5-cyano-6-(2-thienyl)-3-(2-pyridyl)-1,2,4-triazine | 517876-24-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 三嗪类
• 英文名称: 5-cyano-6-(2-thienyl)-3-(2-pyridyl)-1,2,4-triazine
• 英文别名: 3-Pyridin-2-yl-6-thiophen-2-yl-1,2,4-triazine-5-carbonitrile
• CAS: 517876-24-3
• 化学式: C₁₃H₇N₅S
• 分子量: 265.298
• InChiKey: RWIPOPJSXLCZGX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  104
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4-氟苯胺 、 5-cyano-6-(2-thienyl)-3-(2-pyridyl)-1,2,4-triazine 以 neat (no solvent) 为溶剂， 反应 13.0h， 生成 N‑(4‑fluorophenyl)‑1‑(pyridin‑2‑yl)‑4‑(thiophen‑2‑yl)‑6,7‑dihydro‑5H‑cyclopenta[c]pyridin‑3‑amine
  参考文献：
  名称：

  5-Aryl-2,2′-bipyridines bearing fluorinated anilines residues at C6 position: synthesis and photophysical properties

  摘要：

  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。

  DOI：

  10.1007/s11164-020-04182-z
• 作为产物：
  描述：

  (NE)-N-[(2E)-2-[(E)-pyridin-2-ylmethylidenehydrazinylidene]-2-thiophen-2-ylethylidene]hydroxylamine 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-(2-thienyl)-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

• A Versatile Strategy for the Synthesis of Functionalized 2,2‘-Bi- and 2,2‘:6‘,2‘ ‘-Terpyridines <i>via</i> Their 1,2,4-Triazine Analogues
  作者：Valery N. Kozhevnikov、Dmitry N. Kozhevnikov、Tatiana V. Nikitina、Vladimir L. Rusinov、Oleg N. Chupakhin、Manfred Zabel、Burkhard König

  DOI：10.1021/jo0267955

  日期：2003.4.1

  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.
• 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。