5-cyano-6-(4-methoxyphenyl)-3-(2-pyridyl)-1,2,4-triazine | 517876-23-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5-cyano-6-(4-methoxyphenyl)-3-(2-pyridyl)-1,2,4-triazine
• 英文别名: 6-(4-methoxyphenyl)-3-(pyridin-2-yl)-1,2,4-triazine-5-carbonitrile；6-(4-Methoxyphenyl)-3-pyridin-2-yl-1,2,4-triazine-5-carbonitrile
• CAS: 517876-23-2
• 化学式: C₁₆H₁₁N₅O
• 分子量: 289.296
• InChiKey: GPBIUBUJNJQTEB-UHFFFAOYSA-N

物化性质

• 沸点：
  587.1±60.0 °C(Predicted)
• 密度：
  1.35±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  84.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5-cyano-6-(4-methoxyphenyl)-3-(2-pyridyl)-1,2,4-triazine 在 水 、 sodium hydroxide 、 盐酸 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 3.17h， 以75%的产率得到6-(4-methoxyphenyl)-3-(pyridin-2-yl)-1,2,4-triazin-5(4H)-one
  参考文献：
  名称：

  从6-芳基1,2,4-丁三嗪-5-酮高效一步合成3-芳基-2-吡啶酮

  摘要：

  一种有效的合成取代的2-吡啶酮的方法，它基于1,2,4-三嗪-5-酮与二烯，2,5-降冰片二烯和4-（环戊-1-烯-）的氮杂-狄尔斯-阿尔德反应提出了1-基）吗啉。

  DOI：

  10.1007/s10593-019-02566-7
• 作为产物：
  描述：

  (4-Methoxy-phenyl)-{[1-pyridin-2-yl-meth-(E)-ylidene]-hydrazono}-acetaldehyde oxime 在 lead(II,IV) oxide 、 溶剂黄146 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 5-cyano-6-(4-methoxyphenyl)-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

• New Push-Pull Fluorophores on the Basis of 6-Alkoxy-2,2'-Bipyridines: Rational Synthetic Approach and Photophysical Properties
  作者：Maria I. Savchuk、Albert F. Khasanov、Dmitry S. Kopchuk、Alexey P. Krinochkin、Igor L. Nikonov、Ekaterina S. Starnovskaya、Yaroslav K. Shtaitz、Igor S. Kovalev、Grigory V. Zyryanov、Oleg N. Chupakhin

  DOI：10.1007/s10593-019-02495-5

  日期：2019.6

  We propose an effective synthetic approach to 2(6)-alkoxy(bi)pyridines as new push-pull fluorophores via their 1,2,4-triazine analogs. The photophysical properties of the new compounds were studied and the first study of their structure-property relationship was performed.

  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。
• 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。
• An Efficient Cyanide-Free Approach towards 1-(2-Pyridyl)isoquinoline-3-carbonitriles via the Reaction of 5-Phenacyl-1,2,4-triazines with 1,2-Dehydrobenzene in the Presence of Alkyl Nitrites
  作者：Sougata Santra、Dmitry Kopchuk、Alexey Krinochkin、Albert Khasanov、Igor Kovalev、Pavel Slepukhin、Ekaterina Starnovskaya、Anindita Mukherjee、Matiur Rahman、Grigory Zyryanov、Adinath Majee、Vladimir Rusinov、Oleg Chupakhin

  DOI：10.1055/s-0036-1590961

  日期：2018.3

  -1,2,4-triazines with 1,2-dehydrobenzene generated in situ from anthranilic acid and an excess of amyl nitrites afforded the target compounds in good yields. The proposed mechanism involves the in situ transformation of the 5-phenacyl group into the 5-cyano group under the action of alkyl nitrite and the following inverse demand aza-Diels–Alder reaction of thus formed 5-cyano-1,2,4-triazines with 1

  开发了一种用于制备 1-(2-pyridyl)isoquinoline-3-carbonitriles (3-cyanoisoquinolines) 的无氰化物方法。5-phenacyl-3-(2-pyridyl)-1,2,4-triazines 与由邻氨基苯甲酸和过量亚硝酸戊酯原位生成的 1,2-脱氢苯相互作用，以良好的产率得到目标化合物。所提出的机制涉及在亚硝酸烷基酯的作用下 5-苯酰基基团原位转化为 5-氰基基团，以及由此形成的 5-氰基-1,2,4- 的逆向需求 aza-Diels-Alder 反应三嗪与 1,2-脱氢苯反应得到目标产物。5-苯甲酰基取代基的存在是反应的关键，如在 5-苯乙烯基-或 5-苯基乙炔基-3-(2-吡啶基)-1,2,4-三嗪的情况下，1,2观察到,4-三嗪环转化产物
• 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。
• One-pot Synthesis and Photophysical Studies of Α-cycloamino-substituted 5-aryl-2,2'-bipyridines
  作者：Mallikarjuna R. Guda、Maria I. Valieva、Dmitry S. Kopchuk、Rammohan Aluru、Albert F. Khasanov、Olga S. Taniya、Alexander S. Novikov、Grigory V. Zyryanov、Brindaban C. Ranu

  DOI：10.1007/s10895-023-03304-1

  日期：2024.3

  A series of α-cycloamine substituted 2,2’-bipyridines 3ae’-3ce’ was obtained via the one-pot approach based on ipso-substitution of a cyano-group in 1,2,4-triazines, followed by aza-Diels–Alder reaction in good yields. Photophysical properties, including fluorosolvatochromism, were studied for 3ae’-3ce’ and were compared with α-unsubstituted 2,2’-bipyridines. In addition, dipole moments differences

  基于1,2,4-三嗪中氰基的原位取代，然后是氮杂-Diels，通过一锅法获得了一系列α-环胺取代的2,2'-联吡啶3ae'-3ce' – 桤木反应收率良好。研究了3ae'-3ce'的光物理性质，包括氟溶剂化显色现象，并与α -未取代的 2,2'-联吡啶进行比较。此外，通过 Lippert-Mataga 方程和 DFT 研究计算了基态和激发态的偶极矩差异，并进行了相互比较。观察到环胺单元的大小与偶极矩差值（基于Lippert-Mataga方程）之间的相关性。此外还计算了电荷转移指数（ D CT 、 Λ 、 H和t ）以证明分子结构对分子内电荷转移程度的影响。