2-(2-bromo-4-methylphenyl)pyridine | 1252207-52-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 2-(2-bromo-4-methylphenyl)pyridine
• CAS: 1252207-52-5
• 化学式: C₁₂H₁₀BrN
• 分子量: 248.122
• InChiKey: HRKRBZQNHODKQV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-(2-bromo-4-methylphenyl)pyridine 、 3-cyclopentylpropiolaldehyde 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 1.5h， 以76%的产率得到3-cyclopentyl-1-(5-methyl-2-(pyridin-2-yl)phenyl)prop-2-yn-1-ol
  参考文献：
  名称：

  碳中间体合成喹啉鎓类杂芳烃

  摘要：

  通过Pt（II）催化2-芳基吡啶炔丙醇的环化反应，可以有效合成喹啉鎓型杂芳族化合物。质子酸的存在对于反应成功至关重要。机理研究表明，反应是通过铂-卡宾中间体进行的。另外，对合成的杂芳族化合物的荧光性质进行了研究，以提供潜在的应用前景。

  DOI：

  10.1021/acs.orglett.7b03964
• 作为产物：
  描述：

  [PdCl(MeC₆H₃C₅H₄N)(1-hydroxy-1,1'-bis(2-pyridyl)methoxide)]Br 在 重水 作用下， 反应 24.0h， 以90%的产率得到2-(2-bromo-4-methylphenyl)pyridine
  参考文献：
  名称：

  Preparation and C−X Reductive Elimination Reactivity of Monoaryl Pd^IV−X Complexes in Water (X = OH, OH₂, Cl, Br)

  摘要：

  Monohydrocarbyl palladium(IV) complexes bearing OH, OH2, Br, and Cl ligands at the metal and supported by facially chelating 1-hydroxy-1,1-bis(2-pyridyl)methoxide were readily prepared in water at 0 degrees C. These complexes reductively eliminate Ar-X (X = OH, Br, Cl) in water at room temperature in high yield, and the corresponding first-order rate constants k(OH), k(Cl), and k(Br) are on the same order of magnitude.

  DOI：

  10.1021/ja107185w

文献信息

• Efficient <scp>Pd‐Catalyzed</scp> C—H Oxidative Bromination of Arenes with Dimethyl Sulfoxide and Hydrobromic Acid ^†
  作者：Yizhi Yuan、Yujie Liang、Shihui Shi、Yu‐Feng Liang、Ning Jiao

  DOI：10.1002/cjoc.202000055

  日期：2020.11

  We have developed an efficient Pd‐catalyzed directed C—H bromination protocol, in which dimethyl sulfoxide (DMSO) is employed as oxidant with hydrobromic acid aqueous solution (HBr(aq)) as bromide source. The DMSO/HBr(aq) system, which is novelly and efficiently utilized in transition‐metal catalyzed C—H activation, illustrates its practicability by the operational simplicity, inexpensive and readily

  我们已经开发了一种有效的Pd催化的定向C-H溴化方案，其中使用二甲基亚砜（DMSO）作为氧化剂，氢溴酸水溶液（HBr （aq））作为溴化物源。DMSO / HBr （aq）系统在过渡金属催化的CH活化中得到了新颖而有效的利用，其操作简便，价格低廉且易于获得的起始原料以及高溴原子经济性说明了其实用性。
• Cu-Mediated Direct Aryl CH Halogenation: a Strategy to Control Mono- and Di-Selectivity
  作者：Zhi-Jun Du、Lian-Xun Gao、Ying-Jie Lin、Fu-She Han

  DOI：10.1002/cctc.201300734

  日期：2014.1

  A protocol for the copper‐mediated direct aryl CH halogenation is presented. Highly selective mono‐ and di‐halogenations are achieved by using acyl hypohalites, generated in situ from the readily available carboxylic acid and N‐halosuccinimides (NXS; X=Br and Cl) as powerful halogenating reagents. The correct choice of carboxylic acid additives and solvents is essential for both high yield and selectivity

  提出了铜介导的直接芳基CH卤化的方案。通过使用酰基次卤酸盐来实现高度选择性的单卤化和二卤化，酰基次卤酸盐是由现成的羧酸和N-卤代琥珀酰亚胺（NXS； X = Br和Cl）原位生成的，作为强力卤化试剂。正确选择羧酸添加剂和溶剂对于高收率和选择性都至关重要。因此，使用廉价的铜催化剂和从容易负担得起且易于处理的羧酸和NXS（X = Br和Cl）原位生成酰基次卤酸盐卤化试剂的新策略为实际应用提供了优势。
• Salen-based hypercrosslinked polymer-supported Pd as an efficient and recyclable catalyst for C–H halogenation
  作者：Di Meng、Jiajun Bi、Yahao Dong、Bo Hao、Kaiwei Qin、Tao Li、Dajian Zhu

  DOI：10.1039/c9cc09781c

  日期：——

  In this work, we report the first use of a salen-based hypercrosslinked polymer-supported Pd catalyst to carry out C-H halogenation. This catalyst can effectively catalyze C-H bromination and chlorination even better than its homogeneous counterpart Pd(OAc)2. It also showed excellent reusability without loss of catalytic activity for ten cycles. A broad substrate scope was explored and moderate to

  在这项工作中，我们报告了首次使用一种基于Salen的超交联聚合物负载的Pd催化剂进行CH卤化。该催化剂比其均相对应的Pd（OAc）2可以更好地催化CH的溴化和氯化反应。在十个循环中它也显示出极好的可重复使用性，而没有失去催化活性。探索了广泛的底物范围，并获得了中等至优异的产量。
• Functionalizations of Aryl CH Bonds in 2-Arylpyridines via Sequential Borylation and Copper Catalysis
  作者：Liting Niu、Haijun Yang、Daoshan Yang、Hua Fu

  DOI：10.1002/adsc.201100930

  日期：2012.8.13

  sequential borylation and aerobic oxidative copper catalysis, and the corresponding aryl halides, sulfones, azides and arylamines were obtained in good yields. The protocol uses cheap and readily available boron tribromide (BBr3) as the borylating reagent, and inorganic salts (potassium iodide, ammonium bromide, sodium alkylsulfinates, sodium azide) as the functional group sources. This method makes

  通过顺序硼化和需氧氧化铜催化，已开发了2-芳基吡啶中芳基CH键的选择性官能化，并以良好的收率获得了相应的芳基卤化物，砜，叠氮化物和芳基胺。该协议使用便宜且容易获得的三溴化硼（BBr 3）作为硼化试剂，并使用无机盐（碘化钾，溴化铵，烷基亚磺酸钠，叠氮化钠）作为官能团来源。该方法使芳基CH键的官能化变得容易。
• Boron‐Mediated Regioselective Aromatic C−H Functionalization via an Aryl BF ₂ Complex
  作者：Ganesh H. Shinde、Henrik Sundén

  DOI：10.1002/chem.202203505

  日期：2023.2.16

  Regioselective functionalization of 2-aryl-azaarenes N-heteroarenes and aryl aldehydes has been achieved. The reaction proceeds via a BBr3 promoted 5 and 6-membered boracycle that undergoes a ligand exchange promoted by Selectfluor to give a previously scarce aryl BF2 species. The aryl BF2 is a bench stable intermediate that can be used for the deborylative functionalization of the 2-aryl-azaarenes

  已经实现了2-芳基氮杂芳烃N-杂芳烃和芳基醛的区域选择性功能化。该反应通过 BBr 3促进的 5 元和 6 元硼环进行，该环经过 Selectfluor 促进的配体交换，得到以前稀缺的芳基 BF 2物质。芳基 BF 2是一种稳定的中间体，可用于 2-芳基-氮杂芳烃支架的脱硼功能化。