5,5',6,6'-tetrahydroxy-2,7'-biindolyl (4) led to semiquinones absorbing around 450 nm, which decayed with second-order kinetics (2k=2.8x10(9) and 1.4x10(9)

  已经研究了由 5,6-二羟基吲哚 (1) 的三个二聚体氧化形成的瞬态物种，这是天然生物聚合物真黑色素的主要组成部分。5,5',6,6'-四羟基-2,4'-二吲哚基 (3) 和 5,5',6,6'-四羟基-2,7'-二吲哚基 (4) 的脉冲辐解氧化导致半醌吸收大约 450 nm，它以二级动力学（分别为 2k=2.8x10(9) 和 1.4x10(9) M-1 s-1）衰减，得到相应的醌（500-550 nm）。另一方面，5,5',6, 6'-四羟基-2,2'-二吲哚基 (2) 提供了一种半醌 (lamdamax=480 nm)，其歧化速率相当 (2k=3x10(9) M -1 s-1) 得到相对稳定的醌 (lamdamax=570 nm)。邻醌、醌亚胺的量子力学研究 2-4 的醌甲基化物结构表明氧化的 2-4 主要以 2-取代的扩展醌甲基化物互变异构体形式存在。最后，首次分离出 3 的氧化产物，并将其配制成羟基化衍生物