1-溴-2-[(4-氰基苯氧基)甲基]苯 | 831239-25-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 中文名称: 1-溴-2-[(4-氰基苯氧基)甲基]苯
• 英文名称: 1-bromo-2-[(4-cyanophenoxy)methyl]benzene
• 英文别名: 4-((2-Bromobenzyl)oxy)benzonitrile；4-[(2-bromophenyl)methoxy]benzonitrile
• CAS: 831239-25-9
• 化学式: C₁₄H₁₀BrNO
• mdl: MFCD06627042
• 分子量: 288.143
• InChiKey: XWPNRRLPTICAKE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.071
• 拓扑面积：
  33
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-溴-2-[(4-氰基苯氧基)甲基]苯 在 四氯化钛 、 potassium carbonate 作用下， 以 二氯甲烷 、 丁酮 为溶剂， 反应 24.0h， 生成 4-Benzyloxy-3-(2-bromo-benzyl)-benzonitrile
  参考文献：
  名称：

  2'-位具有羰基的2-芳基甲基苯酚的分子内9元氢键

  摘要：

  通过可变温度1 H NMR研究和van't Hoff分析，确定了具有甲氧基羰基，二甲基氨基甲酰基和甲酰基的2-芳基甲基苯酚的羰基和酚羟基之间的九元分子内氢键的热力学参数。氢键的焓与苯酚上的取代基的吸电子能力和羰基的碱性有关。氢键的熵损失取决于酚基团的旋转自由度。

  DOI：

  10.1016/j.tet.2004.08.007
• 作为产物：
  描述：

  2-溴甲苯 在 N-溴代丁二酰亚胺(NBS) 、 potassium carbonate 、 过氧化苯甲酰 作用下， 以 四氯化碳 、 丁酮 为溶剂， 反应 5.0h， 生成 1-溴-2-[(4-氰基苯氧基)甲基]苯
  参考文献：
  名称：

  2'-位具有羰基的2-芳基甲基苯酚的分子内9元氢键

  摘要：

  通过可变温度1 H NMR研究和van't Hoff分析，确定了具有甲氧基羰基，二甲基氨基甲酰基和甲酰基的2-芳基甲基苯酚的羰基和酚羟基之间的九元分子内氢键的热力学参数。氢键的焓与苯酚上的取代基的吸电子能力和羰基的碱性有关。氢键的熵损失取决于酚基团的旋转自由度。

  DOI：

  10.1016/j.tet.2004.08.007

文献信息

• Catalytic Direct Arylation with Aryl Chlorides, Bromides, and Iodides:  Intramolecular Studies Leading to New Intermolecular Reactions
  作者：Louis-Charles Campeau、Mathieu Parisien、Annie Jean、Keith Fagnou

  DOI：10.1021/ja055819x

  日期：2006.1.1

  and heterocyclic arenes with aryl iodides, bromides, and chlorides has been developed. These reactions occur in excellent yield and are highly selective. Studies with aryl iodides substrates revealed that catalyst poisoning occurs due to the accumulation of iodide in the reaction media. This can be overcome by the addition of silver salts which also permits these reactions to occur at lower temperature

  已开发出一种用于将多种简单和杂环芳烃与芳基碘化物、溴化物和氯化物进行分子内直接芳基化的催化剂。这些反应以极好的收率发生并且具有高度选择性。对芳基碘化物底物的研究表明，由于碘化物在反应介质中的积累，会发生催化剂中毒。这可以通过添加银盐来克服，银盐也允许这些反应在较低温度下发生。该方法的效用通过咔唑天然产物的快速合成和通过直接芳基化产物的开环反应合成空间位阻四邻位取代的联芳基来说明。机理研究提供了对催化剂的深入了解 s 作用模式并显示在钯催化的简单芳烃的直接芳基化中存在动力学上显着的 CH 键裂解。从这些研究中获得的知识导致了以前无法获得的芳烃的新分子间芳基化反应的发展，为其他新的直接芳基化过程的发展打开了大门。
• Steric Effect of Carboxylate Ligands on Pd-Catalyzed Intramolecular C(sp² )-H and C(sp³ )-H Arylation Reactions
  作者：Yutaka Tanji、Naoya Mitsutake、Tetsuaki Fujihara、Yasushi Tsuji

  DOI：10.1002/anie.201804566

  日期：2018.8.6

  carboxylic acid bearing three cyclohexylmethyl substituents at the α‐position, namely, tri(cyclohexylmethyl)acetic acid, is demonstrated to act as an efficient ligand source in Pd‐catalyzed intramolecular C(sp2)−H and C(sp3)−H arylation reactions. The reactions proceed smoothly under mild reaction conditions, even at room temperature due to the steric bulk of the carboxylate ligands, which accelerates the

  在α-位置带有三个环己基甲基取代基的大分子羧酸，即三（环己基甲基）乙酸被证明是Pd催化的分子内C（sp 2）-H和C（sp 3）的有效配体来源-H芳基化反应。由于羧酸盐配体的空间体积较大，即使在室温下，反应也可在温和的反应条件下顺利进行，这加快了催化循环中确定C H键活化步骤的速度。
• Direct Arylation Reactions Catalyzed by Pd(OH)₂/C:  Evidence for a Soluble Palladium Catalyst
  作者：Mathieu Parisien、Damien Valette、Keith Fagnou

  DOI：10.1021/jo051039v

  日期：2005.9.1

  Palladium hydroxide on carbon (Pearlman's catalyst) effectively catalyzes direct arylation reactions of aryl iodides and bromides, providing excellent arylation-to-hydrodehalogenation ratios (> 30:1) with broad scope for both intra- and intermolecular arylation processes. Studies aimed at determining the nature of the active catalyst indicate that an active homogeneous palladium species is produced under the reaction conditions.
• 1,4,5-Trisubstituted Imidazole-Based p53–MDM2/MDMX Antagonists with Aliphatic Linkers for Conjugation with Biological Carriers
  作者：Aleksandra Twarda-Clapa、Sylwia Krzanik、Katarzyna Kubica、Katarzyna Guzik、Beata Labuzek、Constantinos G. Neochoritis、Kareem Khoury、Kaja Kowalska、Miroslawa Czub、Grzegorz Dubin、Alexander Dömling、Lukasz Skalniak、Tad A. Holak

  DOI：10.1021/acs.jmedchem.7b00104

  日期：2017.5.25

  The tumor suppressor protein p53, the "guardian of the genome", is inactivated in nearly all cancer types by mutations in the TPS3 gene or by overexpression of its negative regulators, oncoproteins MDM2/MDMX. Recovery of p53 function by disrupting the p53-MDM2/MDMX interaction using small-molecule antagonists could provide an efficient nongenotoxic anticancer therapy. Here we present the syntheses, activities, and crystal structures of the p53-MDM2/MDMX inhibitors based on the 1,4,5-trisubstituted imidazole scaffold which are appended with aliphatic linkers that enable coupling to bioactive carriers. The compounds have favorable properties at both biochemical and cellular levels. The most effective compound 19 is a tight binder of MDM2 and activates p53 in cancer cells that express the wild-type p53, leading to cell cycle arrest and growth inhibition. Crystal structures reveal that compound 19 induces MDM2 dimerization via the aliphatic linker. This unique dimerization-binding mode opens new prospects for the optimization of the p53-MDM2/MDMX inhibitors and conjugation with bioactive carriers.
• Intramolecular 9-membered hydrogen bonding of 2-arylmethylphenols having carbonyl groups at 2′-position
  作者：Yasuharu Yoshimi、Hajime Maeda、Minoru Hatanaka、Kazuhiko Mizuno

  DOI：10.1016/j.tet.2004.08.007

  日期：2004.10

  Thermodynamic parameters of nine-membered intramolecular hydrogen bonding between carbonyl groups and phenolic hydroxyl groups of 2-arylmethylphenols having methoxycarbonyl, dimethylcarbamoyl, and formyl groups were determined by variable temperature 1H NMR studies and van't Hoff analysis. The enthalpy of the hydrogen bonding was related to the electron-withdrawing ability of the substituents on the

  通过可变温度1 H NMR研究和van't Hoff分析，确定了具有甲氧基羰基，二甲基氨基甲酰基和甲酰基的2-芳基甲基苯酚的羰基和酚羟基之间的九元分子内氢键的热力学参数。氢键的焓与苯酚上的取代基的吸电子能力和羰基的碱性有关。氢键的熵损失取决于酚基团的旋转自由度。