3-(三氟甲基)喹喔啉-2-羧酸乙酯 | 3885-40-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 中文名称: 3-(三氟甲基)喹喔啉-2-羧酸乙酯
• 英文名称: ethyl 3-(trifluoromethyl)quinoxaline-2-carboxylate
• CAS: 3885-40-3
• 化学式: C₁₂H₉F₃N₂O₂
• 分子量: 270.211
• InChiKey: HBIZLJRVCDTEIZ-UHFFFAOYSA-N

物化性质

• 熔点：
  82-86 °C
• 沸点：
  325.8±42.0 °C(Predicted)
• 密度：
  1.365±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  52.1
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3-(三氟甲基)喹喔啉-2-羧酸乙酯 在 叠氮磷酸二苯酯 、 三乙胺 作用下， 以 甲醇 、 水 为溶剂， 反应 28.0h， 生成 tert-butyl [3-(trifluoromethyl)quinoxalin-2-yl]carbamate
  参考文献：
  名称：

  由3-（三氟甲基）喹喔啉-2（1 H）-一和3-（三（二）氟甲基）喹喔啉-2-羧酸合成新的2-取代的3-（三（二）氟甲基）-喹喔啉

  摘要：

  从3-（三氟甲基）喹喔啉-2（1 H）-1开始，获得了许多新的2-取代的3-（三氟甲基）喹喔啉，包括氨基，溴，氯，肼基，苯基，α-呋喃基，甲酰基。 ，甲硫基和甲磺酰基衍生物。首次获得3-（三（二）-氟甲基）喹喔啉-2-羧酸，用于合成2-氨基-3-（三（二）-氟甲基）喹喔啉和2-（2-氨基噻唑） -4-基）-3-（三氟甲基）喹喔啉。

  DOI：

  10.1007/s10593-015-1694-5
• 作为产物：
  描述：

  ethyl 4,4,4-trifluoro-3-(phenylamino)but-2-enoate 在 碘苯二乙酸 、 叠氮基三甲基硅烷 、 potassium iodide 作用下， 以 二甲基亚砜 为溶剂， 反应 6.0h， 以91 mg的产率得到3-(三氟甲基)喹喔啉-2-羧酸乙酯
  参考文献：
  名称：

  Potassium Iodide-Promoted One-Pot Synthesis of Fluoroalkylated Quinoxalines via a Tandem Michael Addition/Azidation/Cycloamination Approach

  摘要：

  Fluoroalkylated quinoxlines with various groups were efficiently synthesized via a one-pot tandem Michael addition/azidation/cydoamination process. Under the mild and metal-free conditions, a bis-imine intermediate (4a) was detected and isolated for the first time. KI played a crucial role in this reaction. The mechanism was described.

  DOI：

  10.1021/acs.joc.8b01030

文献信息

• Mechanistic Insight into Copper-Mediated Trifluoromethylation of Aryl Halides: The Role of CuI
  作者：He Liu、Jian Wu、Yuxuan Jin、Xuebing Leng、Qilong Shen

  DOI：10.1021/jacs.1c07408

  日期：2021.9.8

  or I, Q = PPh4) in copper-mediated trifluoromethylation of aryl halides were studied. Qualitative and quantitative studies showed [Cu(CF3)2]−Q+ and [Cu(CF3)(I)]−Q+ were not highly reactive. Instead, a much more reactive species, ligandless [CuCF3] or DMF-ligated species [(DMF)CuCF3], was generated in the presence of excess CuI. On the basis of these results, a general mechanistic map for CuI-promoted

  研究了铜介导的芳基卤化物三氟甲基化中关键中间体 [Cu(CF 3 )(X)] - Q + (X = CF 3或 I, Q = PPh 4 )的合成、表征和反应性。定性和定量研究表明[Cu(CF 3 ) 2 ] - Q +和[Cu(CF 3 )(I)] - Q +的反应性不高。取而代之的是一种更具反应性的物质，无配体 [CuCF 3 ] 或 DMF 配体物质 [(DMF)CuCF 3]，在过量的 CuI 存在下产生。在这些结果的基础上，提出了 CuI 促进芳基卤化物三氟甲基化的一般机理图。此外，基于这种机理理解，开发了一种 HOAc 促进的方案，用于用 [Ph 4 P] + [Cu(CF 3 ) 2 ] -对芳基卤化物进行三氟甲基化。
• Correction to “Mechanistic Insight into Copper-Mediated Trifluoromethylation of Aryl Halides: The Role of CuI”
  作者：He Liu、Jian Wu、Yuxuan Jin、Xuebing Leng、Qilong Shen

  DOI：10.1021/jacs.2c07580

  日期：2022.8.17

  disorders in both structures. The crystals of complex 1b exist as a mixture of two species, [Cu(CF3)(Cl)]− and [Cu(CF3)2]−, while the crystals of complex 1c are a mixture of three species, [Cu(CF3)(I)]−, [Cu(CF3)2]−, and [CuI2]−. The structures of complexes 1b and 1c were tentatively assigned as [Cu(CF3)(Cl)]− and [Cu(CF3)(I)]−, since the unit-cell parameters of the crystal lattices of [Cu(CF3)2]− and [CuI2]−

  第14368页。已发表作品中的方案1应替换为以下版本，其中添加了E部分。以下句子应添加到方案 1 的文本讨论中，在开始的段落末尾，“为了阐明观察到的 [CF 3 Cu] 物种的结构，......”：Grushin 和同事准备并表征了无配体 CuCF 3（DMF 中 -26.9 ppm）并研究了无配体 CuCF 3与芳基碘化物的反应机理（方案 1E）。19b第 14370 页。应在引用图 2 的段落末尾添加以下句子： 配合物1b和1c的单晶的 X 射线衍射研究表明两种结构都存在显着的静态障碍。配合物1b的晶体以两种物质的混合物存在，[Cu(CF 3 )(Cl)] -和 [Cu(CF 3 ) 2 ] -，而配合物1c的晶体是三种物质的混合物，[Cu (CF 3 )(I)] -、[Cu(CF 3 ) 2 ] -和[CuI 2 ] -。配合物1b和1c的结构暂定为[Cu(CF 3 )(Cl)] -和[Cu(CF
• An electrochemical tandem oxidative azidation and intramolecular cyclization strategy for the synthesis of quinoxaline derivatives
  作者：Kai Zhou、Shendan Xia、Zhiwei Chen

  DOI：10.1039/d3ob00558e

  日期：——

  An electrochemical-oxidation-induced intramolecular annulation for the synthesis of quinoxalines was developed under undivided electrolytic conditions. N-Aryl enamines and TMSN3 as the starting materials could smoothly participate in the transformation to achieve the construction of two C–N bonds through tandem azidation and cyclic amination reactions. The reaction could be easily handled and avoided

  在未分开的电解条件下开发了用于合成喹喔啉的电化学氧化诱导的分子内环化。N-芳基烯胺和TMSN 3作为起始原料可以顺利参与转化，通过串联叠氮化和循环胺化反应实现两个C-N键的构建。该反应易于操作，避免使用过渡金属催化剂和化学氧化剂，符合绿色化学的可持续发展。
• Quinoxaline synthesis in novel tandem one-pot protocol
  作者：B.S.P. Anil Kumar、B. Madhav、K. Harsha Vardhan Reddy、Y.V.D. Nageswar

  DOI：10.1016/j.tetlet.2011.03.110

  日期：2011.6

  A variety of quinoxalines were synthesized via tandem one-pot procedure for the first time in water medium. The key strategy was the in situ preparation of alpha-halo-beta-keto esters by the reaction of N-bromo succinimide with beta-keto esters and further condensation with phenylene diamines. This novel eco-friendly approach offers an easy, efficient, and mild synthesis of highly substituted quinoxalines in good yields. (C) 2011 Elsevier Ltd. All rights reserved.
• One-pot synthesis of quinoxaline-2-carboxylate derivatives using ionic liquid as reusable reaction media
  作者：H.M. Meshram、P. Ramesh、G. Santosh Kumar、B. Chennakesava Reddy

  DOI：10.1016/j.tetlet.2010.05.099

  日期：2010.8

  The catalyst-free one-pot synthesis of quinoxaline-2-carboxylate is reported by the reaction of alpha-halo-beta-ketoesters with 1,2-diamines using an ionic liquid as an environmentally benign solvent The recovered ionic liquid was reused for four to five cycles Moreover, the method is applicable for a variety of 1,2-diamines and alpha-halo-beta-ketoesters (c) 2010 Elsevier Ltd All rights reserved