4-methyl-2-(o-tolyl)quinoline

• 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: 4-methyl-2-(o-tolyl)quinoline
• 英文别名: 4-Methyl-2-(2-methylphenyl)quinoline
• 化学式: C₁₇H₁₅N
• 分子量: 233.313
• InChiKey: OVEWOSYWFUGPCH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  勒皮啶 N-氧化物 在 sodium persulfate 、 silver nitrate 、 三氟乙酸 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 4.5h， 生成 4-methyl-2-(o-tolyl)quinoline
  参考文献：
  名称：

  由N-甲氧基喹啉-1-四氟硼酸盐和芳基硼酸直接芳基化合成2-芳基喹啉

  摘要：

  发现N-甲氧基喹啉-1-四氟硼酸衍生物与芳基硼酸在室温下具有快速区域选择性的快速直接芳基化反应。该反应对喹啉衍生物和芳基硼​​酸均显示出优异的官能团耐受性和广泛的底物范围。

  DOI：

  10.1016/j.tetlet.2018.02.008

文献信息

• Nickel complexes supported by quinoline-based ligands: synthesis, characterization and catalysis in the cross-coupling of arylzinc reagents and aryl chlorides or aryltrimethylammonium salts
  作者：Qiang Zhang、Xue-Qi Zhang、Zhong-Xia Wang

  DOI：10.1039/c2dt30886j

  日期：——

  Lithium and nickel complexes bearing quinoline-based ligands have been synthesized and characterized. Reaction of 8-azidoquinoline with Ph2PNHR (R = p-MeC6H4, But) affords N-(8-quinolyl)iminophosphoranes RNHP(Ph2)N(8-C9H6N) (1a, R = p-MeC6H4; 1b, R = But. C9H6N = quinolyl)). Reaction of 1a with (DME)NiCl2 generates a nickel complex [NiCl2N(8-C9H6N)P(Ph2)NH(p-MeC6H4)}] (2a). Treatment of 1b with (DME)NiCl2 and following with NaH produces [NiCl(1,2-C6H4)P(Ph)(NHBut)N(8-C9H6N)}] (4). Complex 4 was also obtained by reaction of (DME)NiCl2 with [Li(1,2-C6H4)P(Ph)(NHBut)N(8-C9H6N)}] (5) prepared through lithiation of 1b. Reaction of 2-PyCH2P(Ph2)N(8-C9H6N) (6, Py = pyridyl) and PhNC(Ph)CH2P(Ph2)N(8-C9H6N) (8), respectively, with (DME)NiCl2 yields two five-coordinate N,N,N-chelate nickel complexes, [NiCl22-PyCH2P(Ph2)N(8-C9H6N)}] (7) and [NiCl2PhNC(Ph)CH2P(Ph2)N(8-C9H6N)}] (9). Similar reaction between Ph2PCH2P(Ph2)N(8-C9H6N) (10) and (DME)NiCl2 results in five-coordinate N,N,P-chelate nickel complex [NiCl2Ph2PCH2P(Ph2)N(8-C9H6N)}] (11). Treatment of [(8-C9H6N)NP(Ph2)]2CH2 (12) [prepared from (Ph2P)2CH2 and 2 equiv. of 8-azidoquinoline] with LiBun and (DME)NiCl2 successively affords [NiCl(8-C9H6N)NP(Ph2)}2CH] (13). The new compounds were characterized by 1H, 13C and 31P NMR spectroscopy (for the diamagnetic compounds), IR spectroscopy (for the nickel complexes) and elemental analysis. Complexes 2a, 4, 7, 9, 11 and 13 were also characterized by single-crystal X-ray diffraction techniques. The nickel complexes were evaluated for the catalysis in the cross-coupling reactions of arylzinc reagents with aryl chlorides and aryltrimethylammonium salts. Complex 7 exhibits the highest activity among the complexes in catalyzing the reactions of arylzinc reagents with either aryl chlorides or aryltrimethylammonium bromides.

  含喹啉基配体的锂和镍配合物已被合成和表征。8-叠氮喹啉与Ph2PNHR(R = p-MeC6H4, But)反应得到N-(8-喹啉基)亚氨基膦烷RNHP(Ph2)N(8-C9H6N)(1a, R = p-MeC6H4; 1b, R = But. C9H6N = 喹啉基))。1a与(DME)NiCl2反应生成镍配合物[NiCl2N(8-C9H6N)P(Ph2)NH(p-MeC6H4)}] (2a)。1b与(DME)NiCl2反应后，再用NaH处理得到[NiCl(1,2-C6H4)P(Ph)(NHBut)N(8-C9H6N)}] (4)。配合物4也可通过(DME)NiCl2与[Li(1,2-C6H4)P(Ph)(NHBut)N(8-C9H6N)}] (5)反应得到，后者是通过1b的锂化制备的。2-吡啶基甲基P(Ph2)N(8-C9H6N)(6, Py = 吡啶基)和PhNC(Ph)CH2P(Ph2)N(8-C9H6N)(8)分别与(DME)NiCl2反应，得到两个五配位的N,N,N-螯合镍配合物[NiCl22-PyCH2P(Ph2)N(8-C9H6N)}] (7)和[NiCl2PhNC(Ph)CH2P(Ph2)N(8-C9H6N)}] (9)。Ph2PCH2P(Ph2)N(8-C9H6N)(10)与(DME)NiCl2的类似反应生成五配位的N,N,P-螯合镍配合物[NiCl2Ph2PCH2P(Ph2)N(8-C9H6N)}] (11)。[(8-C9H6N)NP(Ph2)]2CH2(12)[由(Ph2P)2CH2和2当量的8-叠氮喹啉制备]依次与LiBun和(DME)NiCl2反应得到[NiCl(8-C9H6N)NP(Ph2)}2CH] (13)。新化合物通过1H、13C和31P NMR光谱(对于抗磁性化合物)、IR光谱(对于镍配合物)和元素分析进行表征。配合物2a、4、7、9、11和13还通过单晶X射线衍射技术进行表征。这些镍配合物被评估用于芳基锌试剂与芳基氯和芳基三甲基铵盐的交叉偶联反应的催化活性。在催化芳基锌试剂与芳基氯或芳基三甲基溴化铵的反应中，配合物7显示出最高的活性。
• Ytterbium(III) Triflate Catalyzed Synthesis of Quinoline Derivatives from N-Arylaldimines and Vinyl Ethers
  作者：Yoshikazu Makioka、Takaaki Shindo、Yuki Taniguchi、Ken Takaki、Yuzo Fujiwara

  DOI：10.1055/s-1995-4002

  日期：1995.7

  [4+2] Cycloaddition reaction of N-arylaldimines with vinyl ethers is effectively catalyzed by ytterbium(III) triflate to give quinoline derivatives in good yields. Furthermore, the reaction with silyl enol ethers affords 4-siloxytetrahydroquinolines, whereas an imino aldol reaction takes place in the reaction with ketene silyl acetals.

  [4+2]环加成反应中，N-芳基亚胺与乙烯基醚在三氟甲磺酸镱(III)的有效催化下，可高产率地生成喹啉衍生物。此外，与硅基烯醇醚进行反应则得到4-硅氧基四氢喹啉，而与烯酮硅缩醛反应则发生亚胺醇醛缩合反应。
• The synthesis of quinolines <i>via</i> denitrogenative palladium-catalyzed cascade reaction of <i>o</i>-aminocinnamonitriles with arylhydrazines
  作者：Jing Xie、Hang Huang、Tong Xu、Renhao Li、Jiuxi Chen、Xueting Ye

  DOI：10.1039/d0ra01043j

  日期：——

  example of the palladium-catalyzed cascade reaction of o-aminocinnamonitriles with arylhydrazines has been achieved, providing an efficient synthetic pathway to access quinolines with moderate to good yields. Preliminary mechanistic experiments indicate that this cascade process involves sequential denitrogenative addition followed by an intramolecular cyclization.

  已经实现了邻氨基肉桂腈与芳基肼的钯催化级联反应的第一个例子，为以中等至高产率获得喹啉提供了一种有效的合成途径。初步机械实验表明，这种级联过程涉及顺序脱氮加成，然后是分子内环化。
• Iron‐Catalyzed Transfer Hydrogenation: Divergent Synthesis of Quinolines and Quinolones from <i>ortho</i>‐Nitrobenzyl Alcohols
  作者：Simin Chun、Ramachandra Reddy Putta、Junhwa Hong、Seung Hyun Choi、Dong‐Chan Oh、Suckchang Hong

  DOI：10.1002/adsc.202300661

  日期：2023.10.13

  report the divergent synthesis of quinolines and quinolones via a transfer hydrogenative condensation of ortho-nitrobenzyl alcohols in one step. The reaction proceeded using the cyclopentadienone iron complex without any additional redox reagents. After transfer hydrogenation between ortho-nitrobenzyl alcohols and secondary alcohols, the subsequent Friedländer annulation affords polysubstituted quinoline

  在此，我们报道了通过邻硝基苯甲醇的转移氢化缩合一步合成喹啉和喹诺酮的不同合成方法。使用环戊二烯酮铁络合物进行反应，无需任何额外的氧化还原试剂。在邻硝基苯甲醇和仲醇之间进行转移氢化后，随后进行 Friedländer 环化反应，得到 22-90% 的多取代喹啉产物（39 个例子）。所开发的方法还应用于使用伯醇代替仲醇合成喹诺酮类药物（12 个实例）。获得的喹啉产品被转化为几种候选药物，以证明其合成潜力。
• Palladium Catalyzed Annulation of <i>o</i>-Iodo-Anilines with Propargyl Alcohols: Synthesis of Substituted Quinolines
  作者：Zhi Zhang、Jing-Tong Deng、Jia-Yi Feng、Jin-Yan Liang、Xue-Tao Xu、Jin-Bao Peng

  DOI：10.1021/acs.joc.3c01451

  日期：2023.8.18

  A palladium catalyzed annulation of o-iodo-anilines with propargyl alcohols for the synthesis of substituted quinolines has been developed. The reaction tolerates diverse functional groups under mild conditions, providing direct access to 2,4-disubstituted quinolines from easily available starting materials. A broad range of 2,4-disubstituted quinolines were efficiently prepared in good to excellent

  已经开发出一种钯催化的邻碘苯胺与炔丙醇的环化反应，用于合成取代的喹啉。该反应在温和条件下耐受多种官能团，从而可以从容易获得的起始材料中直接获得 2,4-二取代喹啉。有效制备了多种 2,4-二取代喹啉，收率良好至优异。