3-fluoro-N-methyl-N-phenylaniline

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 3-fluoro-N-methyl-N-phenylaniline
• 化学式: C₁₃H₁₂FN
• 分子量: 201.243
• InChiKey: UWXQUQRWBSYPKY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-fluoro-N-methyl-N-phenylaniline 、 tert-butyl(iodoethynyl)diphenylsilane 在 1-(phenylthio)cyclopropanecarboxylic acid 、 silver(I) acetate 、 palladium diacetate 作用下， 以 氯仿 为溶剂， 反应 16.0h， 以42%的产率得到4-((tert-butyldiphenylsilyl)ethynyl)-3-fluoro-N-methyl-N-phenylaniline
  参考文献：
  名称：

  Pd/S,O-配体催化苯胺衍生物的选择性对位 C−H 炔基化

  摘要：

  通过 Pd/S,O-配体催化的 C−H 炔基化反应无需对起始苯胺进行预官能化即可获得对炔基化芳香胺。

  DOI：

  10.1002/chem.202104107
• 作为产物：
  描述：

  间氟苯甲醚 在 正丁基锂 、 (三甲基硅基)甲基氯化镁 、 三溴化硼 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 16.75h， 生成 3-fluoro-N-methyl-N-phenylaniline
  参考文献：
  名称：

  通过从易于合成的邻碘芳基三氟甲磺酸酯型前体高效生成 3-卤代芳烃中间体来提高其合成效用

  摘要：

  据报道，从邻碘芳基三氟甲磺酸酯类前体生成 3-卤代芳烃。该方法能够在-78°C 下生成具有显着高亲电性的 3-氟苄，从而在 3-氟苄、用作溶剂的四氢呋喃和硫醇之间形成三组分偶联产物。前体的易得性和从邻甲硅烷芳基三氟甲磺酸酯型前体生成芳烃的条件的正交性也增强了 3-卤代芳烃中间体的合成效用，使各种芳香族化合物易于获得。

  DOI：

  10.1246/cl.170136

文献信息

• Direct arylation of tertiary amines via aryne intermediates using diaryliodonium salts
  作者：Zhiang Zhang、Xunshen Wu、Jianwei Han、Wenjun Wu、Limin Wang

  DOI：10.1016/j.tetlet.2018.03.067

  日期：2018.5

  With a strategy by using diaryliodonium salts as the precursors of benzynes, direct N-arylation of tertiary amines with diaryliodonium salts was reported. Thus, the desired aromatic tertiary amines with a wide range of substituents were synthesized in moderate to excellent yields of 55–91%.

  通过使用二芳基碘鎓盐作为苯并炔的前体的策略，已报道了叔胺与二芳基碘鎓盐的直接N-芳基化。因此，合成了所需的具有广泛取代基的芳族叔胺，产率中等至55-91％。
• Transition-Metal-Free, Potassium tert-Butoxide/Dimethyl Sulfoxide Mediated Amination between Tertiary Amines and Aryl Halides
  作者：Jian-Mei Lu、Pei Huang、Bang-Yue He、Hui-Min Wang

  DOI：10.1055/s-0034-1379367

  日期：——

  C–N bond-formation reaction between tertiary amines and aryl halides is reported. Under the optimal conditions, various aromatic and aliphatic tertiary amines react with aryl halides, including iodides, bromides, and chlorides, to give mono-aminated products, N,N-dialkylanilines and N-alkyl-N-arylanilines, in good to high yields. Based on the experimental results, the reaction is believed to occur

  摘要 据报道，叔胺和卤代芳基之间没有过渡金属的C–N键形成反应。在最佳条件下，各种芳族和脂肪族叔胺与芳基卤化物（包括碘化物，溴化物和氯化物）反应，以高收率或高收率得到单胺化产物N，N-二烷基苯胺和N-烷基-N-芳基苯胺。 。根据实验结果，认为该反应通过衍生自芳基卤化物的芳烃中间体发生。 据报道，叔胺和卤代芳基之间没有过渡金属的C–N键形成反应。在最佳条件下，各种芳族和脂肪族叔胺与芳基卤化物（包括碘化物，溴化物和氯化物）反应，以高收率或高收率得到单胺化产物N，N-二烷基苯胺和N-烷基-N-芳基苯胺。 。根据实验结果，认为该反应通过衍生自芳基卤化物的芳烃中间体发生。
• Effective, transition metal free and selective C–F activation under mild conditions
  作者：Xianqiang Kong、Huizi Zhang、Yunqing Xiao、Changsheng Cao、Yanhui Shi、Guangsheng Pang

  DOI：10.1039/c4ra13753a

  日期：——

  reaction for the synthesis of aromatic amines via selective C–F bond cleavage of various fluoroarenes (mono-, di-, tri-, tetra-, penta- and perfluorobenzene) with primary and secondary aromatic amines under transition metal free conditions is demonstrated. The reaction conditions were investigated thoroughly for a wide range of fluoroarene substrates bearing different numbers of fluorine atoms, and the

  一种简单有效的芳族亲核单取代反应，可通过过渡级联的伯和仲芳族胺选择性地裂解各种氟代芳烃（单，二，三，四，五和全氟苯）的CF键进行芳族胺的合成证明了无金属条件。对含不同数量氟原子的多种氟芳烃底物的反应条件进行了深入研究，结果表明，溶剂和反应温度对成功进行取代反应至关重要。既定的方法能够以良好至优异的产率形成非氟化和部分氟化的芳族胺。在优化的条件下可以耐受几个官能团。
• <i>meta</i>‐C−H Arylation of Aniline Derivatives via Palladium/ S,O‐Ligand/Norbornene Cooperative Catalysis
  作者：Verena Sukowski、Manuela van Borselen、Simon Mathew、Bas de Bruin、M. Ángeles Fernández‐Ibáñez

  DOI：10.1002/anie.202317741

  日期：2024.1.25

  Aromatic amines are ubiquitous moieties in organic molecules and their direct functionalization is of great interest in many research areas due to their prevalence in pharmaceuticals and organic electronics. While several synthetic tools exist for the ortho‐ and para‐functionalization of anilines, the functionalization of the less reactive meta‐position is not easy to achieve with current methods. To date, the meta‐C−H arylation of aniline derivatives has been restricted to either the use of directing groups & templates, or their transformation into anilides & quaternary anilinium salts. Herein, we report the first general and efficient meta‐C−H‐arylation of non‐directed aniline derivatives via cooperative catalysis with a palladium–S,O‐ligand–norbornene system. The reaction proceeds under mild conditions with a wide range of aniline derivatives and aryl iodides, while being operationally simple and scalable. Our preliminary mechanistic investigation–including the isolation of several palladium complexes and deuterium experiments–reveal useful insights into the substituent‐effects of both the aniline‐substrate and the norbornene‐mediator during the meta‐C−H activation step.

  摘要 芳香胺是有机分子中无处不在的分子，由于芳香胺在医药和有机电子产品中的广泛应用，其直接官能化在许多研究领域都引起了极大的兴趣。虽然有多种合成工具可以实现苯胺的正官能化和对官能化，但目前的方法却难以实现反应性较低的元位的官能化。迄今为止，苯胺衍生物的元-C-H 芳基化仅限于使用定向基团和模板，或将其转化为苯胺类和季胺盐。在此，我们首次报道了通过钯-S,O-配体-降冰片烯体系的协同催化，对非定向苯胺衍生物进行通用而高效的元-C-H-芳基化反应。该反应在温和的条件下进行，适用于多种苯胺衍生物和芳基碘化物，同时操作简单、规模可控。我们的初步机理研究--包括分离几种钯配合物和氘实验--揭示了在元-C-H 活化步骤中苯胺底物和降冰片烯介质的取代效应。
• Transition metal complex ligand and olefin polymerization catalyst containing transition metal complex
  申请人：Otomaru Yuka

  公开号：US20070135600A1

  公开（公告）日：2007-06-14

  The invention provides a transition metal complex of formula (3) below: wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are the same or different and each independently represents a hydrogen atom, a halogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atom(s); R 5 represents a hydrogen atom, a fluorine atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atom(s); X 1 represents a hydrogen atom, a halogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atom(s); L represents a balancing counter ion or neutral ligand similar to X 1 that is bonding or coordinating to metal M; and q represents an integer of 0 or 1, and G 20 represents any one of G 21 to G 26 below: where A 1 represents an element of Group 15 of the periodic table, wherein A 1 in G 23 represents an anion of an element of Group 15 of the periodic table, and A 1 in G 21 represents a nitrogen atom; R 9 , R 14 , R 12 , R 13 , R 19 , R 20 , R 10 , R 11 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 and R 22 each independently represents, a hydrogen atom; or a substituted or unsubstituted alkyl groups having 1 to 10 carbon atom(s), and the line linking M and R 20 represents that M is coordinated or linked to an element of Group 15 or 16 of the periodic table or to a fluorine atom constituting R 20 .