4-hydroxy-3-methyl-4-(2-nitrophenyl)butan-2-one

• 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: 4-hydroxy-3-methyl-4-(2-nitrophenyl)butan-2-one
• 化学式: C₁₁H₁₃NO₄
• 分子量: 223.229
• InChiKey: WKHCQWFADOTADN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.85
• 重原子数：
  16.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  80.44
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  4-hydroxy-3-methyl-4-(2-nitrophenyl)butan-2-one 在 盐酸 、 铁粉 、 对甲苯磺酸 作用下， 以 乙醇 、 水 、 甲苯 为溶剂， 生成 4-(2-aminophenyl)-3-methyl-(3E)-buten-2-one
  参考文献：
  名称：

  蓝光促进的碳-碳双键异构化及其在喹啉合成中的应用

  摘要：

  据报道在没有任何光氧化还原催化剂的情况下，蓝光促进的碳-碳双键异构化。在简单的有氧条件下，它可以快速获得一系列喹啉，收率好至极好。该方案是直接，无催化剂且操作方便的。

  DOI：

  10.1039/c7ob00558j
• 作为产物：
  描述：

  邻硝基苯甲醛 、 丁酮 在 [Zn₂(formate)(Fe^III(H₂O)(tetrakis(4-carboxyphenyl)porphyrin(6-)))]·3DMF·H₂O 作用下， 以 neat (no solvent) 为溶剂， 反应 72.0h， 以96%的产率得到4-hydroxy-3-methyl-4-(2-nitrophenyl)butan-2-one
  参考文献：
  名称：

  四种金属卟啉骨架作为非均相催化剂进行选择性氧化和羟醛反应

  摘要：

  四种多孔金属卟啉骨架材料，[（CH 3）2 NH 2 ] [Zn 2（HCOO）2（Mn III -TCPP）]·5DMF·2H 2 O（1 ; H 6 TCPP =四（4-羧基苯基）卟啉，[（CH 3）2 NH 2 ] [Cd 2（HCOO）2（Mn III –TCPP）]·5DMF·3H 2 O（2），[Zn 2（HCOO）（Fe III（H 2 O）–TCPP ）]·3DMF·H 2 O（3）和[Cd 3（H 2 O）6（μ 2 -O）（铁III -HTCPP）2 ]·5DMF（4）通过加热M的混合物，合成III氯-H 4 TCPP（M = Mn和Fe）和M'（ DMF和乙酸的混合溶剂中的M'= Zn或Cd）硝酸盐。化合物1 - 3是从M'建立2（COO）4桨轮亚基桥接由M III -TCPP和甲酸盐配体，以形成其三维连接。甲酸盐柱与1和2中的M和M'阳离子异质连接，并在3中均匀地连接M'阳离子。该μ

  DOI：

  10.1021/ic3019502

文献信息

• The Baylis–Hillman approach to quinoline derivatives
  作者：Oluwole B. Familoni、Phindile J. Klaas、Kevin A. Lobb、Vusumzi E. Pakade、Perry T. Kaye

  DOI：10.1039/b608592j

  日期：——

  Baylis-Hillman reactions of 2-nitrobenzaldehydes with various activated alkenes afford adducts that undergo reductive cyclisation to quinoline derivatives. The chemo- and regioselectivity of cyclisation appears to be influenced by the choice of both the substrate and the reagent system, and competing reactions have been observed.

  2-硝基苯甲醛与各种活化烯烃的Baylis-Hillman反应提供加合物，该加合物经过还原环化生成喹啉衍生物。环化反应的化学和区域选择性似乎受底物和试剂系统选择的影响，并且观察到竞争反应。
• A Simple Primary−Tertiary Diamine−Brønsted Acid Catalyst for Asymmetric Direct Aldol Reactions of Linear Aliphatic Ketones
  作者：Sanzhong Luo、Hui Xu、Jiuyuan Li、Long Zhang、Jin-Pei Cheng

  DOI：10.1021/ja069372j

  日期：2007.3.1

  regio- and diastereoselectivity and enantioselectivity under ambient temperature. Significantly, the reactions accommodate the synthetically important but challenging substrates, such as linear aliphatic ketones, with high regioselectivity and unprecedented syn diastereoselectivity. These results are in sharp contrast with the secondary amine mediated similar reactions wherein anti diastereoselectivity

  与已充分探索的带有仲胺的烯胺催化相比，开发高效的基于烯胺的伯胺催化剂直到最近仍然是一个难以捉摸的目标。我们在本文中提出了一种简单的手性伯-叔二胺 1d 与 TfOH 结合用作有效的基于烯胺的伯胺催化剂。1d-TfOH催化体系可以有效催化不对称直接醛醇反应，底物范围广，在环境温度下具有高区域选择性和非对映选择性以及对映选择性。值得注意的是，这些反应适应了合成上重要但具有挑战性的底物，例如线性脂肪族酮，具有高区域选择性和前所未有的顺式非对映选择性。
• Binaphthyl-based chiral bifunctional organocatalysts for water mediated asymmetric List–Lerner–Barbas aldol reactions
  作者：Veeramanoharan Ashokkumar、Chinnadurai Chithiraikumar、Ayyanar Siva

  DOI：10.1039/c6ob01558a

  日期：——

  Novel binaphthyl-based chiral bifunctional organocatalysts were designed, synthesized and successfully applied to the asymmetric List–Lerner–Barbas aldol reaction in the presence of water. These organocatalysts were found to be effective catalysts for the reactions of symmetrical, unsymmetrical and cyclic ketones with different aldehydes to give the corresponding aldol products with higher yields (up

  设计，合成了新型的基于双萘基的手性双官能有机催化剂，并成功地将其用于存在水的不对称List–Lerner–Barbas aldol反应中。发现这些有机催化剂对于对称，不对称和环状酮与不同醛的反应是有效的催化剂，从而以更高的产率（高达98％）和非常好的ee高达99％给出相应的羟醛产物。与先前报道的众所周知的基于脯氨酸的有机催化剂相比，该催化系统导致更高的产率和选择性。除了溶剂的影响外，还研究了添加剂，催化剂浓度，温度和反应的底物范围。
• Concerning the mechanism of the Friedländer quinoline synthesis
  作者：Joseph M Muchowski、Michael L Maddox

  DOI：10.1139/v03-211

  日期：2004.3.1

  Detailed experiments regarding the mechanism of the Friedländer synthesis of quinolines from o-aminobenzaldehydes and simple aldehydes or ketones are described. Under the basic or acidic conditions commonly used in this reaction, it is concluded that the first step involves a slow intermolecular aldol condensation of the aldehyde or ketone with the o-aminobenzaldehyde. The aldol adduct 5 generated in this manner then undergoes very rapid cyclization to 4, which subsequently loses water to produce the quinoline derivative 8. Both 5 and 4 are too short lived to be detectable (TLC), even when deliberately generated by other means. It is also shown that E-enones corresponding to 6, i.e., the aldol dehydration product, are converted into quinolines (e.g., 21a and 21b from 17a and 17b) under basic or acidic conditions. Such enones are not detected as intermediates in the base-induced Friedländer synthesis, even though certain congeners (17b) would be easily observable. Under acidic conditions these enones are too short lived to be detectable. Schiff bases derived from 2-aminobenzaldehyde (18a) and aldehydes or ketones can be generated under special conditions, but they show reactivity patterns different from those seen in the usual Friedländer condensations. Thus, the ytterbium-triflate-catalyzed reaction of aldehydes with 18a at room temperature in toluene generates the E-Schiff bases (33, R¹ = H), from which isomeric mixtures of tetrahydroquinoline derivatives 26 are formed exclusively. At higher temperatures, the E-Schiff bases 33 are isomerized to the Z-Schiff bases 34, from which the 3-substituted quinoline derivatives 24 are formed as the major products under appropriate conditions. Also, the ytterbium-triflate-catalyzed reaction of 18a with the pyrrolidine enamines of the methyl-n-alkylketones 38a,b produces mixtures in which the 2-monosubstituted kinetic products 37b,d predominate over the 2,3-disubstituted thermodynamic products 21c,e by a factor of 4:1 to 5:1. These results are opposite to those observed under the usual basic or acidic Friedländer reactions with methyl-n-alkylketones, where the thermodynamic products are usually strongly favored. The unusual kinetic:thermodynamic product ratios observed with 38a,b are ascribed to the generation and rapid cyclization of mixtures of the Schiff bases 35 and 36, in which the kinetic isomer 35 is highly predominant. Key words: mechanism, Friedländer synthesis, quinolines, intramolecular aldol reactions, Schiff bases, tetrahydroquinolines, high kinetic:thermodynamic product ratios.

  描述了关于从o-氨基苯甲醛和简单醛或酮合成喹啉的 Friedländer 合成机制的详细实验。在这种反应中常用的碱性或酸性条件下，得出结论第一步涉及醛或酮与o-氨基苯甲醛的缓慢分子间醛缩反应。以这种方式生成的醛缩加合物5随后经历非常快速的环化反应形成4，然后失去水生成喹啉衍生物8。即使通过其他方式故意生成，5和4都太短暂而无法检测到（TLC）。还表明与6相对应的E-烯酮，即醛缩脱水产物，在碱性或酸性条件下会转化为喹啉（例如，从17a和17b生成的21a和21b）。尽管某些同系物（17b）很容易观察到，但在碱性诱导的 Friedländer 合成中并未检测到这些烯酮作为中间体。在酸性条件下，这些烯酮太短暂而无法检测到。从2-氨基苯甲醛（18a）和醛或酮生成的席夫碱可以在特殊条件下产生，但它们显示出与通常的 Friedländer 缩合反应中看到的反应性模式不同。因此，醛在甲苯中与18a在室温下催化的钇三氟乙酸盐反应生成E-席夫碱（33，R1 = H），从中仅生成异构混合物四氢喹啉衍生物26。在较高温度下，E-席夫碱33异构为Z-席夫碱34，在适当条件下主要生成3-取代喹啉衍生物24。此外，18a与甲基-n-烷基酮38a，b的吡咯啉烯胺反应在产物中产生2-单取代动力学产物37b，d，其比例为4：1至5：1，优于2,3-二取代热力学产物21c，e。这些结果与通常与甲基-n-烷基酮进行的基本或酸性 Friedländer 反应中观察到的情况相反，通常情况下热力学产物通常受到强烈青睐。观察到的与38a，b相反的不寻常的动力学：热力学产物比例归因于席夫碱35和36的混合物的生成和快速环化，其中动力学异构体35占主导地位。关键词：机制，Friedländer 合成，喹啉，分子内醛缩反应，席夫碱，四氢喹啉，高动力学：热力学产物比。
• Stereoselective Aldol Reactions Catalyzed by Acyclic Amino Acids in Aqueous Micelles
  作者：Dong-Sheng Deng、Jiwen Cai

  DOI：10.1002/hlca.200790003

  日期：2007.1

  The catalytic properties of all proteinogenic, acyclic amino acids for direct aldol reaction in H2O, assisted by various surfactants, were investigated. The basic and neutral amino acids were shown to be efficient catalysts, giving rise to good-to-excellent yields of adducts (up to 95%), with moderate-to-good diastereoselectivities (up to 86%), L-arginine being the most-effective catalyst. The syn/anti

  在各种表面活性剂的辅助下，研究了所有蛋白原性，无环氨基酸在H 2 O中直接进行羟醛反应的催化性能。碱性和中性氨基酸被证明是有效的催化剂，可产生良好至优异的加合物收率（高达95％），中等至良好的非对映选择性（高达86％），L-精氨酸为最有效的催化剂。的顺式/反非对映体比率可以通过所使用的氨基酸的适当选择可以容易地调整。同样，进行该反应的底物范围扩大到带有给电子性Br取代基的反应性较低的醛。