1,3-二(溴甲基)-2-氯苯 | 25006-87-5

• 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: 1,3-二(溴甲基)-2-氯苯
• 中文别名: 1-哌啶羧酸,3-乙基-2-甲基-,1,1-二甲基乙基酯,(2R,3R)-
• 英文名称: 1,3-bis(bromomethyl)-2-chlorobenzene
• 英文别名: 2-Chlor-1.3-dibrommethyl-benzol
• CAS: 25006-87-5
• 化学式: C₈H₇Br₂Cl
• 分子量: 298.405
• InChiKey: YHSHGVABTKZEKC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1,3-二(溴甲基)-2-氯苯 在 四(乙腈)三氟甲磺酸铜(I) 、 氢溴酸 、 caesium carbonate 、 溶剂黄146 、 sodium iodide 、 苯酚 作用下， 以 氘代丙酮 、 乙腈 为溶剂， 反应 96.0h， 生成 17-Iodo-7-methyl-3,7,11-triazabicyclo[11.3.1]heptadeca-1(17),13,15-triene
  参考文献：
  名称：

  Nucleophilic Aryl Fluorination and Aryl Halide Exchange Mediated by a Cu^I/Cu^III Catalytic Cycle

  摘要：

  Copper-catalyzed halide exchange reactions under very mild reaction conditions are described for the first time using a family of model aryl halide substrates. All combinations of halide exchange (I, Br, Cl, F) are observed using catalytic amounts of Cu-I. Strikingly, quantitative fluorination of aryl X substrates is also achieved catalytically at room temperature, using common F- sources, via the intermediacy of aryl-Cu-III-X species. Experimental and computational data support a redox Cu-I/Cu-III catalytic cycle involving aryl X oxidative addition at the Cu-I center, followed by halide exchange and reductive elimination steps. Additionally, defluorination of the aryl-F model system can be also achieved with Cu-I at room temperature operating under a Cu-I/Cu-III redox pair.

  DOI：

  10.1021/ja2058567
• 作为产物：
  描述：

  2,6-二甲基苯胺 在 N-溴代丁二酰亚胺(NBS) 、 过氧化苯甲酰 作用下， 生成 1,3-二(溴甲基)-2-氯苯
  参考文献：
  名称：

  Host-guest complexation. 5. Convergent functional groups in macrocyclic polyethers

  摘要：

  DOI：

  10.1021/ja00461a037

文献信息

• Fine-tuning dirhodium compounds with bridging ligands: Synthesis, structure, catalytic efficiency
  作者：Yangbo Ning、Jiantao Tan、Zhifan Wang、Yuanhua Wang

  DOI：10.1016/j.jorganchem.2021.122078

  日期：2021.12

  out a study on the effect of fine-tuning of the bridging ligand on the dirhodium compound. Several dirhodium compounds were designed and synthesized. During this process, we have successfully found Rh2(5-Br-esp)2 and Rh2(5-tBu-esp)2, which are closer to the ideal geometric configuration of the dirhodium(II) compounds. Rh2(5-Br-esp)2 has been applied in the oxidation of propargyl position and Rh2(5-tBu-esp)2

  铑化合物的结构包含一个独特的Rh-Rh键、两个轴向配体和四个桥连配体。在二铑(II)化合物中，在催化过程中桥接配体的配位原子很容易发生迁移，从而导致催化剂的降解。在桥连配体中发现了配位原子迁移。为了提高催化剂的稳定性，我们对桥接配体的微调对二铑化合物的影响进行了研究。设计并合成了几种铑化合物。在这个过程中，我们成功地发现了Rh 2 (5-Br-esp) 2和Rh 2 (5 - t Bu-esp) 2，这更接近于 dirhodium(II) 化合物的理想几何构型。Rh 2 (5-Br-esp) 2已应用于炔丙基位置的氧化，Rh 2 (5 - t Bu-esp) 2已应用于C-N键的形成反应。
• [EN] SYMMETRIC OR SEMI-SYMMETRIC COMPOUNDS USEFUL AS IMMUNOMODULATORS<br/>[FR] COMPOSÉS SYMÉTRIQUES OU SEMI-SYMÉTRIQUES UTILES COMME IMMUNOMODULATEURS
  申请人：ARISING INT LLC

  公开号：WO2018026971A1

  公开（公告）日：2018-02-08

  A compound having Formula I:(I), or a pharmaceutical acceptable salt thereof. A is a bivalent arene or a bivalent heteroarene; Ring B and Ring B' are independently a 6-membered aromatic hydrocarbon ring, a 6-membered heterocyclic ring, a 8- to 10-membered aromatic hydrocarbon ring, or a 8- to 10-membered heterocyclic ring; Y and Y' are independently, null (direct bond), -CHR1-, -CH2-CH2-, -NR1-, -0-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -SOCH2-, -CH2SO-, or -SO2CH2-, and R1 is H, C1-6 alkyl, or C3-6 cycloalkyl.

  具有Formula I:(I)的化合物，或其药用可接受的盐。A是二价芳烃或二价杂芳烃；环B和环B'分别是6-成员芳香碳氢环，6-成员杂环，8-到10-成员芳香碳氢环，或8-到10-成员杂环；Y和Y'分别是null（直接键），-CHR1-，-CH2-CH2-，-NR1-，-0-，-OCH2-，-CH2O-，-SCH2-，-CH2S-，-SOCH2-，-CH2SO-，或-SO2CH2-，而R1是H，C1-6烷基或C3-6环烷基。
• C–C Bond Elimination from High-Valent Mn Aryl Complexes
  作者：Yu-Tao He、Ayumu Karimata、Olga Gladkovskaya、Eugene Khaskin、Robert R. Fayzullin、Abir Sarbajna、Julia R. Khusnutdinova

  DOI：10.1021/acs.organomet.1c00047

  日期：2021.7.26

  alternative to commonly used precious metal catalysts in C–C bond coupling reactions. Although high-valent Mn aryl intermediates have been proposed in such reactions, a mechanistic understanding of possible organometallic intermediates in Mn-mediated C–C coupling is still lacking due to their high reactivity. We report the synthesis of stable, isolable Mn(III) aryl complexes obtained by oxidative addition of

  锰配合物被认为是 C-C 键偶联反应中常用贵金属催化剂的廉价且易于获得的替代品。尽管已经在此类反应中提出了高价锰芳基中间体，但由于其高反应性，仍然缺乏对锰介导的 C-C 偶联中可能的有机金属中间体的机理理解。我们报告了通过芳基溴或芳基氯的氧化加成获得的稳定、可分离的 Mn(III) 芳基配合物的合成。这些配合物与一系列有机金属烷基化或芳基化试剂（烷基和芳基格氏试剂、MeLi、ZnMe 2）反应，发生 C(sp 2 )–C(sp 3 ) 或 C(sp 2 )–C(sp 2) 键偶联，并且可以证明初步的催化系统。C(sp 2 )–C(sp 3 ) 偶联产物的反应范围和产率可以通过添加 TEMPO 作为氧化剂进一步增加，产生烷基自由基。
• Activation of Aryl Halides at Gold(I): Practical Synthesis of (P,C) Cyclometalated Gold(III) Complexes
  作者：Johannes Guenther、Sonia Mallet-Ladeira、Laura Estevez、Karinne Miqueu、Abderrahmane Amgoune、Didier Bourissou

  DOI：10.1021/ja412432k

  日期：2014.2.5

  phosphine chelation, direct evidence for oxidative addition of Csp(2)-X bonds (X = I, Br) to a single gold atom is reported. NMR studies and DFT calculations provide insight into this unprecedented transformation, which gives straightforward access to stable (P,C) cyclometalated gold(III) complexes.

  利用膦螯合，报道了 Csp(2)-X 键 (X = I, Br) 氧化加成到单个金原子上的直接证据。NMR 研究和 DFT 计算提供了对这种前所未有的转化的深入了解，从而可以直接获得稳定的 (P,C) 环金属化金 (III) 配合物。
• Locking the Conformation of a Paddlewheel Rhodium Complex: Design, Synthesis, and Applications in Catalytic Nitrene Transfers
  作者：Xinxin Tang、Hidetoshi Noda、Masakatsu Shibasaki

  DOI：10.1002/anie.202311027

  日期：2023.12.18

  modification of Rh2(esp)2 is presented. The introduction of a subtle substituent can freeze the conformational dynamics of the parent catalyst, allowing for the isolation of two conformationally distinct complexes. The utility of the conformational fixation in the development of stereoselective catalysts has been demonstrated in three model cases.

  提出了Rh 2 (esp) 2修饰的新设计原理。引入微妙的取代基可以冻结母体催化剂的构象动力学，从而允许分离两种构象不同的复合物。构象固定在立体选择性催化剂开发中的实用性已在三个模型案例中得到证明。