acetic acid 9-acetoxy-11-diazo-2-methyl-5,10-dioxo-10,11-dihydro-5H-benzo[b]fluoren-4-yl ester | 120796-27-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: acetic acid 9-acetoxy-11-diazo-2-methyl-5,10-dioxo-10,11-dihydro-5H-benzo[b]fluoren-4-yl ester
• CAS: 120796-27-2
• 化学式: C₂₂H₁₄N₂O₆
• 分子量: 402.363
• InChiKey: MWXWXMZHUCLPFP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  30.0
• 可旋转键数：
  2.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  123.14
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  acetic acid 9-acetoxy-11-diazo-2-methyl-5,10-dioxo-10,11-dihydro-5H-benzo[b]fluoren-4-yl ester 在 吡啶 、 4-二甲氨基吡啶 、 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 acetic acid 4,5-diacetoxy-2-methyl-10-oxo-11-phenyl-10H-benzo[b]fluoren-9-yl ester
  参考文献：
  名称：

  Studies on the Mechanism of Action of Prekinamycin, a Member of the Diazoparaquinone Family of Natural Products:  Evidence for Both sp² Radical and Orthoquinonemethide Intermediates

  摘要：

  The putative reductive activation chemistry of the diazoparaquinone antibiotics was modeled with Bu3Sn-H and prekinamycin dimethyl ether along with prekinamycin itself. Reaction in various combinations of aromatic solvents, with and without the nucleophile benzylmercaptan present, led to isolation of both radical-trapping arene adducts and nucleophilic capture benzyl thioether products. On the basis of these product distribution studies, the intermediacies of, first, a cyclopentenyl radical and, next, an orthoquinonemethide electrophile are postulated.

  DOI：

  10.1021/ja0642616
• 作为产物：
  描述：

  乙酸酐 、 prekinamycin 在 吡啶 、 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以85%的产率得到acetic acid 9-acetoxy-11-diazo-2-methyl-5,10-dioxo-10,11-dihydro-5H-benzo[b]fluoren-4-yl ester
  参考文献：
  名称：

  Studies on the Mechanism of Action of Prekinamycin, a Member of the Diazoparaquinone Family of Natural Products:  Evidence for Both sp² Radical and Orthoquinonemethide Intermediates

  摘要：

  The putative reductive activation chemistry of the diazoparaquinone antibiotics was modeled with Bu3Sn-H and prekinamycin dimethyl ether along with prekinamycin itself. Reaction in various combinations of aromatic solvents, with and without the nucleophile benzylmercaptan present, led to isolation of both radical-trapping arene adducts and nucleophilic capture benzyl thioether products. On the basis of these product distribution studies, the intermediacies of, first, a cyclopentenyl radical and, next, an orthoquinonemethide electrophile are postulated.

  DOI：

  10.1021/ja0642616

文献信息

• A Proposal for the Mechanism-of-Action of Diazoparaquinone Natural Products
  作者：Ken S. Feldman、Kyle J. Eastman

  DOI：10.1021/ja053880w

  日期：2005.11.1

  Treatment of the representative diazoparaquinone prekinamycin dimethyl ether with Bu3SnH/AIBN in aromatic solvents furnishes moderate-to-good yields of formal aryl adducts wherein a molecule of solvent is attached to the carbon (C(11)) previously bearing the diazo function. Substituent studies provide evidence in support of a radical aromatic substitution mechanism, in which radical addition to the diazoparaquinone function generates an intermediate C(11) vinylic radical.