(2-氨基苯基)(邻甲苯基)甲酮 | 36804-45-2

• 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: (2-氨基苯基)(邻甲苯基)甲酮
• 英文名称: (2-aminophenyl)(o-tolyl)methanone
• 英文别名: 2-amino-2'-methylbenzophenone；(2-aminophenyl)(2-methylphenyl)methanone；2-Amino-2'-methyl-benzophenon；(2-Aminophenyl)-(2-methylphenyl)methanone
• CAS: 36804-45-2
• 化学式: C₁₄H₁₃NO
• 分子量: 211.263
• InChiKey: ASDIDCKLLOQMSN-UHFFFAOYSA-N

物化性质

• 熔点：
  81-82 °C
• 沸点：
  369.4±25.0 °C(Predicted)
• 密度：
  1.135±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  43.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2-氨基苯基)(邻甲苯基)甲酮 在 盐酸 、 manganese(IV) oxide 、 氢氧化钾 、 盐酸肼 、 环己烷 、 silica gel 、 一水合肼 、 sodium sulfate 、 sodium nitrite 作用下， 以 乙醇 为溶剂， 反应 16.5h， 生成 1-甲基芴
  参考文献：
  名称：

  Chemistry of 1-Alkylfluorenylidenes. Steric Effects on Arylcarbene Reactivities

  摘要：

  9-Diazofluorenes (RDAF, 1) having a series of alkyl (R) groups from Me to tBu at the 1-position were prepared and decomposed to generate the corresponding fluorenylidenes (RFL, 2) under various conditions in order to examine steric effects on the reactivities of carbenes. Thus, in cyclohexane, singlet fluorenylidenes ((1)RFLs) gave 9-cyclohexylfluorenes while triplet states ((3)RFLs) underwent H abstraction to give 9-fluorenyl (RFLH(.)), which eventually led to fluorene (4, RFLH(2)) and 9,9'bifluorenyl (5), and the ratio of the triplet products to the singlet was increased as more bulky R groups were introduced at the 1-position. These results are interpreted in terms of the steric effects on singlet reactivity, which requires formation of two bonds simultaneously. Generation of tBuFL resulted in the almost exclusive formation of intramolecular reaction products which involved not only insertion of carbene into the delta-C-H bonds of the tert-butyl group but also insertion of the 1,5-biradical, followed by neophyl-type rearrangement. The results are understood as indicating that abstraction of the delta-H by (3)tBuFL gains over the concerted intramolecular C-H insertion in (1)tBuFL. Generation of 1-RFL (R = Et, iPr, tBu) in the gas phase at high temperature gave intramolecular reaction products both in singlet and in triplet states, but the ratio of the singlet to the triplet product increased in going from Et to iPr to tBu presumably due to the increased opportunities of (1)FL to be trapped by delta-C-H bonds. Spectroscopic studies using matrix isolation techniques as well as laser flash photolysis were also carried out to gain information on the intermediates.

  DOI：

  10.1021/ja00121a007
• 作为产物：
  描述：

  N-(2-(2-甲基苯甲酰基)苯基)乙酰胺 在 盐酸 、 potassium carbonate 作用下， 以 水 、 丙酮 为溶剂， 反应 2.0h， 以97%的产率得到(2-氨基苯基)(邻甲苯基)甲酮
  参考文献：
  名称：

  Carbonyl group coordination preferences in square-planar NiII and PdII complexes of pentadentate ligands by electron-withdrawing/donating substituents

  摘要：

  A series of chirally switchable Ni-II and Pd-II complexes were synthesized and fully characterized by X-ray crystallography and additionally by NMR. It was found that control of the stereochemical preference between (S*,S*) and (S*,R*) diastereomers by substituent modification of the ligand sidearms was possible in the process of crystallization with the preferred coordination of the sidearms generally consistent with expectations based on the electron-donating or -withdrawing properties of the sidearm substituent groups. There were however, quite interesting and unanticipated exceptions counter to chemical intuition and it seems that only for complexes with ortho substituents are strong preferences for the coordination manner necessarily displayed in the solid state based on the electron-withdrawing or -donating properties of the substituents. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2015.04.029

文献信息

• Palladium-catalyzed synthesis of polysubstituted quinolines from 2-amino aromatic ketones and alkynes
  作者：Wang Zhou、Jianhua Lei

  DOI：10.1039/c4cc00939h

  日期：——

  A palladium-catalyzed one-pot method for the synthesis of quinolines from commercial or readily available 2-amino aromatic ketones and alkynes is reported for the first time. This transformation offers an alternative method for the synthesis of polysubstituted quinoline.

  首次报道了钯催化的一锅法，由市售或易于获得的2-氨基芳族酮和炔烃合成喹啉。这种转化为合成多取代喹啉提供了另一种方法。
• Indium-Catalyzed Annulation of o-Acylanilines with Alkoxyheteroarenes: Synthesis of Heteroaryl[b]quinolines and Subsequent Transformation to Cryptolepine Derivatives
  作者：Kyohei Yonekura、Mika Shinoda、Yuko Yonekura、Teruhisa Tsuchimoto

  DOI：10.3390/molecules23040838

  日期：——

  We disclose herein the first synthetic method that is capable of offering heteroaryl[b]quinolines (HA[b]Qs) with structural diversity, which include tricyclic and tetracyclic structures with (benzo)thienyl, (benzo)furanyl, and indolyl rings. The target HA[b]Q is addressed by the annulation of o-acylanilines and MeO-heteroarenes with the aid of an indium Lewis acid that effectively works to make two

  我们在此公开了第一种合成方法，该方法能够提供具有结构多样性的杂芳基[b]喹啉（HA [b] Qs），包括具有（苯并）噻吩基，（苯并）呋喃基和吲哚基环的三环和四环结构。通过邻-苯丙氨酸和MeO-杂芳烃的环化反应，借助铟路易斯酸解决了目标HA [b] Q的问题，该路易斯酸有效地完成了一批中两种不同类型的NC和CC键的制备。随后可以将此处制备的一系列吲哚并[3,2-b]喹啉转化为结构上前所未有的隐血藤碱衍生物。机理研究表明，NC键形成之后是CC键形成。因此，铟催化的环化反应开始于邻酰基丙氨酸的NH 2基团以SNAr方式亲核连接到杂芳基环的MeO连接的碳原子上，从而形成NC键。然后，所得的中间体通过基于杂芳基环的碳原子对羰基碳原子的亲核攻击而环化以形成CC键，从而在芳香化脱水后提供HA [b] Q。
• Metal‐Free Synthesis of Anthranils by PhIO Mediated Heterocyclization of <i>ortho</i> ‐Carbonyl Anilines
  作者：Alankrita Garia、Jatin Grover、Nidhi Jain

  DOI：10.1002/ejoc.202100756

  日期：2021.8.6

  A metal-free synthesis of anthranils from ortho-carbonyl anilines using PhIO as a sole reagent under ambient conditions is described. No external additives are required, the reaction has broad substrate scope and delivers anthranils in excellent yields via oxidative heterocyclization.

  描述了在环境条件下使用 PhIO 作为唯一试剂从邻羰基苯胺无金属合成邻氨基苯甲酸。不需要外部添加剂，该反应具有广泛的底物范围，并通过氧化杂环化以优异的产率提供邻氨基苯甲酸。
• Organocatalytic Atroposelective Friedländer Quinoline Heteroannulation
  作者：You-Dong Shao、Meng-Meng Dong、You-An Wang、Pei-Ming Cheng、Tao Wang、Dao-Juan Cheng

  DOI：10.1021/acs.orglett.9b01731

  日期：2019.6.21

  An atroposelective Friedländer heteroannulation reaction of 2-aminoaryl ketones with α-methylene carbonyl derivatives has been developed for the first time with chiral phosphoric acid as an efficient organocatalyst. The desired enantioenriched axially chiral polysubstituted 4-arylquinoline architectures were prepared with good to high yields and enantioselectivities (up to 94% yield and up to 97% ee)

  利用手性磷酸作为有效的有机催化剂，首次开发了2-氨基芳基酮与α-亚甲基羰基衍生物的对位选择性弗里德兰德异环反应。制备了所需的对映体富集的轴向手性多取代的4-芳基喹啉结构，具有良好到高的产率和对映选择性（高达94％的产率和高达97％的ee）。此外，可以容易地将产品衍生化，以提供一系列新的含喹啉的异质异构体，这些异构体在不对称催化和药物发现中具有巨大的潜力。
• Palladium-catalyzed direct addition of arylboronic acids to 2-aminobenzonitrile derivatives: synthesis, biological evaluation and in silico analysis of 2-aminobenzophenones, 7-benzoyl-2-oxoindolines, and 7-benzoylindoles
  作者：Jiuxi Chen、Leping Ye、Weike Su

  DOI：10.1039/c4ob00978a

  日期：——

  A palladium-catalyzed direct addition of arylboronic acids to unprotected 2-aminobenzonitriles has been developed, leading to a wide range of 2-aminobenzophenones with moderate to excellent yields. The transformation has broad scope and high functional group tolerance. Moreover, 2-oxoindoline-7-carbonitrile and indole-7-carbonitrile were applicable to this process for the construction of 7-benzoyl-2-oxoindolines and 7-benzoylindoles, respectively. Among the compounds examined, compound 4e possessed the most potent anticancer activity against H446 and HGC-27 in vitro, with IC50 values of 0.02 μmol L−1 and 0.09 μmol L−1, respectively, while compound 4a showed the best potent anticancer activity against SGC-7901 with an IC50 value of 0.01 μmol L−1. Furthermore, we also performed in silico molecular docking calculations to investigate the interaction mode and binding affinity between the examined compounds and their tubulin target.

  开发了一种钯催化的芳基硼酸与未保护的2-氨基苯腈直接加成反应，得到了一系列中等至优异收率的2-氨基二苯甲酮。该反应具有广阔的应用范围和高度的官能团耐受性。此外，2-氧代吲哚啉-7-腈和吲哚-7-腈也适用于该过程，分别用于构建7-苯甲酰基-2-氧代吲哚啉和7-苯甲酰基吲哚。在检测的化合物中，化合物4e对H446和HGC-27细胞具有最强的体外抗癌活性，IC50值分别为0.02 μmol L−1和0.09 μmol L−1，而化合物4a对SGC-7901细胞显示出最佳的抗癌活性，IC50值为0.01 μmol L−1。此外，我们还进行了计算机分子对接计算，以研究检测化合物与其微管蛋白靶点之间的相互作用模式和结合亲和力。