2-(2,2-二溴-乙烯基)-6-甲氧基-苯基胺 | 880154-19-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 中文名称: 2-(2,2-二溴-乙烯基)-6-甲氧基-苯基胺
• 英文名称: 2-(2,2-dibromo-vinyl)-6-methoxy-phenylamine
• 英文别名: 6-methoxy-2-gem-dibromovinylaniline；2-(2,2-Dibromoethenyl)-6-methoxyaniline
• CAS: 880154-19-8
• 化学式: C₉H₉Br₂NO
• 分子量: 306.985
• InChiKey: RSZPUCMVUGWQKW-UHFFFAOYSA-N

物化性质

• 沸点：
  356.4±42.0 °C(Predicted)
• 密度：
  1.845±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  35.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(2,2-二溴-乙烯基)-6-甲氧基-苯基胺 在 palladium diacetate 、 potassium carbonate 、 tri tert-butylphosphoniumtetrafluoroborate 作用下， 以 甲苯 为溶剂， 反应 14.08h， 以80%的产率得到2-bromo-7-methoxy-1H-indole
  参考文献：
  名称：

  The Role of Reversible Oxidative Addition in Selective Palladium(0)-Catalyzed Intramolecular Cross-Couplings of Polyhalogenated Substrates: Synthesis of Brominated Indoles

  摘要：

  A Pd(0)-catalyzed C-N bond-forming reaction leading to the synthesis of brominated indoles is described. The use of the phosphine ligand PtBu3 is necessary for reactivity. It is proposed that the bulky ligand serves to prevent inhibition of the catalyst by facilitating reversible oxidative addition into the product C-Br bond. Intramolecular coupling of a vinyl bromide in the presence of an aryl iodide can take place, demonstrating unprecedented levels of selectivity.

  DOI：

  10.1021/ja1052335
• 作为产物：
  描述：

  3-甲氧基-2-硝基苯甲醛 在 三苯基膦 、 tin(ll) chloride 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 2.25h， 生成 2-(2,2-二溴-乙烯基)-6-甲氧基-苯基胺
  参考文献：
  名称：

  CuI-Catalyzed Tandem Intramolecular Amidation Using gem-Dibromovinyl Systems

  摘要：

  Imidazoindolones are present as the key structural motif in the family of antifungals, fumiquinazolines, and the antagonist asperlicin. The first example of a Cul-catalyzed tandem intramolecular amidation forming substituted imidazoindolones from readily accessible ortho gem-dibromovinylanilines is described.

  DOI：

  10.1021/ol052840u

文献信息

• Synthesis of 2-Vinylic Indoles and Derivatives via a Pd-Catalyzed Tandem Coupling Reaction
  作者：Aude Fayol、Yuan-Qing Fang、Mark Lautens

  DOI：10.1021/ol061374l

  日期：2006.9

  A novel one-step synthesis of valuable 2-vinylic indoles and their tricycle derivatives is described. This reaction, which utilizes a gem-dibromovinyl unit as a readily available starting material, occurs via an efficient Pd-catalyzed tandem Buchwald-Hartwig/Heck reaction.

  描述了有价值的2-乙烯基吲哚及其三环衍生物的新颖的一步合成。利用宝石-二溴乙烯基单元作为容易获得的起始原料的该反应通过有效的Pd催化的串联Buchwald-Hartwig / Heck反应进行。
• Tandem Pd-Catalyzed Double C−C Bond Formation: Effect of Water
  作者：David I. Chai、Mark Lautens

  DOI：10.1021/jo900053b

  日期：2009.4.17

  A highly efficient water-accelerated palladium-catalyzed reaction of gem-dibromoolefins with a boronic acid via a tandem Suzuki−Miyaura coupling and direct arylation is reported. A wide range of aryl, alkenyl, and alkyl boronic acids, as well as a variety of substitution patterns on the phenyl ring, are tolerated. Additionally, mechanistic studies were conducted to ascertain the order of the couplings

  据报道，通过串联的Suzuki-Miyaura偶联和直接芳基化反应，宝石-二溴代烯烃与硼酸进行了高效的水促进钯催化反应。宽范围的芳基，烯基和烷基硼酸，以及苯环上的各种取代方式都可以使用。此外，进行了机械研究，以确定耦合的顺序以及水的作用。这项研究的结果表明，主要途径是Suzuki-Miyaura偶联/直接芳基化序列，水加速了Pd（0）的形成和Suzuki-Miyaura偶联。
• WO2007/134421
  申请人：——

  公开号：——

  公开（公告）日：——
• Palladium-Catalyzed Synthesis of 2-Cyanoindoles from 2-<i>gem</i>-Dihalovinylanilines
  作者：Nicolas Zeidan、Sabine Bognar、Sophia Lee、Mark Lautens

  DOI：10.1021/acs.orglett.7b02244

  日期：2017.10.6

  An efficient Pd(0)-catalyzed synthesis of 2-cyanoindoles from 2-gem-dihalovinylanilines is reported. Few methods have aimed to synthesize these scaffolds, which are found in many natural products and have high bioactivity. This protocol features a robust catalyst system utilizing Zn(TFA)(2) to prolong the catalytic activity. Additionally, the amount of cyanide in the reaction phase is minimized by taking advantage of the solubility of Zn(CN)(2) in a two-solvent mixture.
• Rapid, robust, clean, catalyst-free synthesis of 2-halo-3-carboxyindoles
  作者：Aaron R. Kunzer、Michael D. Wendt

  DOI：10.1016/j.tetlet.2011.02.037

  日期：2011.4

  A novel synthesis of 2-halo-3-carboxyindoles from 2-(2,2-dihalovinyl)anilines was discovered. Reaction conditions and substrate applicability were studied. Optimally, the reaction takes only minutes when these substrates are heated in DMSO at 120 degrees C in the presence of cesium carbonate. However, the reaction is robust and takes place at a wide range of temperatures, is tolerant of aqueous reaction conditions, and can be performed in a variety of polar solvent/carbonate base combinations where the limiting factor is base solubility. A wide range of substituents is tolerated on the 2-(2,2-dihalovinyl)anilines, and yields are generally high, requiring only acidic aqueous work-up to obtain pure products. No catalyst is required for the transformation. The mechanism is believed to involve initial formation of an alkynyl bromide intermediate followed by ring closure and carbon dioxide trapping, leading to product formation. (C) 2011 Elsevier Ltd. All rights reserved.