4,6-dibromo-benzotriazole

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并三唑类
• 英文名称: 4,6-dibromo-benzotriazole
• 英文别名: 4,6-dibromo-2H-benzotriazole
• 化学式: C₆H₃Br₂N₃
• 分子量: 276.918
• InChiKey: ORSPDIRKYTUZSC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  41.6
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  5,7-dibromobenzo-1,2,3,4-tetrazine 1,3-dioxide 在 tin(ll) chloride 作用下， 以 乙醇 、 乙酸乙酯 为溶剂， 以95%的产率得到4,6-dibromo-benzotriazole
  参考文献：
  名称：

  Release of Nitrosating Species in the Course of Reduction of Benzo-1,2,3,4-tetrazine 1,3-Dioxides

  摘要：

  The reduction of benzo-1,2,3,4-tetrazine 1,3-dioxides (BTDOs) 1 with Na2S2O4 or SnCl2 is suggested to proceed via intermediate N-nitrosobenzotriazoles 3 to afford benzotriazoles 2. The N-15-labeling experiments exhibit that the N-3 atom of the tetrazine ring is incorporated into the nitroso group of 3 that is ultimately released into solution. It is possible that the biological activity of BTDOs is due to their ability to release nitrosating species, i.e., N-nitrosotriazol 3 or HNO2, in the course of reduction.

  DOI：

  10.1021/ol026437o

文献信息

• Making endo-cyclizations favorable again: a conceptually new synthetic approach to benzotriazoles <i>via</i> azide group directed lithiation/cyclization of 2-azidoaryl bromides
  作者：Alexandra A. Ageshina、Gleb A. Chesnokov、Maxim A. Topchiy、Igor V. Alabugin、Mikhail S. Nechaev、Andrey F. Asachenko

  DOI：10.1039/c9ob00615j

  日期：——

  in aryl azides containing several bromine atoms. Furthermore, (2-bromophenyl)diazomethane undergoes similar cyclization to give an indazole. Thus, cyclizations of aryl lithiums containing an ortho–X = Y = Z group emerge as a new general approach for the synthesis of aromatic heterocycles. DFT computations suggested that the observed endo-selectivity applies to the anionic cyclizations of other functionalities

  尽管苯并三唑是重要的且无处不在，但目前仅有一种概念上的合成方法：将两个邻氨基与亲电氮原子桥连。在此，我们公开了新的可行的选择-将内获得2 azidoaryl lithiums -cyclization原位从2 azidoaryl溴化物。使用二十四个带有各种烷基，烷氧基，全氟烷基和卤素取代基的实例来说明反应的范围。我们发现叠氮化物基团的导向作用允许在含有几个溴原子的芳基叠氮化物中进行选择性的金属-卤素交换。此外，（2-溴苯基）重氮甲烷经历类似的环化以生成吲唑。因此，芳基锂的环化包含邻-X = Y = Z基团是合成芳族杂环的一种新的通用方法。DFT计算表明，观察到的内选择性适用于经历“ 1,1-加成”（即叠氮化物，重氮化合物和异腈）的其他官能团的阴离子环化反应。与此相反，与遵循“1,2-加成”图案（氰酸酯，硫氰酸酯，异氰酸酯，异硫氰酸酯，和腈）的杂原子官能团的环化反应倾向于外-cyclizat
• Does the partial molar volume of a solute reflect the free energy of hydrophobic solvation?
  作者：Anna Szymaniec-Rutkowska、Ewa Bugajska、Sławomir Kasperowicz、Kinga Mieczkowska、Agnieszka M. Maciejewska、Jarosław Poznański

  DOI：10.1016/j.molliq.2019.111527

  日期：2019.11

  thermal shift assay. According to the hierarchical clustering procedure, the excess volume, defined as the difference between the experimentally determined partial molar volume and the calculated in silico molecular volume, was found to be distant from any commonly used hydrophobicity descriptors of the ligand. The excess volume, however, properly predicts solute binding affinity. On the way, we have proved

  卤代杂环配体被广泛用作蛋白激酶的有效且经常选择性的抑制剂。然而，很少有游离配体的疏水溶剂化的确切贡献解释了有助于配体结合的自由能的相互作用的平衡。在这里，我们提出了一种基于体积数据的新实验方法，以估计配体的疏水性。我们已经针对一系列十种不同卤代的苯并三唑测试了该方法，并使用热移分析法评估了其与靶蛋白激酶CK2的结合亲和力。根据分级聚类程序，将多余体积定义为实验确定的部分摩尔体积与计算机计算得出的摩尔数之差发现分子体积与配体的任何常用疏水性描述符相距甚远。但是，过量会正确预测溶质结合亲和力。在途中，我们已经证明卤代苯并三唑与蛋白激酶CK2的结合主要是由疏水相互作用驱动的。
• Synthesis and Physico-Chemical Properties in Aqueous Medium of All Possible Isomeric Bromo Analogues of Benzo-1H-Triazole, Potential Inhibitors of Protein Kinases
  作者：Romualda Wąsik、Patrycja Wińska、Jarosław Poznański、David Shugar

  DOI：10.1021/jp301561x

  日期：2012.6.21

  In ongoing studies on the role of the individual bromine atoms of 4,5,6,7-tetrabromobenzotriazole (TBBt) in its relatively selective inhibition of protein kinase CK2 alpha, we have prepared all the possible two mono-, four di-, and two tri-bromobenzotriazoles and determined their physicochemical properties in aqueous medium. They exhibited a general trend of a decrease in solubility with an increase in the number of bromines on the benzene ring, significantly modulated by the pattern of substitution. For a given number of attached bromines, this was directly related to the electronic effects resulting from different sites of substitution, leading to marked variations of pK(a) values for dissociation of the triazole proton. Experimental data (pK(a), solubility) and ab initio calculations demonstrated that hydration of halogenated benzotriazoles is driven by a subtle balance of hydrophobic and polar interactions. The combination of QM-derived free energies for solvation and proton dissociations was found to be a reasonably good predictor of inhibitory activity of halogenated benzotriazoles vs CK2 alpha. Since the pattern of halogenation of the benzene ring of benzotriazole has also been shown to be one of the determinants of inhibitory potency vs some viruses and viral enzymes, the present comprehensive description of their physicochemical properties should prove helpful in efforts to elucidate reaction mechanisms, including possible halogen bonding, and the search for more selective and potent inhibitors.
• Itai; Miyake, Yakugaku Zasshi/Journal of the Pharmaceutical Society of Japan, 1942, vol. 62, p. 377
  作者：Itai、Miyake

  DOI：——

  日期：——
• US7635181B2
  申请人：——

  公开号：US7635181B2

  公开（公告）日：2009-12-22