2-(2-nitrophenyl)-1-(p-tolyl)ethan-1-one | 58751-65-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 2-(2-nitrophenyl)-1-(p-tolyl)ethan-1-one
• 英文别名: 1-(4-Methylphenyl)-2-(2-nitrophenyl)ethanone
• CAS: 58751-65-8
• 化学式: C₁₅H₁₃NO₃
• 分子量: 255.273
• InChiKey: RDHDEJRULGJOFE-UHFFFAOYSA-N

物化性质

• 熔点：
  67-70 °C(Solv: ethanol (64-17-5))
• 沸点：
  408.8±25.0 °C(Predicted)
• 密度：
  1.216±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  62.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(2-nitrophenyl)-1-(p-tolyl)ethan-1-one 在 吡啶 、 硼烷四氢呋喃络合物 、 盐酸羟胺 、 sodium acetate 作用下， 以 乙醇 、 水 为溶剂， 生成 (+/-)-N-formyl-α-(4-methylphenyl)-2-nitrobenzeneethanamine
  参考文献：
  名称：

  (.+-.)-4-Aryl-4,5-dihydro-3H-1,3-benzodiazepines. 2. Nuclear substituted analogs of (.+-.)-4,5-dihydro-2,3-dimethyl-4-phenyl-3H-1,3-benzodiazepine and (.+-.)-4,5-dihydro-2-ethyl-3-methyl-4-phenyl-3H-1,3-benzodiazepine as potential antidepressant agents

  摘要：

  Antidepressant-like activity, as evidenced by marked inhibition of tetrabenazine-induced ptosis, was previously reported for (+/-)-4,5-dihydro-4-phenyl-3H-1,3-benzodiazepine derivatives. Since optimal antitetrabenazine activity was associated with (+/-)-4,5-dihydro-2,3-dimethyl-4-phenyl-3H-1,3-benzodiazepine (9k, HRP 543) and the 2-ethyl-3-methyl analogue (10k), the synthesis and evaluation of nuclear-substituted derivatives of these two compounds was also investigated. The initial synthesis involved Friedel-Crafts acylation of substituted benzenes with 2-nitrophenylacetyl chloride to afford 1-aryl-2-(2-nitrophenyl)ethanones 2, which were converted in five steps to (+/-)-alpha-aryl-N-methyl-2-nitrobenzeneethanamines 7. Greater flexibility with respect to the introduction of nuclear substituents was achieved by conversion of 2-nitrotoluene derivatives to 2 via acylation of intermediate beta-(dimethylamino)-2-nitrostyrenes with various aroyl chlorides and hydrolysis. Reductive amination of 2 with methylamine and sodium cyanoborohydride afforded 7 directly and significantly reduced the number of synthetic steps. Reduction of 7a-j to diamines 8a-j and cyclization with appropriate ortho esters gave nuclear-substituted analogues of 9k and 10k. Marked antitetrabenazine activity was associated with many of these compounds. Significant enhancement of activity with respect to the unsubstituted analogues 9k and 10k was not observed, with the exception of 9c which appeared to be slightly more potent than 9k.

  DOI：

  10.1021/jm00346a004
• 作为产物：
  描述：

  (E)-3-(dimethylamino)-1-(4-methylphenyl)-2-(2-nitrophenyl)prop-2-en-1-one 以86%的产率得到
  参考文献：
  名称：

  MARTIN, L. L.;SETESCAK, L. L.;WORM, M.;CHICHLOW, C. A.;GEYER, H. M. ,, II+, J. MED. CHEM., 1982, 25, N 4, 346-351

  摘要：

  DOI：

文献信息

• Atroposelective Arene Formation by Carbene‐Catalyzed Formal [4+2] Cycloaddition
  作者：Ke Xu、Wenchang Li、Shaoheng Zhu、Tingshun Zhu

  DOI：10.1002/anie.201910049

  日期：2019.12.2

  Atroposelective arene formation is an efficient method to build axially chiral molecules with multi-substituted arenes. Reported here is an organocatalyzed atroposelective arene formation reaction by an N-heterocyclic carbene (NHC) catalyzed formal [4+2] cycloaddition of conjugated dienals and α-aryl ketones. This study expands the synthetic potential of NHC organocatalysis and provides a competitive

  阻转性选择性芳烃的形成是用多取代的芳烃构建轴向手性分子的有效方法。此处报道的是通过N-杂环卡宾（NHC）催化的共轭二烯醛和α-芳基酮的正式[4 + 2]环加成反应进行的有机催化的对映选择性芳烃形成反应。这项研究扩大了NHC有机催化的合成潜力，并为轴向手性配体，催化剂和其他功能分子的合成提供了竞争途径。
• Palladium-catalyzed synthesis of α-aryl acetophenones from styryl ethers and aryl diazonium salts <i>via</i> regioselective Heck arylation at room temperature
  作者：Rapelly Venkatesh、Adesh Kumar Singh、Yong Rok Lee、Jeyakumar Kandasamy

  DOI：10.1039/d1ob01503f

  日期：——

  Preparation of α-aryl acetophenones from styryl ethers and aryldiazonium salts is described. The reaction is catalyzed by palladium acetate at room temperature in the absence of ligand and base. The developed method is highly attractive in terms of reaction conditions, substrate scope, functional group tolerance and yields. Synthetic applications of the present method are demonstrated by preparing

  描述了从苯乙烯基醚和芳基重氮盐制备 α-芳基苯乙酮。该反应在室温下在没有配体和碱的情况下由乙酸钯催化。所开发的方法在反应条件、底物范围、官能团耐受性和产率方面极具吸引力。本方法的合成应用通过从苯乙烯醚制备 α-芳基吲哚和 3-芳基异香豆素来证明。
• Synthesis of 3-Acyloxyindolenines by TiCl₃-Mediated Reductive Cyclization of 2-(<i>ortho</i>-Nitroaryl)-Substituted Enol Esters
  作者：Dina V. Boyarskaya、Alberto Ongaro、Cyril Piemontesi、Qian Wang、Jieping Zhu

  DOI：10.1021/acs.orglett.2c02860

  日期：2022.9.30

  In the presence of TiCl3, the reductive cyclization of tetrasubstituted enol esters bearing a 2-(ortho-nitroaryl) substituent affords 3-acyloxy-2,3-disubstituted indolenines in good yields. A domino process involving the partial reduction of nitro to a nitroso group followed by 5-center-6π-electrocyclization, 1,2-acyloxy migration, and the further reduction of the resulting nitrone intermediate accounts

  在TiCl 3存在下，带有2-(邻-硝基芳基)取代基的四取代烯醇酯的还原环化以良好的收率得到3-酰氧基-2,3-二取代的二氢吲哚。多米诺骨牌过程涉及将硝基部分还原为亚硝基，然后进行 5-中心-6π-电环化、1,2-酰氧基迁移以及所得硝酮中间体的进一步还原，这是反应结果的原因。如此获得的二氢吲哚通过一系列皂化和半频哪醇重排顺利转化为 2,2-二取代羟吲哚。
• Atroposelective Synthesis of Triaryl α‐Pyranones with 1,2‐Diaxes by N‐Heterocyclic Carbene Organocatalysis
  作者：Simiao Zhang、Xiaoxue Wang、Li‐Li Han、Jibin Li、Zheng Liang、Donghui Wei、Ding Du

  DOI：10.1002/anie.202212005

  日期：2022.12.23

  The single-step atroposelective construction of triaryl α-pyranones with stereogenic 1,2-diaxes was accomplished by NHC organocatalysis. The structure of the substrates and the catalytic system play a critical role in the success of this protocol. DFT calculations were performed to rationalize the origin of the high stereoselectivity.

  通过 NHC 有机催化完成了具有立体异构 1,2-二轴的三芳基 α-吡喃酮的单步阻转选择性构建。底物的结构和催化系统对该协议的成功起着至关重要的作用。进行 DFT 计算以合理化高立体选择性的起源。
• Enantioselective Access to Triaryl-2-pyrones with Monoaxial or Contiguous C–C Diaxes via Oxidative NHC Catalysis
  作者：Si-Chen Zhang、Shengping Liu、Xia Wang、Shao-Jie Wang、Hui Yang、Lin Li、Binmiao Yang、Ming Wah Wong、Yu Zhao、Shenci Lu

  DOI：10.1021/acscatal.2c05570

  日期：2023.2.17

  materials. This N-heterocyclic carbene catalysis method adopts an atroposelective annulation of 2-aryketones with ynals under oxidative conditions. The annulation includes the construction of one or two axes in a single operation, achieves step economy, and affords axially chiral triaryl-2-pyrones in moderate to good yields, with high to excellent enantioselectivities. DFT calculations of the relative energies

  我们在此展示了一种前所未有的立体选择性合成三芳基-2-吡喃酮的方法，该方法由现成的起始材料制成，具有单轴或连续双轴。这种N-杂环卡宾催化方法采用氧化条件下2-芳酮与炔烃的阻转选择性环化。环化包括在单个操作中构建一个或两个轴，实现步骤经济，并以中等至良好的收率提供轴向手性三芳基-2-吡喃酮，具有高至优异的对映选择性。对立体异构体和旋转势垒的相对能量进行了 DFT 计算。