N,N'-bis-(p.hyroxyphenyl)-2-hydroxy-5-amino-1,4-benzoquinone | 71082-02-5

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: N,N'-bis-(p.hyroxyphenyl)-2-hydroxy-5-amino-1,4-benzoquinone
• 英文别名: N,N'-bis(p-hydroxyphenyl)-2-hydroxy-5-amino-1,4-benzoquinone diimine
• CAS: 71082-02-5
• 化学式: C₁₈H₁₅N₃O₃
• 分子量: 321.335
• InChiKey: BSLBYBXCGTZDFK-UHFFFAOYSA-N

物化性质

• 沸点：
  521.2±50.0 °C(Predicted)
• 密度：
  1.36±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.24
• 重原子数：
  24.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  111.43
• 氢给体数：
  4.0
• 氢受体数：
  6.0

反应信息

• 作为产物：
  描述：

  对氨基苯酚 在 5%-palladium/activated carbon 作用下， 以 异丙醇 为溶剂， 生成 N,N'-bis-(p.hyroxyphenyl)-2-hydroxy-5-amino-1,4-benzoquinone
  参考文献：
  名称：

  4-硝基苯酚一锅法机械化学加氢乙酰化制4-氨基苯酚和对乙酰氨基酚

  摘要：

  在球磨反应器中检查了 4-硝基苯酚的机械化学氢化。在 Pd/C 催化剂和乙酸酐存在下，氢气在环境温度和压力下流过反应器。在优化条件下，一锅同时进行氢化和乙酰化，避免了 4-氨基苯酚的不良副反应，从而提高了对乙酰氨基酚的选择性。通过允许将乙酸酐蒸气输送至反应容器的新型起泡器配置，进一步减少了副产物的形成。将球磨机结果与帕尔反应器中的传统搅拌罐氢化进行比较，结果显示其具有优异的产率和工艺质量强度。

  DOI：

  10.1039/d3gc04281b

文献信息

• Simple cyclodextrin aldehydes as excellent artificial oxidases
  作者：Thomas Hauch Fenger、Mikael Bols

  DOI：10.1007/s10847-010-9771-y

  日期：2011.4

  Cyclodextrin based oxidases, with a ketone as functional group are well known as good artificial enzyme mimics (Fenger et al. Org Biomol Chem 7:933–943; Marinescu and Bols Angew Chem Int Ed 45:4590–4593; Bjerre et al. Eur J Org Chem 704–710; Marinescu et al. J Am Chem Soc 127:17578–17579). We here report a series of modified cyclodextrins, having aldehydes as functional groups. The aldehyde based artificial enzymes have, in most cases, better catalysis than the ketones, because of their powerful covalent binding of hydrogen peroxide. Among the modified cyclodextrins studied are mono and di aldehydes on the 6 positions, with or without methylated hydroxyl groups. The aldehyde functionality was also introduced close to the secondary side, by attaching ethoxy-2-al or propoxy-3-al to the 2 position. The modified cyclodextrins showed excellent enzymatic activity towards oxidation of different aminophenols, and 4-methoxy benzyl alcohol with hydrogen peroxide as a stoichiometric oxidant. Rate enhancements up to 4,600 were achieved for oxidation of 4-methoxy benzyl alcohol, where as oxidation of amines gave rate enhancements up to 3,400. The artificial oxidases catalyses oxidations under enzymatic conditions (water, pH 7, 25 °C), following Michaelis–Menten kinetics. To confirm the enzyme activity, inhibition studies with sodium naphthalene-2-sulfonate were carried out. These studies showed competitive inhibition of the enzymes, verifying the cyclodextrins enzyme like character.

  众所周知，以酮为官能团的环糊精氧化酶是良好的人工酶模拟物（Fenger et al.Org Biomol Chem 7:933-943; Marinescu and Bols Angew Chem Int Ed 45:4590-4593; Bjerre et al.Eur J Org Chem 704-710; Marinescu et al.J Am Chem Soc 127:17578-17579）。我们在此报告了一系列以醛为官能团的改性环糊精。在大多数情况下，以醛为基础的人工酶比酮类具有更好的催化作用，因为它们能与过氧化氢产生强大的共价结合。在所研究的改性环糊精中，有 6 个位置上的单醛和二醛，有或没有甲基化羟基。此外，还通过在 2 位上连接乙氧基-2-al 或丙氧基-3-al，在靠近仲侧的位置引入了醛官能团。修饰后的环糊精对不同氨基苯酚和 4-甲氧基苯甲醇（以过氧化氢作为定量氧化剂）的氧化显示出卓越的酶活性。氧化 4-甲氧基苯甲醇的速率可提高到 4 600，而氧化胺的速率可提高到 3 400。人工氧化酶在酶促条件下（水、pH 值 7、25 °C），按照 Michaelis-Menten 动力学催化氧化。为了证实酶的活性，还用萘-2-磺酸钠进行了抑制研究。这些研究显示了对酶的竞争性抑制，验证了环糊精的酶类似特性。
• Two Diastereomeric Artificial Enzymes with Different Catalytic Activity
  作者：Emil Lindbäck、You Zhou、Christian Marcus Pedersen、Mikael Bols

  DOI：10.1002/ejoc.201200699

  日期：2012.9

  Two epimeric cyclodextrin-6-C-aldehydes were synthesised in 10 steps from β-cyclodextrin. The synthesis involved protection/partial deprotection, oxidation to a 6-aldehyde, olefination, dihydroxylation, selective protection of the secondary alcohol and oxidation. The two isomers catalysed theoxidation of aromatic amines by hydrogen peroxide but predominantly outside the cavity. Hydrolysis of aryl glycosides

  由β-环糊精分10步合成了两种差向异构环糊精-6-C-醛。合成涉及保护/部分脱保护、氧化成 6-醛、烯化、二羟基化、仲醇的选择性保护和氧化。这两种异构体通过过氧化氢催化芳香胺的氧化，但主要是在空腔外。另一方面，芳基糖苷的水解在遵循 Michaelis-Menten 动力学的反应中被催化。S 异构体是比 R 异构体好 5-20 倍的催化剂，这从模型中得到了解释。
• Cyclodextrin-based artificial oxidases with high rate accelerations and selectivity
  作者：You Zhou、Emil Lindbäck、Christian M. Pedersen、Mikael Bols

  DOI：10.1016/j.tetlet.2014.02.100

  日期：2014.4

  Three cyclodextrin derivatives with one to four 2-O-formylmethyl groups attached to the secondary rim were prepared and investigated as catalysts for the oxidation of aminophenols in buffered dilute hydrogen peroxide. The derivatives were found to be Michaelis-Menten catalysts and to give rate accelerations of up to 20,000 for the oxidation of 2-aminophenol to 2-amino-phenoxazin-3-one, and 12,000 for the oxidation of 2-amino-p-cresol to 2-nitro-p-cresol. While a range of differently substituted substrates was oxidized the success of the reaction was highly dependent on the substituent pattern. The ability of one of the new artificial enzymes to oxidize selectively one aminophenol from a mixture of two was investigated giving substrate selectivities of up to 16:1. (C) 2014 Elsevier Ltd. All rights reserved.