1,4-dimethoxy-2-nitrobenzene-3,6-dicarboxylic acid dimethyl ester | 143430-20-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,4-dimethoxy-2-nitrobenzene-3,6-dicarboxylic acid dimethyl ester
• 英文别名: dimethyl 3-nitro-2,5-dimethoxybenzene-1,4-dicarboxylate；Dimethyl 2,5-dimethoxy-3-nitrobenzene-1,4-dicarboxylate
• CAS: 143430-20-0
• 化学式: C₁₂H₁₃NO₈
• 分子量: 299.237
• InChiKey: GCXQFVFSFWHWQI-UHFFFAOYSA-N

物化性质

• 沸点：
  450.9±40.0 °C(Predicted)
• 密度：
  1.329±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  117
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1,4-dimethoxy-2-nitrobenzene-3,6-dicarboxylic acid dimethyl ester 在 palladium on activated charcoal 吡啶 、 nitronium tetrafluoborate 、 硫酸 、 氢气 作用下， 以 甲醇 、 乙醇 、 溶剂黄146 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， -78.0~100.0 ℃ 、344.73 kPa 条件下， 反应 14.0h， 生成 2,7-bis(methoxymethyl)-5,10-dimethoxy-3,8-dimethylpyrimido<4,5-g>quinazoline-4,9(3H,8H)-dione
  参考文献：
  名称：

  Design of pyrimido[4,5-g]quinazoline-based anthraquinone mimics. Structure-activity relationship for quinone methide formation and the influence of internal hydrogen bonds on quinone methide fate

  摘要：

  Pyrimido[4,5-g]quinazolinequinone derivatives were synthesized as a anthraquinone-like reductive alkylating agents. Like many naturally-occurring antibiotics, these quinone derivatives are designed to afford an alkylating quinone methide species upon reduction and leaving-group elimination. Kinetic studies of pyrimido[4,5-g]quinazoline hydroquinones provided evidence of quinone methide intermediate able to trap nucleophiles (alkylation) and protons (ketonization). The rate of quinone methide formation is determined by the hydroquinone free energy. Thus, a linear free energy relationship for quinone methide formation was obtained by plotting rates of quinone methide formation as the log versus the quinone reduction potential. The pyrimido[4,5-g]quinazoline quinone methides fall on this free energy plot, showing that these species are formed by the same mechanism as the other structurally-diverse quinone methides previously studied in this research group. Internal hydrogen bonds present in pyrimido[4,5-g]quinazoline derivatives influence the fate of the quinone methide species as well as the rate of hydroquinone oxidation in the presence of oxygen Such hydrogen bonds stabilize the hydroquinone species, thereby resulting in slow rates of hydroquinone oxidation to quinone in alkaline aerobic buffer. Stabilization of the hydroquinone also results in substantial nucleophile trapping by the quinone methide. Without internal hydrogen bonds, hydroquinone oxidations are rapid and the quinone methide traps only electrophiles.

  DOI：

  10.1021/jo00047a017
• 作为产物：
  描述：

  2,5-Dimethoxy-1,4-benzoldicarbonitril 在 sodium hydroxide 、 硫酸 、 双氧水 、 硝酸 、 乙酸酐 、 sodium nitrite 作用下， 以 乙醇 为溶剂， 反应 0.58h， 生成 1,4-dimethoxy-2-nitrobenzene-3,6-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Design of pyrimido[4,5-g]quinazoline-based anthraquinone mimics. Structure-activity relationship for quinone methide formation and the influence of internal hydrogen bonds on quinone methide fate

  摘要：

  Pyrimido[4,5-g]quinazolinequinone derivatives were synthesized as a anthraquinone-like reductive alkylating agents. Like many naturally-occurring antibiotics, these quinone derivatives are designed to afford an alkylating quinone methide species upon reduction and leaving-group elimination. Kinetic studies of pyrimido[4,5-g]quinazoline hydroquinones provided evidence of quinone methide intermediate able to trap nucleophiles (alkylation) and protons (ketonization). The rate of quinone methide formation is determined by the hydroquinone free energy. Thus, a linear free energy relationship for quinone methide formation was obtained by plotting rates of quinone methide formation as the log versus the quinone reduction potential. The pyrimido[4,5-g]quinazoline quinone methides fall on this free energy plot, showing that these species are formed by the same mechanism as the other structurally-diverse quinone methides previously studied in this research group. Internal hydrogen bonds present in pyrimido[4,5-g]quinazoline derivatives influence the fate of the quinone methide species as well as the rate of hydroquinone oxidation in the presence of oxygen Such hydrogen bonds stabilize the hydroquinone species, thereby resulting in slow rates of hydroquinone oxidation to quinone in alkaline aerobic buffer. Stabilization of the hydroquinone also results in substantial nucleophile trapping by the quinone methide. Without internal hydrogen bonds, hydroquinone oxidations are rapid and the quinone methide traps only electrophiles.

  DOI：

  10.1021/jo00047a017

文献信息

• Nitrene insertion into an adjacent o -methoxy group followed by nucleophilic addition to the heterocumulene intermediate: Experimental and computational studies
  作者：Sambasivan V. Eswaran、Divneet Kaur、Kalyanashis Jana、Krishnendu Khamaru、Sripadi Prabhakar、Partha Raghunathan、Bishwajit Ganguly

  DOI：10.1016/j.tet.2017.07.024

  日期：2017.8

  The chemistry of aryl azides and aryl nitrenes is rich and varied in nature with different products being obtained with minor changes in reaction conditions. Thermolysis of azido- dimethylsuccinylosuccinate has been carried out to study the behaviour of this new azide during thermolysis. The products obtained have been studied by various spectroscopic and DFT calculations. These results reveal formation

  芳基叠氮化物和芳基腈的化学性质丰富且变化多端，在反应条件稍有变化的情况下获得了不同的产物。已进行叠氮基二甲基琥珀酰琥珀酸琥珀酸酯的热解以研究这种新叠氮化物在热解过程中的行为。已经通过各种光谱和DFT计算研究了获得的产物。这些结果揭示了由在热解过程中产生的腈中间体（1）形成化合物-II和化合物-III。DFT结果使由稳定的中间体2和4形成热力学稳定的化合物II和化合物III合理化在热解过程中形成的。此外，DFT结果表明，与中间体4进一步热降解为吡啶基卡宾（4b）和卡宾中间体（5）相比，4和2之间的反应在热力学上更有利，这证实了在热解过程中未形成此类产物。
• US5639881A
  申请人：——

  公开号：US5639881A

  公开（公告）日：1997-06-17
• Design of pyrimido[4,5-g]quinazoline-based anthraquinone mimics. Structure-activity relationship for quinone methide formation and the influence of internal hydrogen bonds on quinone methide fate
  作者：Robert H. Lemus、Edward B. Skibo

  DOI：10.1021/jo00047a017

  日期：1992.10

  Pyrimido[4,5-g]quinazolinequinone derivatives were synthesized as a anthraquinone-like reductive alkylating agents. Like many naturally-occurring antibiotics, these quinone derivatives are designed to afford an alkylating quinone methide species upon reduction and leaving-group elimination. Kinetic studies of pyrimido[4,5-g]quinazoline hydroquinones provided evidence of quinone methide intermediate able to trap nucleophiles (alkylation) and protons (ketonization). The rate of quinone methide formation is determined by the hydroquinone free energy. Thus, a linear free energy relationship for quinone methide formation was obtained by plotting rates of quinone methide formation as the log versus the quinone reduction potential. The pyrimido[4,5-g]quinazoline quinone methides fall on this free energy plot, showing that these species are formed by the same mechanism as the other structurally-diverse quinone methides previously studied in this research group. Internal hydrogen bonds present in pyrimido[4,5-g]quinazoline derivatives influence the fate of the quinone methide species as well as the rate of hydroquinone oxidation in the presence of oxygen Such hydrogen bonds stabilize the hydroquinone species, thereby resulting in slow rates of hydroquinone oxidation to quinone in alkaline aerobic buffer. Stabilization of the hydroquinone also results in substantial nucleophile trapping by the quinone methide. Without internal hydrogen bonds, hydroquinone oxidations are rapid and the quinone methide traps only electrophiles.