5,5',6,6'-tetraacetoxy-2,4'-biindolyl | 131248-81-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 5,5',6,6'-tetraacetoxy-2,4'-biindolyl
• 英文别名: [6-acetyloxy-2-(5,6-diacetyloxy-1H-indol-4-yl)-1H-indol-5-yl] acetate
• CAS: 131248-81-2
• 化学式: C₂₄H₂₀N₂O₈
• 分子量: 464.431
• InChiKey: GORXIEGZTZAOAJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  34
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  137
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  5,5',6,6'-tetraacetoxy-2,4'-biindolyl 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-2,4'-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
• 作为产物：
  描述：

  5,6-二羟基吲哚 、 乙酸酐 在 吡啶 、 酪氨酸酶 作用下， 生成 5,5',6,6'-tetraacetoxy-2,4'-biindolyl
  参考文献：
  名称：

  New intermediates in the oxidative polymerisation of 5,6-dihydroxyindole to melanin promoted by the peroxidase/H2O2 system

  摘要：

  DOI：

  10.1016/s0040-4020(01)87775-9

文献信息

• 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.
• The First 5,6-Dihydroxyindole Tetramer by Oxidation of 5,5‘,6,6‘-Tetrahydroxy- 2,4‘-biindolyl and an Unexpected Issue of Positional Reactivity en Route to Eumelanin-Related Polymers
  作者：Lucia Panzella、Alessandro Pezzella、Alessandra Napolitano、Marco d'Ischia

  DOI：10.1021/ol070268w

  日期：2007.3.1

  The first tetramer of the eumelanin precursor 5,6-dihydroxyindole has been obtained, as the acetyl derivative, by peroxidase/H2O2-induced oxidative coupling of 5,5',6,6'-tetrahydroxy-2,4'-biindolyl (2) in the presence of Zn2+ ions. The tetramer, 5,5',5' ',5' '',6,6',6' ',6' ''-octaacetoxy-2,4':2',3' ':2' ',4' ''-tetraindolyl (acetylated 7), incorporates an unprecedented 2,3'-biindolyl substructure suggestive of a different positional reactivity of the 5,6-dihydroxyindole system when framed into a dimeric scaffold.
• New intermediates in the oxidative polymerisation of 5,6-dihydroxyindole to melanin promoted by the peroxidase/H2O2 system
  作者：Marco d'Ischia、Alessandra Napolitano、Kostantino Tsiakas、Giuseppe Prota

  DOI：10.1016/s0040-4020(01)87775-9

  日期：1990.1
• 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