5-cyano-6-(4-methylphenyl)-3-(2-pyridyl)-1,2,4-triazine | 517876-22-1

• 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: 5-cyano-6-(4-methylphenyl)-3-(2-pyridyl)-1,2,4-triazine
• 英文别名: 6-(4-Methylphenyl)-3-pyridin-2-yl-1,2,4-triazine-5-carbonitrile
• CAS: 517876-22-1
• 化学式: C₁₆H₁₁N₅
• 分子量: 273.297
• InChiKey: GDTXUCXWIRAMIN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  75.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5-cyano-6-(4-methylphenyl)-3-(2-pyridyl)-1,2,4-triazine 以 邻二氯苯 为溶剂， 反应 19.08h， 生成 6-methoxy-5-(p-tolyl)-2,2'-bipyridine
  参考文献：
  名称：

  基于6-烷氧基-2,2'-联吡啶的新型推挽荧光团：合理的合成方法和光物理性质

  摘要：

  我们提出了一种有效的合成方法，通过其1,2,4-三嗪类似物将2（6）-烷氧基（bi）吡啶作为新的推挽式荧光团。研究了新化合物的光物理性质，并首次研究了它们的结构-性质关系。

  DOI：

  10.1007/s10593-019-02495-5
• 作为产物：
  描述：

  4-methyl-α-oximinoacetophenone hydrazone 在 lead(II,IV) oxide 、 溶剂黄146 、 三乙胺 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 生成 5-cyano-6-(4-methylphenyl)-3-(2-pyridyl)-1,2,4-triazine
  参考文献：
  名称：

  A Versatile Strategy for the Synthesis of Functionalized 2,2‘-Bi- and 2,2‘:6‘,2‘ ‘-Terpyridines via Their 1,2,4-Triazine Analogues

  摘要：

  A general synthetic route for the synthesis of functionalized bi- and terpyridines is reported. Functionalized 1,2,4-triazene 4-oxides 7 and 8-obtained from the reaction of hydrazones 1 with pyridine aldehydes and followed by oxidation-are functionalized by introduction of a cyano group via nucleophilic aromatic substitution. The thus-obtained 5-cyano-1,2,4-triazines 9 and 10 undergo facile inverse-electron-demand Diels-Alder reactions with enamines and alkenes to yield functionalized bi- and terpyridines, respectively. The substituent at position 6 of the 1,2,4-triazene 4-oxides must be aromatic or heteroaromatic in order to allow their facile synthesis, but other substituents and reagents may vary. Each step of the synthetic route allows diversification, which makes the approach particularly useful for the facile synthesis of a large variety of functionalized bi- and terpyridines.

  DOI：

  10.1021/jo0267955

文献信息

• Studies on the interactions of 5-<i>R</i>-3-(2-pyridyl)-1,2,4-triazines with arynes: inverse demand aza-Diels–Alder reaction <i>versus</i> aryne-mediated domino process
  作者：Dmitry S. Kopchuk、Igor L. Nikonov、Albert F. Khasanov、Kousik Giri、Sougata Santra、Igor S. Kovalev、Emiliya V. Nosova、Sravya Gundala、Padmavathi Venkatapuram、Grigory V. Zyryanov、Adinath Majee、Oleg N. Chupakhin

  DOI：10.1039/c8ob00847g

  日期：——

  aza-Diels–Alder products or 1,2,4-triazine ring rearrangement (domino) products as major ones depending on the nature of both the substituents at the C5 position of the 1,2,4-triazine core or in the aryne moiety. The structures of the key products were confirmed based on X-ray data. Based on the density functional theoretical (DFT) studies of the Diels–Alder transition state geometries, the influence of the nature

  已经研究了取代的5 - R -3-（吡啶基-2）-1,2,4-三嗪与原位生成的取代的芳烃中间体之间的相互作用。根据1,2,5碳原子上两个取代基的性质，反应可提供反需求（ID）的aza-Diels-Alder产品或1,2,4-三嗪环重排（domino）产品作为主要产品。 4-三嗪核或在芳烃部分。根据X射线数据确定了关键产品的结构。基于Diels–Alder过渡态几何的密度泛函理论（DFT）研究，提出了芳烃性质对1,2,4-三嗪转化方向的影响。
• 2-Aminooxazoles as novel dienophiles in the inverse demand Diels–Alder reaction with 1,2,4-triazines
  作者：Alexey P. Krinochkin、Guda Mallikarjuna Reddy、Dmitry S. Kopchuk、Pavel A. Slepukhin、Yaroslav K. Shtaitz、Igor A. Khalymbadzha、Igor S. Kovalev、Grigory A. Kim、Ilya N. Ganebnykh、Grigory V. Zyryanov、Oleg N. Chupakhin、Valery N. Charushin

  DOI：10.1016/j.mencom.2021.07.035

  日期：2021.7

  of 6-aryl-5-cyano-3-(pyridin-2-yl)-1,2,4-triazines with 2-amino-4-aryloxazoles proceeds as the inverse demand Diels–Alder reaction between the oxazole moiety as dienophile and the 1,2,4-triazine moiety as diene to construct new 4,5-diaryl-6-cyano-3-hydroxypyridin-2-yl fragment. A reaction mechanism is proposed, and the structure of the key-product is proved by the X-ray diffraction analysis.

  6-芳基-5-氰基-3-(吡啶-2-基)-1,2,4-三嗪与2-氨基-4-芳基恶唑的高温偶联随着恶唑部分之间的逆向狄尔斯-阿尔德反应而进行作为亲二烯体和 1,2,4-三嗪部分作为二烯构建新的 4,5-diaryl-6-cyano-3-hydroxypyridin-2-yl 片段。提出了反应机理，并通过X射线衍射分析证明了关键产物的结构。
• 5-Aryl-2,2′-bipyridines bearing fluorinated anilines residues at C6 position: synthesis and photophysical properties
  作者：Dmitry S. Kopchuk、Ekaterina S. Starnovskaya、Yaroslav K. Shtaitz、Albert F. Khasanov、Grigory A. Kim、Emiliya V. Nosova、Alexey P. Krinochkin、Grigory V. Zyryanov、Vladimir L. Rusinov、Oleg N. Chupakhin

  DOI：10.1007/s11164-020-04182-z

  日期：2020.8

  A convenient synthetic approach to 5-aryl-2,2′-bipyridines bearing a (poly)fluorine-containing aniline residue at position C6 based on sequential ipso-substitution of the cyano group at position C5 of 3-(2-pyridyl)-1,2,4-triazines and the aza-Diels–Alder reaction has been proposed. The influence of the number and the position of the fluorine atoms on the reactivity of fluoroanilines has been estimated by means of DFT calculations. It was shown that the reaction cannot be realized if a nitro group is present in the ortho-position or two fluorine atoms occupied the ortho-positions in aniline. Photophysical properties of prospective “push–pull” fluorophores have been studied. Incorporation of fluorine atom into position 4 of aniline fragment in 5-p-tolylbipyridines causes small bathochromic shift of emission maximum, whereas the replacement of the methoxy group at the position C4 of the aniline moiety in 5-(4-methoxyphenyl)-2,2′-bipyridine with fluorine atom leads to a significant hypsochromic shift of emission maximum and to significant increase in quantum yield; the positive solvatochromism has been observed.

  基于 3-(2-吡啶基)-1,2,4-三嗪 C5 位氰基的顺序同位取代和偶氮-Diels-Alder 反应，提出了一种在 C6 位含有（多）含氟苯胺残基的 5-芳基-2,2′-联吡啶的简便合成方法。通过 DFT 计算，估算了氟原子的数量和位置对氟苯胺反应性的影响。结果表明，如果苯胺的正交位置存在一个硝基或两个氟原子占据正交位置，则无法实现反应。对未来 "推拉 "荧光团的光物理特性进行了研究。在 5 对甲苯联吡啶中苯胺片段的第 4 位掺入氟原子会导致发射最大值发生微小的浴色偏移，而在 5-（4-甲氧基苯基）-2,2′-联吡啶中，用氟原子取代苯胺分子第 C4 位的甲氧基会导致发射最大值发生明显的低色偏移，并显著增加量子产率；还观察到了正溶解色。
• Solvent-free synthesis of 5-(aryl/alkyl)amino-1,2,4-triazines and α-arylamino-2,2′-bipyridines with greener prospects
  作者：Dmitry S. Kopchuk、Nikolay V. Chepchugov、Igor S. Kovalev、Sougata Santra、Matiur Rahman、Kousik Giri、Grigory V. Zyryanov、Adinath Majee、Valery N. Charushin、Oleg N. Chupakhin

  DOI：10.1039/c6ra26305d

  日期：——

  A green and highly efficient method has been developed for the synthesis of 5-(aryl/alkyl)amino-1,2,4-triazines and α-arylamino-2,2′-bipyridines according to the principles of atom economy. It has been performed by two consecutive solvent-free reaction pathways: the ipso-substitution of a cyano-group in 5-cyano-1,2,4-triazines and the aza-Diels-Alder reaction of the resulting 5-arylamino-1,2,4-triazines

  根据原子经济性的原理，已经开发出一种绿色且高效的方法来合成5-（芳基/烷基）氨基-1,2,4-三嗪和α-芳基氨基-2,2'-联吡啶。它是通过两个连续的无溶剂反应途径进行的：5-氰基1,2,4-三嗪中氰基的ipso取代和所得5-芳基氨基-1的aza-Diels-Alder反应带有2-吗啉代环戊烯的2,4-三嗪用作亲二烯体。该方法的显着优点是无溶剂和无催化剂条件，操作简便，与各种官能团的相容性，非色谱纯化技术和高收率。本方法具有低的E因子。
• 1 <i>H</i> ‐Pyrazole‐Appended Pyridines and Their 1,2,4‐Triazine Precursors: A Rational Synthesis and <i>in silico</i> and <i>in vitro</i> Evaluation of Anti‐Cancer Activity
  作者：Alexey P. Krinochkin、Yaroslav K. Shtaitz、Aluru Rammohan、Ilya I. Butorin、Maria I. Savchuk、Igor A. Khalymbadzha、Dmitry S. Kopchuk、Pavel A. Slepukhin、Vsevolod V. Melekhin、Anna V. Shcheglova、Grigory V. Zyryanov、Oleg N. Chupakhin

  DOI：10.1002/ejoc.202200227

  日期：2022.6.13

  A straightforward one-pot pathway for the preparation of pyrazole-appended pyridines was developed. The most promising compound exhibited considerable cytotoxicity with IC50 values <50 μM in A-172 and HepG2 cell lines.

  开发了一种直接的一锅法制备吡唑附加的吡啶。最有希望的化合物在 A-172 和 HepG2 细胞系中表现出相当大的细胞毒性，IC 50值 <50 μM。