2-bromoethynylphenylamine | 1290035-30-1

• 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: 2-bromoethynylphenylamine
• 英文别名: 2-(bromoethynyl)aniline；2-(2-Bromoethynyl)aniline
• CAS: 1290035-30-1
• 化学式: C₈H₆BrN
• 分子量: 196.046
• InChiKey: PUMPXWOAQYDJDD-UHFFFAOYSA-N

物化性质

• 沸点：
  288.7±42.0 °C(Predicted)
• 密度：
  1.59±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  26
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-bromoethynylphenylamine 以 甲醇 、 乙醚 、 二甲基亚砜 、 乙酸乙酯 为溶剂， 反应 0.22h， 生成 2-bromo-1H-indole-3-carboxylic acid methyl ester
  参考文献：
  名称：

  Rapid, robust, clean, catalyst-free synthesis of 2-halo-3-carboxyindoles

  摘要：

  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.

  DOI：

  10.1016/j.tetlet.2011.02.037
• 作为产物：
  描述：

  1-(2,2-二溴乙烯基)-2-硝基苯 在 tin(II) chloride dihdyrate 、 potassium carbonate 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 生成 2-bromoethynylphenylamine
  参考文献：
  名称：

  钯催化合成连接双杂环─合成及光物理性质研究

  摘要：

  报道了钯催化的多米诺骨牌 C-N 偶联/Cacchi 反应。在密度泛函理论计算的辅助下，进行了光致发光双杂环的设计，合成收率高达 98%。通过该策略获得的产品的光物理特性是一项综合研究的一部分，该研究导致了宽发射光谱和高达 0.59 的量子产率。机理实验证实溴炔是有效的中间体，密度泛函理论研究表明了一条涉及初始氧化加成到偕二卤代烯烃的顺式 C-Br 键的途径。

  DOI：

  10.1021/jacs.3c07234

文献信息

• Gold(I)-Catalyzed Reactions of 1-(<i>ortho</i>-Alkynylaryl)ureas: Highly Selective Heterocyclization and Synthesis of Mixed<i>N</i>,<i>O</i>-Acetals
  作者：Ana Gimeno、Ana B. Cuenca、Mercedes Medio-Simón、Gregorio Asensio

  DOI：10.1002/adsc.201300730

  日期：2014.1.13

  The open chain amino O,O‐acetals and a series of new cyclic mixed N,O‐acetals containing the trifluoroethyl group were synthesized when the reactions were performed in ethanol or trifluoroethanol, respectively, as solvent. The procedure allows for an easy access to this versatile class of key intermediates in organic synthesis from simple starting materials. The effect of using either DMF or protic

  现成的1-（邻乙炔基芳基）脲衍生物在二甲基甲酰胺（DMF ）中经历选择性的金/银[AuCl（IPr）] / AgSbF 6 }催化的N -6 exo- dig或N -5- endo dig杂环化过程）在60°C下。苯并恶嗪衍生物，即通过尿素氧进行O -6- exo- dig环闭合的产物，只有在N-3碱度大大降低时才能在催化条件下观察到，但在低化学计量比过程中很容易分离。温度。开链氨基O，O-乙缩醛和一系列新的环状混合当分别在乙醇或三氟乙醇中作为溶剂进行反应时，会合成含有三氟乙基的N，O-缩醛。该方法可以轻松地从简单的起始原料获得有机合成中这类通用的关键中间体。报道了使用DMF或质子溶剂对反应过程的影响。
• Screening Methods
  申请人：Lautens Mark

  公开号：US20080039625A1

  公开（公告）日：2008-02-14

  Disclosed are processes for the preparation of 2-substituted indole compounds wherein the 2-substituent comprises an R 4 group, wherein R 4 is selected from the group consisting of monocyclic aromatic, polycyclic aromatic, monocyclic heteroaromatic, polycyclic heteroaromatic, 1° alkyl, and alkenyl, all of which are optionally substituted at one or more substitutable positions with one or more suitable substituents, and wherein R 4 is bonded to the 2-position of the indole ring via a C—C bond; the process comprising reacting an orthogem-dihalovinylaniline compound of the formula (I): wherein Halo comprises Br, Cl, or I; each of the one or more R 1 is independently selected from the group consisting of H, fluoro, lower alkyl, lower alkenyl, lower alkoxy, aryloxy, lower haloalkyl, lower alkenyl, —C(O)O-lower alkyl, monocyclic or polycyclic aryl or heteroaryl moiety, or R 1 is an alkenyl group bonded so to as to form a 4- to 20-membered fused monocycle or polycyclic ring with the indole ring; all of which are optionally substituted with one or more suitable substituents at one or more substitutable positions; R 2 comprises H, alkyl, cycloalkyl, aryl, heteroaryl, aryl-loweralkyl-, or heteroaryl-loweralkyl-, all of which are optionally substituted at one or more substitutable positions with one or more suitable substituents; R 3 comprises H, alkyl, haloalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocycle, aryl-(C 1-6 )alkyl-, or heteroaryl-loweralkyl-, all of which are optionally substituted at one or more substitutable positions with one or more suitable substituents; with an organoboron reagent selected from the group consisting of a boronic ester of R 4 , a boronic acid of R 4 , a boronic acid anhydride of R 4 , a trialkylborane of R 4 and a 9-BBN derivative of R 4 ; in the presence of a base, a palladium metal pre-catalyst and a ligand under reaction conditions effective to form the 2-substituted indole compound. Also disclosed are processes for the preparation of ortho-gem-dihalovinylaniline compounds. Novel compounds prepared by the processes and novel uses of the compounds are likewise disclosed.

  本发明涉及制备2-取代吲哚化合物的方法，其中2-取代基包括R4基团，其中R4从单环芳香族、多环芳香族、单环杂芳族、多环杂芳族、1°烷基和烯基中选择，所有这些基团都可以在一个或多个可替换的位置上用一个或多个适当的取代基替换，并且其中R4通过C-C键与吲哚环的2-位置结合；该方法包括将式（I）的正交二卤代乙烯基苯胺化合物与来自以下组的有机硼试剂反应：其中Halo包括Br、Cl或I；其中一个或多个R1各自独立地选择自H、氟、低烷基、低烯基、低烷氧基、芳氧基、低卤代烷基、低烯基、-C（O）O-低烷基、单环或多环芳基或杂芳基基团，或者R1是一个烯基团，通过与吲哚环形成一个4到20个成员的融合的单环或多环环，所有这些基团都可以在一个或多个可替换的位置上用一个或多个适当的取代基替换；R2包括H、烷基、环烷基、芳基、杂芳基、芳基-低烷基-或杂芳基-低烷基-，所有这些基团都可以在一个或多个可替换的位置上用一个或多个适当的取代基替换；R3包括H、烷基、卤代烷基、烯基、炔基、芳基、杂芳基、环烷基、杂环、芳基-(C1-6)烷基-或杂芳基-低烷基-，所有这些基团都可以在一个或多个可替换的位置上用一个或多个适当的取代基替换；在碱、钯金属预催化剂和配体存在下，以有效的反应条件形成2-取代吲哚化合物。本发明还涉及制备正交二卤代乙烯基苯胺化合物的方法。本发明还涉及通过上述方法制备的新化合物以及化合物的新用途。
• 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.