1,4-二甲氧基-2-硝基苯-3,6-二羧酸 | 143430-21-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 1,4-二甲氧基-2-硝基苯-3,6-二羧酸
• 英文名称: 1,4-dimethoxy-2-nitrobenzene-3,6-dicarboxylic acid
• 英文别名: 2,5-dimethoxy-3-nitroterephthalic acid
• CAS: 143430-21-1
• 化学式: C₁₀H₉NO₈
• 分子量: 271.183
• InChiKey: SSLHDQMCYAYDHI-UHFFFAOYSA-N

物化性质

• 沸点：
  511.7±50.0 °C(Predicted)
• 密度：
  1.555±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  139
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1,4-二甲氧基-2-硝基苯-3,6-二羧酸 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 1,4-二甲氧基-2-硝基苯-3,6-二羧酸
  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

• Flexibility in metal–organic frameworks derived from positional and electronic effects of functional groups
  作者：Hyeonbin Ha、Hyungwoo Hahm、Dong Gyun Jwa、Kwangho Yoo、Myung Hwan Park、Minyoung Yoon、Youngjo Kim、Min Kim

  DOI：10.1039/c7ce00971b

  日期：——

  position of identical functional groups and the subsequent electron density of structural benzene rings in a zinc-based metal–organic framework (MOF) have been controlled to reveal flexibility (or breathing behavior) differences. Both ortho- and para-positioned bi-functional benzene-1,4-dicarboxylic acid (BDC) ligands were synthesized with amino-, chloro-, methoxy-, and nitro groups. Additionally, two

  在锌基金属-有机骨架（MOF）中，相同官能团的位置以及随后结构苯环的电子密度已得到控制，以显示出柔韧性（或呼吸行为）差异。两个邻位-和对位-positioned双官能苯-1,4-二羧酸（BDC）的配体用氨基- ，氯- ，甲氧基-合成，和硝基。另外，制备了两个三官能化的二甲氧基-氨基和二甲氧基-硝基BDC。除两个不溶且热不稳定的二氨基BDC外，所有双功能和三功能BDC已成功并入DABCO MOF（DMOF）。在这八个双/三官能DMOFs，只对抽空后准备制备N 2等温线时，-二甲氧基在其骨架中表现出柔性。由于该系列中BDC的苯环中的二甲氧基组合具有最富电子的环境，因此表明电子密度在相同双官能化DMOF的柔韧性变化中起作用。然而，仅电子密度不能完全解释挠性变化，表明官能团的位置也很重要。通过合成具有相同官能团位置但电子环境相反的两个三官能化DMOF，证实了这些发现。
• 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.