1-Acetoxy-7-amino-6,9-dimethyl-2,3-dihydro-1H-pyrrolo<1,2-a>indole-5,8-dione | 163013-17-0

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 1-Acetoxy-7-amino-6,9-dimethyl-2,3-dihydro-1H-pyrrolo<1,2-a>indole-5,8-dione
• 英文别名: (6-amino-4,7-dimethyl-5,8-dioxo-2,3-dihydro-1H-pyrrolo[1,2-a]indol-3-yl) acetate
• CAS: 163013-17-0
• 化学式: C₁₅H₁₆N₂O₄
• 分子量: 288.303
• InChiKey: UPRLPMYAESJSLE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  91.4
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-Acetoxy-7-amino-6,9-dimethyl-2,3-dihydro-1H-pyrrolo<1,2-a>indole-5,8-dione 在 palladium on activated charcoal 氢气 作用下， 以 二甲基亚砜 为溶剂， 反应 0.2h， 生成 Acetic acid 7-amino-5,8-dihydroxy-6,9-dimethyl-2,3-dihydro-1H-pyrrolo[1,2-a]indol-1-yl ester
  参考文献：
  名称：

  Determination of the pKa Values for the Mitomycin C Redox Couple by Titration, pH Rate Profiles, and Nernst-Clark Fits. Studies of Methanol Elimination, Carbocation Formation, and the Carbocation/Quinone Methide Equilibrium

  摘要：

  This report provides the results of a study of the mitomycin C (MMC) redox couple pK(a) values employing spectrophotometric titration, pH rate profiles, and Nernst-Clark plots. Oxidized mitomycin C (MMC(OX)) has three acid dissociations: pK(a1) = -1.2 for the protonated quinone, pK(a2) = 2.7 for the protonated indoline nitrogen, and pK(a3) = 7.6 for the protonated aziridino nitrogen. Two-electron reduction to MMC(red) results in a shift to higher pK(a) values: pK(a1) = 1.4 for the protonated 7-amino group, pK(a2) = 5.1 to 6.1 for the protonated indoline nitrogen, and pK,B = 9.1 for the protonated aziridino nitrogen. These pK(a) values were successfully integrated into previous mechanistic studies. The general conclusions are that indoline nitrogen protonation prevents methanol elimination, that methanol elimination from MMC(OX) and MMC(red) are both specific acid catalyzed, and that there is a 100000-fold increase in the second-order rate constant for specific acid-catalyzed elimination of methanol upon reduction of MMC(OX) to MMC(red). Finally, the formation and fate of the mitosene hydroquinone carbocation was studied in a mitosene model bearing an acetate leaving group. The carbocation species undergoes acid dissociation to the quinone methide (pK(a) = 7.1) resulting in a pH dependence for product formation. Below pH 7.1 the carbocation species traps water and above this pH the quinone methide species traps both water and a proton.

  DOI：

  10.1021/jo00112a051
• 作为产物：
  描述：

  乙酸酐 、 7-Amino-2,3-dihydro-1-hydroxy-6,9-dimethyl-1H-pyrrolo<1,2-a>indole-5,8-dione 在 吡啶 作用下， 反应 2.0h， 以71%的产率得到1-Acetoxy-7-amino-6,9-dimethyl-2,3-dihydro-1H-pyrrolo<1,2-a>indole-5,8-dione
  参考文献：
  名称：

  Determination of the pKa Values for the Mitomycin C Redox Couple by Titration, pH Rate Profiles, and Nernst-Clark Fits. Studies of Methanol Elimination, Carbocation Formation, and the Carbocation/Quinone Methide Equilibrium

  摘要：

  This report provides the results of a study of the mitomycin C (MMC) redox couple pK(a) values employing spectrophotometric titration, pH rate profiles, and Nernst-Clark plots. Oxidized mitomycin C (MMC(OX)) has three acid dissociations: pK(a1) = -1.2 for the protonated quinone, pK(a2) = 2.7 for the protonated indoline nitrogen, and pK(a3) = 7.6 for the protonated aziridino nitrogen. Two-electron reduction to MMC(red) results in a shift to higher pK(a) values: pK(a1) = 1.4 for the protonated 7-amino group, pK(a2) = 5.1 to 6.1 for the protonated indoline nitrogen, and pK,B = 9.1 for the protonated aziridino nitrogen. These pK(a) values were successfully integrated into previous mechanistic studies. The general conclusions are that indoline nitrogen protonation prevents methanol elimination, that methanol elimination from MMC(OX) and MMC(red) are both specific acid catalyzed, and that there is a 100000-fold increase in the second-order rate constant for specific acid-catalyzed elimination of methanol upon reduction of MMC(OX) to MMC(red). Finally, the formation and fate of the mitosene hydroquinone carbocation was studied in a mitosene model bearing an acetate leaving group. The carbocation species undergoes acid dissociation to the quinone methide (pK(a) = 7.1) resulting in a pH dependence for product formation. Below pH 7.1 the carbocation species traps water and above this pH the quinone methide species traps both water and a proton.

  DOI：

  10.1021/jo00112a051