6-methyl-3-(trifluoromethyl)phenanthridine | 1319721-03-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: 6-methyl-3-(trifluoromethyl)phenanthridine
• 英文别名: 6-Methyl-3-(trifluoromethyl)phenanthridine
• CAS: 1319721-03-3
• 化学式: C₁₅H₁₀F₃N
• 分子量: 261.246
• InChiKey: XWMSQYGKWGZHFP-UHFFFAOYSA-N

物化性质

• 熔点：
  72 °C
• 沸点：
  358.4±37.0 °C(Predicted)
• 密度：
  1.301±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2'-p-trifluoromethylphenylacetophenone oxime 在 吡啶 、 4-二甲氨基吡啶 、 iron(III)-acetylacetonate 作用下， 以 溶剂黄146 为溶剂， 反应 36.0h， 生成 6-methyl-3-(trifluoromethyl)phenanthridine
  参考文献：
  名称：

  铁催化O-乙酰肟的分子内N-芳基化反应合成菲啶

  摘要：

  在乙酸中催化量的乙酰丙酮铁（III）的存在下，衍生自2'-芳基苯乙酮的O-乙酰基肟进行N-O键裂解/分子内N-芳基化。与常规的交叉偶联或直接的CH芳基化反应相结合，该反应为取代的菲啶提供了便利的途径。

  DOI：

  10.1021/ol4020392

文献信息

• Metal-Free Photoredox Catalyzed Cyclization of O-(2,4-Dinitrophenyl)oximes to Phenanthridines
  作者：Xiubin Liu、Zhixing Qing、Pi Cheng、Xinyu Zheng、Jianguo Zeng、Hongqi Xie

  DOI：10.3390/molecules21121690

  日期：——

  A metal-free visible-light photoredox-catalyzed intermolecular cyclization reaction of O-2,4-dinitrophenyl oximes to phenanthridines was developed. In this study, the organic dye eosin Y and i-Pr₂NEt were used as photocatalyst and terminal reductant, respectively. The oxime substrates were transformed into iminyl radical intermediates by single-electron reduction, which then underwent intermolecular

  开发了一种无金属的可见光光氧化还原催化的O-2,4-二硝基苯基肟与菲啶的分子间环化反应。在这项研究中，有机染料曙红Y和i-Pr 2 NEt分别用作光催化剂和末端还原剂。通过单电子还原将肟底物转化为亚氨基自由基中间体，然后使其进行分子间均溶芳族取代（HAS）反应，得到菲啶衍生物。
• Electrochemical Decarboxylative Cyclization of α‐Amino‐Oxy Acids to Access Phenanthridine Derivatives
  作者：Yanling Zhan、Changhui Dai、Zitong Zhu、Ping Liu、Peipei Sun

  DOI：10.1002/asia.202101388

  日期：2022.3.14

  compounds found in pharmaceuticals and natural products. Herein, an efficient electrochemical decarboxylative cyclization of α-amino-oxy acids to synthesize phenanthridine derivatives was developed. This reaction proceeded through iminyl radical formation cascade intramolecular cyclization from readily available materials under transition-metal-free and mild conditions.

  菲啶是一类重要的杂环化合物，存在于药物和天然产物中。在此，开发了一种高效的 α-氨基氧基酸电化学脱羧环化合成菲啶衍生物。该反应通过在无过渡金属和温和条件下从容易获得的材料中形成亚氨基自由基级联分子内环化进行。
• UV promoted phenanthridine syntheses from oxime carbonate derived iminyl radicals
  作者：Roy T. McBurney、Alexandra M. Z. Slawin、Laura A. Smart、Yanping Yu、John C. Walton

  DOI：10.1039/c1cc12720a

  日期：——

  Oxime carbonates were found to be excellent precursors for the clean and direct generation of iminyl radicals under UV irradiation. Suitably functionalised iminyls underwent cyclisations yielding various phenanthridines and also substituted quinolines and isoquinolines. EPR and X-ray analyses of oxime carbonates provided insight into the mechanism.

  已发现肟肟酸盐是在紫外线照射下干净，直接生成亚胺基的极好前体。合适地官能化的亚氨基进行环化，产生各种菲啶，以​​及取代的喹啉和异喹啉。碳酸盐肟的EPR和X射线分析提供了对该机理的深入了解。
• Interplay of ortho<i>-</i> with spiro-cyclisation during iminyl radical closures onto arenes and heteroarenes
  作者：Roy T McBurney、John C Walton

  DOI：10.3762/bjoc.9.120

  日期：——

  Sensitised photolyses of ethoxycarbonyl oximes of aromatic and heteroaromatic ketones yielded iminyl radicals, which were characterised by EPR spectroscopy. Iminyls with suitably placed arene or heteroarene acceptors underwent cyclisations yielding phenanthridine-type products from ortho-additions. For benzofuran and benzothiophene acceptors, spiro-cyclisation predominated at low temperatures, but thermodynamic control ensured ortho-products, benzofuro- or benzothieno-isoquinolines, formed at higher temperatures. Estimates by steady-state kinetic EPR established that iminyl radical cyclisations onto aromatics took place about an order of magnitude more slowly than prototypical C-centred radicals. The cyclisation energetics were investigated by DFT computations, which gave insights into factors influencing the two cyclisation modes.

  对芳香和杂芳酮的乙氧羰基肟的敏化光解产生了亚胺基自由基，通过EPR光谱表征。具有适当位置芳烃或杂芳烃受体的亚胺基经历环化反应，从邻加成中产生菲啶类产物。对苯并呋喃和苯并噻吩受体来说，在低温下，螺环化反应占主导地位，但热力学控制确保在较高温度下形成邻产物，苯并呋喃或苯并噻吩异喹啉。通过稳态动力学EPR估算，亚胺基自由基对芳香族的环化反应速度约比原型的C-中心自由基慢一个数量级。通过DFT计算研究了环化反应的能量学，揭示了影响两种环化模式的因素。
• Metal‐Organic Framework Supported Copper Photoredox Catalysts for Iminyl Radical‐Mediated Reactions
  作者：Ben Ma、Qi Xia、Deyang Wang、Ji‐Kang Jin、Zekun Li、Qiu‐Jiang Liang、Meng‐Ying Sun、Dongyi Liu、Li‐Juan Liu、Hui‐Xing Shu、Jun Yang、Dan Li、Jian He

  DOI：10.1002/anie.202300233

  日期：——

  A binap-ligated copper dimer has been heterogenized on a pillar-layered MOF surface for the first time using a hydroxamic acid linker. This MOF-supported dimeric copper photocatalyst demonstrates much higher activity and recyclability than its homogeneous counterparts in intra- and intermolecular radical reactions of N-acyloxy imidates and O-acyl oximes.

  binap 连接的铜二聚体首次使用异羟肟酸接头在柱状层状 MOF 表面异质化。这种 MOF 负载的二聚铜光催化剂在N-酰氧基亚胺酸酯和O-酰基肟的分子内和分子间自由基反应中表现出比其均相对应物更高的活性和可回收性。