3-[(3-nitrophenyl)amino]cyclohex-2-en-1-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: 3-[(3-nitrophenyl)amino]cyclohex-2-en-1-one
• 英文别名: 3-(3-nitroanilino)-cyclohex-2-en-1-one；3-(3-nitrophenylamino)cyclohex-2-enone；3-(3-nitroanilino)cyclohex-2-en-1-one
• 化学式: C₁₂H₁₂N₂O₃
• mdl: MFCD01109152
• 分子量: 232.239
• InChiKey: XSKKZXQWMQORFT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  74.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-[(3-nitrophenyl)amino]cyclohex-2-en-1-one 在 sodium azide 、 羟基甲苯磺酰碘苯 作用下， 以 二氯甲烷 为溶剂， 以69%的产率得到1-(3-nitrophenylamino)-2-oxocyclopentanecarbonitrile
  参考文献：
  名称：

  碘（iii）促进了1-芳基氨基-2-氧代环戊烷-1-腈的环重排反应，从而合成了N-芳基-δ-戊内酰胺。

  摘要：

  报道了通过苯基碘双（三氟乙酸）酯（PIFA）促进的1-芳基氨基-2-氧代环戊烷-1-腈的分子内环重排反应合成N-芳基-δ-戊内酰胺的第一个实例。我们显示，这种由高价碘（PIFA）驱动的前所未有的区域选择性环重排反应涉及C5-H消除，C1-C2键打开和C1-N键重排步骤以及抑制CN基团的离去趋势。内酰胺的结构通过单晶X射线衍射（XRD）分析进一步证实。本方案在反应条件下显示出各种不同的官能团耐受性，并提供了良好的内酰胺收率。

  DOI：

  10.1039/c9ob02598g
• 作为产物：
  描述：

  1,3-环己二酮 、 间硝基苯胺 在 对甲苯磺酸 作用下， 以 甲苯 为溶剂， 以67%的产率得到3-[(3-nitrophenyl)amino]cyclohex-2-en-1-one
  参考文献：
  名称：

  冻结生物活性构象以增强效能：BAY 85-8501的鉴定，BAY 85-8501是人类中性粒细胞弹性蛋白酶对肺部疾病的选择性和强效抑制剂

  摘要：

  Human neutrophil elastase (HNE) is a key protease for matrix degradation. High HNE activity is observed in inflammatory diseases. Accordingly, HNE is a potential target for the treatment of pulmonary diseases such as chronic obstructive pulmonary disease (COPD), acute lung injury (ALI), acute respiratory distress syndrome (ARDS), bronchiectasis (BE), and pulmonary hypertension (PH). HNE inhibitors

  DOI：

  10.1002/cmdc.201500131

文献信息

• Syntheses of N-Alkylated Carbazolones via Pd(OAc)2-Mediated Intramolecular Coupling of N-Substituted 3-(Arylamino)cyclohex-2-enones
  作者：Yunfei Du、Jianhui Huang、Wenying Bi、Xiliu Yun、Yanfeng Fan、Xiuxiang Qi

  DOI：10.1055/s-0030-1259027

  日期：2010.12

  A variety of functionalized N-alkylated carbazolones were prepared via N-alkylation of 3-(arylamino)cyclohex-2-enones followed by an intramolecular oxidative coupling mediated by Pd(OAc)2 under an oxygen atmosphere. This approach adopts an inverted sequence, consisting of the conventional annulation and subsequent N-alkylation.

  通过N-烷基化3-(芳胺基)环己-2-烯酮，然后在氧气氛围下经Pd(OAc)2介导的分子内氧化偶联反应，制备了一系列功能化的N-烷基化咔唑酮。该方法采用逆序策略，包含传统的环化反应和随后的N-烷基化步骤。
• NMR of Enaminones Part 3—1H,13C and17O NMR Spectroscopic Studies of Acyclic and CyclicN-Aryl Enaminones: Substituent Effects and Intramolecular Hydrogen Bonding
  作者：Jin-Cong Zhuo

  DOI：10.1002/(sici)1097-458x(199705)35:5<311::aid-omr94>3.0.co;2-m

  日期：1997.5

  17O, 13C and 1H NMR spectra for para‐ and meta‐substituted 4‐arylaminopent‐3‐en‐2‐ones (acyclic enaminones, 1 and 2) and 3‐arylaminocyclohex‐2‐en‐1‐ones (cyclic enaminones, 3 and 4) are reported. The 17O, 13C and 1H shift values of these enaminones correlate well with σm0 and σp‐ constants in the correlations for meta and para derivatives, and with pKa values of the corresponding anilines. Dual substituent

  对位和间位取代的 4-芳基氨基戊-3-烯-2-酮（无环烯胺酮，1 和 2）和 3-芳基氨基环己-2-烯-1-酮（环烯胺酮，3和 4) 被报告。这些烯胺酮的 17O、13C 和 1H 位移值与间位和对位衍生物相关性中的 σm0 和 σp 常数以及相应苯胺的 pKa 值密切相关。还进行了双取代基参数分析。羰基的 17O 和 13C 化学位移与相应的 N-酰基苯胺化学位移的相关性表明，烯胺酮部分作为一个整体具有与 RCONH 基团相似的电子特性。烯胺酮的羰基 O 原子的 17O 位移值与其 1H 和 13C 数据密切相关。与 3 和 4 相比，观察到 1 和 2 对 O 原子的屏蔽为 33–45 ppm，分别。这归因于分子内氢键。© 1997 John Wiley & Sons, Ltd.
• Freezing the Bioactive Conformation to Boost Potency: The Identification of BAY 85-8501, a Selective and Potent Inhibitor of Human Neutrophil Elastase for Pulmonary Diseases
  作者：Franz von Nussbaum、Volkhart M.-J. Li、Swen Allerheiligen、Sonja Anlauf、Lars Bärfacker、Martin Bechem、Martina Delbeck、Mary F. Fitzgerald、Michael Gerisch、Heike Gielen-Haertwig、Helmut Haning、Dagmar Karthaus、Dieter Lang、Klemens Lustig、Daniel Meibom、Joachim Mittendorf、Ulrich Rosentreter、Martina Schäfer、Stefan Schäfer、Jens Schamberger、Leila A. Telan、Adrian Tersteegen

  DOI：10.1002/cmdc.201500131

  日期：2015.7

  Human neutrophil elastase (HNE) is a key protease for matrix degradation. High HNE activity is observed in inflammatory diseases. Accordingly, HNE is a potential target for the treatment of pulmonary diseases such as chronic obstructive pulmonary disease (COPD), acute lung injury (ALI), acute respiratory distress syndrome (ARDS), bronchiectasis (BE), and pulmonary hypertension (PH). HNE inhibitors

  Human neutrophil elastase (HNE) is a key protease for matrix degradation. High HNE activity is observed in inflammatory diseases. Accordingly, HNE is a potential target for the treatment of pulmonary diseases such as chronic obstructive pulmonary disease (COPD), acute lung injury (ALI), acute respiratory distress syndrome (ARDS), bronchiectasis (BE), and pulmonary hypertension (PH). HNE inhibitors
• Synthesis, polymorphic characterization and structural comparisons of the non-linear optically active and inactive forms of polymorphs of 3-(nitroanilino)cycloalk-2-en-1-ones
  作者：Kin-Shan Huang、Doyle Britton、Margaret C. Etter、Stephen R. Byrn

  DOI：10.1039/jm9960600123

  日期：——

  There 3-(nitroanilino)cycloak-2-en-1-ones have been synthesized and their non-linear optical (NLO) properties investigated. Two of these compounds have been found to exist in two polymorphic forms (α and β) that exhibit different second-order NLO properties. These polymorphic forms were prepared and characterized by second-harmonic generation measurements as well as the more conventional methods of X-ray powder diffraction and infrared spectroscopy. Of these polymorphs, the α- and β-forms of 3-(4-nitroanilino)cyclohex-2-en-1-one (4NACHD) have been further characterized by X-ray single-crystal diffraction and the crystal structures obtained have been compared with each other to rationalize why these two crystalline forms exhibit different second-order NLO properties. The α-form of 4NACHD crystallizes in a centrosymmetric space group (P21/c) with a= 6.863(7), b= 12.767(3), c= 13.410(4)Å, β= 104.59 (5)°, Z= 4, Dc= 1.356 g cm–3 and R= 0.046, whereas the β-form crystallizes in a non-centrosymmetric space group (P212121) with a= 7.228(3), b= 12.064(3), c= 13.104(3)Å, Z= 4, Dc= 1.350 g cm–3 and R= 0.076. Except for the slight difference in bond distances, both the α- and β-forms have the same orientation of the carbonyl group and hydrogen-bonding interactions. The carbonyl group is anti to the N–H group in both the two forms that result in the lambda (A) conformation. The whole molecule of 4NACHD is more twisted in the β-form than in the α-form. Based on structural comparisons of the polymorphs of 4NACHD and other compounds, the more twisted conformation in the β-form may bias molecules to pack into a non-centrosymmetric structure. Preliminary results suggest that 3-(nitroanilino)cycloalk-2-en-1-one compounds may have a higher chance of forming non-centrosymmetric crystal structures than normal achiral organic molecules.

  合成了 3-(硝基苯胺基)环烷-2-en-1-酮并研究了它们的非线性光学 (NLO) 性质。已发现其中两种化合物以两种多晶型（α 和 β）存在，表现出不同的二阶 NLO 特性。这些多晶型物是通过二次谐波产生测量以及更传统的 X 射线粉末衍射和红外光谱方法来制备和表征的。在这些多晶型物中，3-(4-硝基苯胺基)环己基-2-en-1-酮(4NACHD)的α-和β-形式已通过X射线单晶衍射进一步表征，并已获得晶体结构相互比较，以合理解释为什么这两种晶型表现出不同的二阶 NLO 特性。 4NACHD 的 α 型在中心对称空间群 (P21/c) 中结晶，其中 a= 6.863(7), b= 12.767(3), c= 13.410(4)Å, β= 104.59 (5)°, Z= 4，Dc= 1.356 g cm–3，R= 0.046，而β型结晶在非中心对称空间群（P212121），a= 7.228(3)，b= 12.064(3)，c= 13.104(3) )Å，Z= 4，Dc= 1.350 g cm–3，R= 0.076。除了键距略有不同外，α-和β-形式均具有相同的羰基方向和氢键相互作用。两种形式中的羰基都与 N-H 基团相反，从而形成 lambda (A) 构象。 4NACHD 的整个分子在 β 型中比在 α 型中更加扭曲。根据 4NACHD 和其他化合物的多晶型物的结构比较，β 型中更扭曲的构象可能会使分子偏向堆积成非中心对称结构。初步结果表明，3-(硝基苯胺基)环烷-2-en-1-酮化合物可能比普通非手性有机分子有更高的机会形成非中心对称晶体结构。
• 10.1039/d4nj01583e
  作者：Sinha, Goutam、Pramanik, Sayan、Jana, Debashis、Ghosh, Anirban、Mukhopadhyay, Chhanda

  DOI：10.1039/d4nj01583e

  日期：——

  indole-2,4-diones from readily available β-enaminones and glyoxal and subsequent I2/DMSO-mediated oxidation/aromatization of tetrahydro indole-2,4-dione to produce 4-hydroxyisatin derivatives. The key aspect of this protocol includes the dual catalytic activity of molecular iodine in the presence of DMSO. Mechanistic study suggested that this reaction is substrate selective as corresponding aromatization

  我们报道了一种从容易获得的β-烯胺酮和乙二醛合成四氢吲哚-2,4-二酮的有效合成路线，以及随后的I 2 /DMSO介导的四氢吲哚-2,4氧化/芳构化-二酮生产4-羟基靛红衍生物。该协议的关键方面包括分子碘在 DMSO 存在下的双重催化活性。机理研究表明，该反应具有底物选择性，因为相应的芳构化和 sp 3 C-H 氧化在 6,6-二取代四氢吲哚-2,4-二酮存在下停止。此外，对 β-烯胺酮和乙二醛进行酸催化环化/脱水/烯醇-酮互变异构反应后合成四氢吲哚-2,4-二酮进行了彻底的研究。