methyl 4-bromobenzimidate | 26040-83-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl 4-bromobenzimidate
• 英文别名: Methyl p-bromobenziminate；methyl 4-bromobenzenecarboximidate
• CAS: 26040-83-5
• 化学式: C₈H₈BrNO
• 分子量: 214.062
• InChiKey: HLEWKZFDAZECQR-UHFFFAOYSA-N

物化性质

• 熔点：
  64-65 °C(Solv: hexane (110-54-3))
• 沸点：
  223.1±42.0 °C(Predicted)
• 密度：
  1.44±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  33.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl 4-bromobenzimidate 在 五氯化磷 作用下， 以 苯 为溶剂， 生成 4-bromo-benzoic acid-(trichlorophosphoranyliden-amide)
  参考文献：
  名称：

  Derkach,G.I. et al., Journal of general chemistry of the USSR, 1962, vol. 32, p. 155 - 156

  摘要：

  DOI：
• 作为产物：
  描述：

  4-溴基苄基甲醚 在 ([2,5-Me2-3,4-Ph2(η5-C4CNHPh)]Ru(CO)(μ-CO))2 、 碘苯二乙酸 、 叠氮基三甲基硅烷 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 9.33h， 生成 methyl 4-bromobenzimidate
  参考文献：
  名称：

  C–H Activation Guided by Aromatic N–H Ketimines: Synthesis of Functionalized Isoquinolines Using Benzyl Azides and Alkynes

  摘要：

  Aromatic N-H ketimines were in situ generated from various benzylic azides by ruthenium catalysis for the subsequent Rh-catalyzed annulation reaction with alkynes to give the corresponding isoquinolines. In contrast to conventional synthetic methods for aromatic NH ketimines, our protocol works under mild and neutral conditions, which enabled the synthesis of isoquinolines having various functionalities such as carbonyl, ester, alkenyl, and ether groups. In addition, the imidates generated from alpha-azido ethers were successfully used for the synthesis of 1-alkoxyisoquinolines.

  DOI：

  10.1021/jo501465q

文献信息

• Electrochemical Access to Aza‐Polycyclic Aromatic Hydrocarbons: Rhoda‐Electrocatalyzed Domino Alkyne Annulations
  作者：Wei‐Jun Kong、Zhigao Shen、Lars H. Finger、Lutz Ackermann

  DOI：10.1002/anie.201914775

  日期：2020.3.27

  Nitrogen-doped polycyclic aromatic hydrocarbons (aza-PAHs) have found broad applications in material sciences. Herein, a modular electrochemical synthesis of aza-PAHs was developed via a rhodium-catalyzed cascade C-H activation and alkyne annulation. A multifunctional O-methylamidoxime enabled the high chemo- and regioselectivity. The isolation of two key rhodacyclic intermediates made it possible

  氮掺杂多环芳烃（氮杂-PAHs）已在材料科学中得到广泛应用。本文中，通过铑催化的级联CH活化和炔烃环化反应开发了氮杂-PAHs的模块化电化学合成方法。多功能的O-甲基ami胺肟具有很高的化学和区域选择性。两个关键的rhodocyclic中间体的分离使得有可能描绘出三个CH活化步骤的确切顺序。此外，金属电催化的多CH转化具有独特的官能团耐受性，包括高反应性的碘基和叠氮基。
• Quinazoline Synthesis via Rh(III)-Catalyzed Intermolecular C–H Functionalization of Benzimidates with Dioxazolones
  作者：Jie Wang、Shanke Zha、Kehao Chen、Feifei Zhang、Chao Song、Jin Zhu

  DOI：10.1021/acs.orglett.6b00691

  日期：2016.5.6

  An efficient double C–N bond formation sequence to prepare highly substituted quinazolines utilizing benzimidates and dioxazolones under the catalytic redox-neutral [Cp*RhCl2]2/AgBF4 system, where dioxazolones could work as an internal oxidant to maintain the catalytic cycle, is reported. N-Unsubstituted imine not only acts as a directing group but also functions as a nucleophile in postcoupling cyclization

  在催化氧化还原中性[Cp * RhCl 2 ] 2 / AgBF 4体系下，利用苯甲二酸盐和二恶唑酮制备高效取代的C–N键形成顺序的方法，其中二恶唑酮可作为内部氧化剂来维持催化循环，被报道。N-未取代的亚胺在后偶联环化中不仅充当引导基团，而且还充当亲核试剂，并且二恶唑酮充当访问杂环的偶联伴侣。
• An Inverse Electron Demand Azo-Diels–Alder Reaction of <i>o</i>-Quinone Methides and Imino Ethers: Synthesis of Benzocondensed 1,3-Oxazines
  作者：Dmitry V. Osipov、Vitaly A. Osyanin、Guzel’ D. Khaysanova、Elvira R. Masterova、Pavel E. Krasnikov、Yuri N. Klimochkin

  DOI：10.1021/acs.joc.8b00692

  日期：2018.4.20

  the reactions of o-quinone methide precursors with imino ethers. The reaction provides a versatile route to substituted 1,3-benzoxazines. The proposed reaction mechanism involves the generation of the o-quinone methide intermediates, imino-Diels–Alder reaction, and elimination. This cascade process is a rare example of the participation of imino ethers as dienophiles.

  我们已经研究了邻醌甲基化物前体与亚氨基醚的反应。该反应提供了取代的1，3-苯并恶嗪的通用途径。拟议的反应机制涉及邻醌甲基化物中间体的产生，亚氨基-狄尔斯-阿尔德反应和消除。这种级联过程是亚氨基醚作为亲双烯体参与的罕见例子。
• Mechanism of generation of <i>closo</i>-decaborato amidrazones. Intramolecular non-covalent B–H⋯π(Ph) interaction determines stabilization of the configuration around the amidrazone CN bond
  作者：Valeria K. Burianova、Dmitrii S. Bolotin、Alexander S. Mikherdov、Alexander S. Novikov、Pennie Petrus Mokolokolo、Andreas Roodt、Vadim P. Boyarskiy、Dmitry Dar’in、Mikhail Krasavin、Vitalii V. Suslonov、Andrey P. Zhdanov、Konstantin Yu. Zhizhin、Nikolay T. Kuznetsov

  DOI：10.1039/c8nj01018h

  日期：——

  consecutive incorporation of two Nu(H) nucleophiles, with the second responsible for a subsequent rapid proton exchange. The second possible mechanism assumes a pre-formation of a dinuclear [Nu(H)]2 species which subsequently proceeds with the nucleophilic attack on the boron cluster. The activation parameters for hydrazones indicate a small dependence on bond formation [ΔH‡ = 6.8–15 kJ mol−1], but significantly

  三种类型的N（H）-亲核试剂，即。肼，乙酰肼，和一组腙的，被用来研究的亲核加成到C N组的2 propanenitrilium的闭合碳-decaborate簇（PH 3 PCH 2 PH）[B 10 ħ 9 NCET]，得到N-克洛索-decaborato amidrazones。提供了亲核加成的系统机理研究，包括详细的合成，晶体学，计算和动力学工作。结果，已经提出了两种可能的机制，其包括：首先连续掺入两个Nu（H）亲核体，其次是随后的快速质子交换。第二种可能的机制假定是双核[Nu（H）] 2的预先形成，然后继续对硼簇进行亲核攻击。的活化参数表明对键形成的依赖性较小[ ΔH ‡ = 6.8–15 kJ mol -1 ]，但活化的负熵显着[ ΔS ‡范围从-139到-164 JK -1 mol -1 ]，后者贡献了激活的总吉布斯自由能ΔG ‡的70-80％。在（Z）-（Ph 3 PCH 2 Ph）[B
• Synthesis of isoquinolines via Rh-catalyzed C–H activation/C–N cyclization with diazodiesters or diazoketoesters as a C₂ source
  作者：Jie Wang、Shanke Zha、Kehao Chen、Feifei Zhang、Jin Zhu

  DOI：10.1039/c6ob00901h

  日期：——

  Synthesis of isoquinolines based on efficient C–C and C–N bond formation through Rh(III)-catalyzed C–H activation and subsequent intramolecular cyclization is reported. Diazodiesters serving as a C2 source in the newly formed heterocycles are first demonstrated. Additionally, the Rh(III)-catalyzed direct C–H activation/cyclization of benzimidates with diazoketoesters is also described.

  据报道，通过Rh（III）催化的C–H活化和随后的分子内环化作用，基于有效的C–C和C–N键的形成，合成了异喹啉。首先证明了在新形成的杂环中用作C 2源的重氮二酯。此外，还描述了Rh（III）催化的重氮苄酯与重氮酮酸酯的直接CH活化/环化。