2-丁基苯甲酸乙酯 | 94977-15-8

• 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-丁基苯甲酸乙酯
• 英文名称: ethyl 2-butylbenzoate
• CAS: 94977-15-8
• 化学式: C₁₃H₁₈O₂
• 分子量: 206.285
• InChiKey: QNBXGMTTYWYIHE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  正丁基锂 、 2-碘苯甲酸乙酯, 在 双(乙腈)氯化钯(II) zinc(II) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 以93%的产率得到2-丁基苯甲酸乙酯
  参考文献：
  名称：

  Superior Effect of a π-Acceptor Ligand (Phosphine−Electron-Deficient Olefin Ligand) in the Negishi Coupling Involving Alkylzinc Reagents

  摘要：

  [GRAPHICS]Palladium-catalyzed Negishi cross-coupling involving primary and secondary alkyls, even in the presence of beta-H, can be achieved at ambient temperature using chelating ligands containing a phospline and an electron-deficient olefin. The superior effects of the ligands were shown not only in the desired cross-coupling product yields but also in the fast reaction at mild conditions. This reaction has been also scaled up to 50 g in 0.005 mol % catalyst (20,000 TONs) at room temperature.

  DOI：

  10.1021/ol701995t

文献信息

• Gram-Scale, Cheap, and Eco-Friendly Iron-Catalyzed Cross-Coupling between Alkyl Grignard Reagents and Alkenyl or Aryl Halides
  作者：Gérard Cahiez、Guillaume Lefèvre、Alban Moyeux、Olivier Guerret、Eric Gayon、Loïc Guillonneau、Nicolas Lefèvre、Qinzhuo Gu、Edouard Zhou

  DOI：10.1021/acs.orglett.9b00665

  日期：2019.4.19

  A new robust methodology for gram-scale iron-catalyzed cross-coupling between alkyl Grignard reagents and alkenyl or aryl halides is developed. This method does not require toxic additives such as NMP or expensive ligands. Its efficiency relies on the use of simple alkoxide magnesium salts as additives. On the basis of these results, a new procedure for one-pot synthesis of substituted benzamides from

  开发了一种新的鲁棒性方法，用于克氏量级烷基格氏试剂与烯基或芳基卤化物之间的克级铁催化交叉偶联。该方法不需要有毒的添加剂，例如NMP或昂贵的配体。其效率取决于使用简单的醇盐镁盐作为添加剂。基于这些结果，还提出了一种新的程序，用于从氯酸酯一锅法合成取代的苯甲酰胺。
• An Electron-Deficient Diene as Ligand for Palladium-Catalyzed Cross-Coupling Reactions: An Efficient Alkylation of Aryl Iodides by Primary and Secondary Alkylzinc Reagents
  作者：Qiang Liu、Hui Duan、Xiancai Luo、Yang Tang、Gang Li、Rong Huang、Aiwen Lei

  DOI：10.1002/adsc.200800118

  日期：2008.6.9

  An electron-deficient diene, L1, was found to be an effective ligand in facilitating palladium-catalyzed Negishi couplings involving primary and secondary alkylzinc reagents. The reactions took place readily at 60 °C in THF with 5 mol% of a catalyst generated in situ from bis(acetonitrile)palladium dichloride [PdCl2(MeCN)2] and L1, and functional groups such as chloro, bromo, etc. attached to phenyl

  发现缺电子的二烯L 1是促进钯催化的涉及伯烷基锌试剂和仲烷基锌试剂的Negishi偶联的有效配体。反应在60°C的THF中与5 mol％的由双（乙腈）二氯化钯[PdCl 2（MeCN）2 ]和L 1原位生成的催化剂轻松进行，并且对与苯环相连的氯，溴等官能团以及与反应位点相邻的β-H原子具有良好的耐受性。当单独使用异丙基氯化锌作为亲核试剂时，在我们的系统中也观察到了文献报道的反应中涉及的仲烷基锌试剂中存在问题的异构化。然而，当在L 1存在下使用i- Pr 2 Zn时，异构化被显着抑制。
• Pincer Thioamide and Pincer Thioimide Palladium Complexes Catalyze Highly Efficient Negishi Coupling of Primary and Secondary Alkyl Zinc Reagents at Room Temperature
  作者：Haibo Wang、Jing Liu、Yi Deng、Tianyin Min、Ganxiang Yu、Xiaojun Wu、Zhen Yang、Aiwen Lei

  DOI：10.1002/chem.200801860

  日期：2009.1.26

  structures of complexes 2 and 3 were confirmed by X‐ray analysis. Both complexes are efficient catalysts for Negishi couplings involving primary and secondary alkyl zinc reagents bearing β‐hydrogen atoms. At a concentration of 0.1–0.5 mol % both catalysts readily promoted reactions at room temperature or even at 0 °C. The operational simplicity of these processes, in conjunction with the easy accessibility

  制备了钳形硫代酰胺Pd II配合物2，其与氯化环己基锌反应生成了除Pd 0种类外的新型钳形硫代酰亚胺Pd II配合物3。配合物2和3的结构X射线分析证实。两种络合物都是Negishi偶联的有效催化剂，涉及带有β-氢原子的伯烷基锌试剂和仲烷基锌试剂。在0.1-0.5 mol％的浓度下，两种催化剂在室温甚至0°C时都容易促进反应。这些方法的操作简便性，以及催化剂和底物的易于接近性，保证了这种新方法的综合实用性。在极低的催化剂负载量2（周转数：6 100 000）下进行的19.35 g规模的实验强调了该催化体系的潜在应用。单烷基和二烷基锌试剂在与配合物2或2催化的芳基碘化物的反应中显示出不同的反应性和选择性。如图3所示，通过使用适量的二烷基锌试剂，抑制了涉及无环仲烷基锌衍生物的反应中的异构化。基于初步的动力学特征和反应证据，为涉及无环仲烷基锌试剂的反应提出了三种可能的途径，以合理化单烷基锌衍生物和二烷基锌衍生物之间的差异。
• Understanding the Use of Phosphine-(EWO) Ligands in Negishi Cross-Coupling: Experimental and Density Functional Theory Mechanistic Study
  作者：Estefanía Gioria、Juan del Pozo、Agustí Lledós、Pablo Espinet

  DOI：10.1021/acs.organomet.1c00001

  日期：2021.7.26

  2-(trans-CH═CHCOPh)–C6F4 (PhPEWO-F) and other PEWO ligands are well-known promoters of C–C reductive eliminations and very effective in Negishi couplings. As an example, the efficient Negishi coupling of (C6F5)–I and Zn(C6F5)2 is reported. The thorough experimental study of the steps involved in the catalytic cycle uncovers the potential weakness of this ligand that could frustrate at some points the desired

  易于制备的半稳定性配体 1-(PPh 2 ),2-( trans -CH=CHCOPh)–C 6 F 4 (PhPEWO-F) 和其他 PEWO 配体是众所周知的 C–C 还原消除促进剂，并且非常有效根岸联轴器。例如，(C 6 F 5 )–I 和 Zn(C 6 F 5 ) 2的有效 Negishi 耦合被报道。对催化循环中涉及的步骤的彻底实验研究揭示了这种配体的潜在弱点，它可能会在某些时候阻碍所需的循环，并提供一些简单的预防措施来保持催化循环有效工作。密度泛函理论 (DFT) 计算完成了实验研究，并提供了对不可观察的过渡态和中间体的洞察，比较了还原消除和烯烃插入之间的潜在冲突。我们的结果展示了由吸电子配体的强反式效应促进的金属转移步骤的重要性，以及有机锌亲核试剂的选择，这对于确保快速基团交换和催化反应的积极结果至关重要。
• Titanium halide containing catalyst
  申请人：STAUFFER CHEMICAL COMPANY

  公开号：EP0044445A2

  公开（公告）日：1982-01-27

  A novel catalyst system for the polymerization of alpha-olefins is provided. The catalyst system comprises: (a) an organoaluminum containing component, e.g. triethyl aluminum, and (b) a titanium halide containing component. The titanium halide containing component is obtained by reacting a halogen containing magnesium compound, e.g. MgCl2, with an organic phosphite, e.g. triphenyl phosphite, to produce a reaction product. The reaction product is then co-pulverized with a complex of a titanium halide compound and an electron donor compound, e.g. TiCl4 ethyl benzoate, to produce a co-pulverized product. The co-pulverized product is then reacted with a titanium halide compound, e.g. TiCI4. A novel titanium halide containing component is provided as well as a process for producing said component. A process for the polymerization of alpha-olefins is also provided.

  提供了一种用于α-烯烃聚合的新型催化剂体系。该催化剂系统包括 (a) 含有机铝成分，例如三乙基铝，以及 (b) 一种含卤化钛的组分。 卤化钛成分是通过含卤素的镁化合物（如 MgCl2）与有机亚磷酸酯（如亚磷酸三苯酯）反应生成反应产物而得到的。然后将反应产物与卤化钛化合物和电子供体化合物（如 TiCl4 苯甲酸乙酯）的络合物进行共粉碎，生成共粉碎产物。然后再将共粉碎产物与卤化钛化合物（如 TiCI4）反应。 本发明提供了一种新型含卤化钛成分以及生产该成分的工艺。此外，还提供了一种α-烯烃聚合工艺。