3,5-bis(trifluoromethyl)-N-(2-phenylpropan-2-yl)benzenamine | 1182708-54-8

• 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: 3,5-bis(trifluoromethyl)-N-(2-phenylpropan-2-yl)benzenamine
• 英文别名: N-(2-phenylpropan-2-yl)-3,5-bis(trifluoromethyl)aniline
• CAS: 1182708-54-8
• 化学式: C₁₇H₁₅F₆N
• 分子量: 347.303
• InChiKey: NTMDMVUZQXKQQV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.07
• 重原子数：
  24.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  12.03
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  3,5-bis(trifluoromethyl)phenyl azide 、 异丙苯 在 Ru(tetraphenylporphyrin)(pyridine)2 作用下， 反应 0.25h， 以61%的产率得到3,5-bis(trifluoromethyl)-N-(2-phenylpropan-2-yl)benzenamine
  参考文献：
  名称：

  Ru(TPP)(py)2和Ru(TPP)(CO)促进苄基CH键催化胺化的比较研究

  摘要：

  结合实验和基于 DFT 的理论分析阐明了轴向配体 L 对 Ru(卟啉)L 配合物在促进有机叠氮化物 (RN3) 对苄基 C-H 键的胺化方面的催化活性的影响。实验数据表明，Ru(TPP)(CO) (1) (TPP = 四苯基卟啉的二价阴离子) 的催化活性与 Ru(TPP)(py)2 (2) (py = 吡啶) 的催化活性相当。DFT 模型揭示了 2 可以被视为一种前催化剂，它在一个吡啶配体的吸能损失后变得活跃，得到不饱和物质 [Ru](py) (11) {[Ru] = Ru(卟吩)}。该复合物将与 RN3 反应得到单亚胺单线态复合物 [Ru](py)(NR)S (6S)，它可以很容易地转化为在亚氨基 N 原子上具有双自由基特征的三线态异构体 6T。随后苄胺 PhCH2NHR 的形成是通过甲苯底物 (PhCH3) 的一个 C-H 键的自由基均裂活化而发生的。相反，通过停留在单线态势能表面，6S

  DOI：

  10.1002/ejic.201500656

文献信息

• The key intermediate in the amination of saturated C–H bonds: synthesis, X-ray characterization and catalytic activity of Ru(TPP)(NAr)2 (Ar = 3,5-(CF3)2C6H3)
  作者：Simone Fantauzzi、Emma Gallo、Alessandro Caselli、Fabio Ragaini、Nicola Casati、Piero Macchi、Sergio Cenini

  DOI：10.1039/b903238j

  日期：——

  The complex Ru(TPP)(NAr)(2) inserts a nitrene group into allylic and benzylic C-H bonds and is the key intermediate in the ruthenium porphyrin-catalyzed amination of hydrocarbons by aryl azides.

  络合物Ru（TPP）（NAr）（2）将亚硝基插入烯丙基和苄基CH键中，并且是钌卟啉催化的芳基叠氮化物胺化碳氢化合物的关键中间体。
• Ruthenium porphyrins-catalyzed atom-efficient amination of <font>C-H</font> bonds by arylazides
  作者：Daniela Intrieri、Alessandro Caselli、Fabio Ragaini、Sergio Cenini、Emma Gallo

  DOI：10.1142/s1088424610002501

  日期：2010.8

  Benzylic amines are synthesized in yield up to 90% by the Ru(TPP)CO -catalyzed amination of both exocyclic and endocyclic benzylic C-H bonds. The choice of arylazides as nitrogen sources confers to the methodology a good sustainability due to the formation of molecular nitrogen as the only stoichiometric by-product. A preliminary mechanistic investigation evidenced a critical role of the hydrocarbon concentration to drive the chemoselectivity of the reaction.

  通过 Ru(TPP)CO 催化外环和内环苄基 C-H 键的胺化反应，可合成出产率高达 90% 的苄胺。由于分子氮是唯一的化学副产物，选择芳基叠氮化物作为氮源使该方法具有良好的可持续性。初步的机理研究表明，碳氢化合物浓度对反应的化学选择性起着关键作用。
• Synthesis and catalytic activity of μ-oxo ruthenium(IV) porphyrin species to promote amination reactions
  作者：Paolo Zardi、Daniela Intrieri、Daniela Maria Carminati、Francesco Ferretti、Piero Macchi、Emma Gallo

  DOI：10.1142/s1088424616500814

  日期：2016.8

  of their analogous reactivity towards aryl azides to give the same catalytically active bis-imido species RuVI(TPP)(ArN)2. The reaction of [RuIV(TPP)(OCH[Formula: see text]]2O with Ph3CN3 or (CH[Formula: see text]SiN3 afforded [RuIV(TPP)(N[Formula: see text]]2O which was fully characterised, its molecular structure was also determined by single crystal X-ray analysis.

  这项工作描述了钌（IV）的合成[化学式：见正文]-通式[Ru]-氧卟啉配合物四(TPP)(X)]2O 已被用作使用芳基叠氮化物（ArN[公式：见正文]作为氮烯源的氮烯转移反应的催化剂。收集的数据表明[Ru的催化效率四(TPP)(OCH[公式：见正文]]2O与Ru相当二(TPP)CO 因为它们对芳基叠氮化物具有类似的反应性，从而产生相同的催化活性双亚氨基物质 Ru六(TPP)(ArN)2. [Ru的反应四(TPP)(OCH[公式：见正文]]2O 与 Ph3中国3或 (CH[公式：见正文]SiN3提供 [Ru四(TPP)(N[公式：见正文]]2完全表征的O，其分子结构也通过单晶X射线分析确定。
• Glycoporphyrin Catalysts for Efficient C–H Bond Aminations by Organic Azides
  作者：Giorgio Tseberlidis、Paolo Zardi、Alessandro Caselli、Damiano Cancogni、Matteo Fusari、Luigi Lay、Emma Gallo

  DOI：10.1021/acs.organomet.5b00436

  日期：2015.8.10

  We report herein the synthesis of new glycoporphyrin ligands which bear a glucopyranoside derivative on each meso-aryl moiety of the porphyrin skeleton. The saccharide unit is directly conjugated to the porphyrin or a triazole spacer is placed between the carbohydrate and porphyrin ring. The obtained glycoporphyrin ligands were employed to synthesize cobalt(II), ruthenium(II), and iron(III) complexes which were tested as catalysts of C-H bond aminations by organic azides. Two of the synthesized complexes were very efficient in promoting catalytic reactions, and the results achieved indicated that ruthenium and iron complexes show an interesting complementary catalytic activity in several amination reactions. The eco-friendly iron catalyst displayed very good chemical stability in catalyzing the amination reaction for three consecutive runs without losing catalytic activity.