3-chloro-2-(phenylazo)pyridine | 71291-91-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 3-chloro-2-(phenylazo)pyridine
• 英文别名: 4-chloro-2-(phenylazo)pyridine；4-Cl-2-(phenylazo)pyridine；3-Cl-azpy；(4-Chloropyridin-2-yl)-phenyldiazene
• CAS: 71291-91-3
• 化学式: C₁₁H₈ClN₃
• 分子量: 217.658
• InChiKey: KQZPXAULWDXKEA-UHFFFAOYSA-N

物化性质

• 沸点：
  354.2±27.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  37.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  [(η6-bip)OsI2]2 、 3-chloro-2-(phenylazo)pyridine 以 not given 为溶剂， 生成 [Os(η6-bip)(3-chloro-2-(phenylazo)pyridine)I]PF6
  参考文献：
  名称：

  Structure–activity relationships for organometallic osmium arene phenylazopyridine complexes with potent anticancer activity

  摘要：

  我们报告了 32 个半夹心苯并吡啶 OsII 炔配合物 [Os(δ-6-烯)(苯并吡啶)X]+ 的合成和表征，其中 X 是氯化物或碘化物，炔是对伞花烃或联苯，吡啶和苯基环含有各种取代基（F、Cl、Br、I、CF3、OH 或 NO2）。已测定了十种 X 射线晶体结构。对 A2780 人卵巢癌细胞的细胞毒性从纳摩尔浓度的高效力到无活性不等。一般来说，在吡啶环上的特定位置引入一个抽电子基团（如 F、Cl、Br 或 I）可显著提高细胞毒性活性和水溶性。将对伞花烃改为联苯，将单齿配体 X 从氯化物改为碘化物，也会显著提高活性。水解和 DNA 结合活化似乎不是主要的作用机制，因为高活性复合物 [Os(δ-6-bip)(2-F-azpy)I]PF6 (9) 和中度活性复合物 [Os(δ-6-bip)(3-Cl-azpy)I]PF6 (23) 都非常稳定，而且不溶于水。对锇在 A2780 人卵巢癌细胞中的辛醇-水分配系数（log P）和亚细胞分布的研究表明，细胞摄取和细胞器靶向在决定活性方面起着重要作用。虽然复合物 9 能诱导 A2780 细胞产生活性氧（ROS），但 ROS 水平在抗癌活性机制中似乎并不起作用。这一类有机金属锇配合物具有新颖而不寻常的特点，值得在设计新型抗癌药物方面进一步探索。

  DOI：

  10.1039/c1dt10937e

文献信息

• OSMIUM (II) ARENE AZO ANTI-CANCER COMPLEXES
  申请人：Fu Ying

  公开号：US20130040925A1

  公开（公告）日：2013-02-14

  The present invention relates to the use of certain osmium containing complexes such as cytotoxic agents particularly for the treatment of cancer. There is also provided novel osmium containing complexes, as well as pharmaceutical formulations comprising such complexes.

  本发明涉及使用某些含有钌的配合物，如细胞毒性药物，特别用于治疗癌症。还提供了新型含有钌的配合物，以及包括这些配合物的药物配方。
• Tetracarbonylmolybdenum complexes of 2-(phenylazo)pyridine ligands. Correlations of molybdenum-95 chemical shifts with electronic, infrared, and electrochemical properties
  作者：Martin N Ackermann、William G Fairbrother、Neelim S Amin、Charles J Deodene、Carl M Lamborg、Paul T Martin

  DOI：10.1016/0022-328x(96)06346-2

  日期：1996.10

  The complexes cis-Mo(CO)4(X-2-(phenylazo)pyridine) (X = 4-CH3O, 4-CH3, 4-Cl, 5-Br, 5-CF3, 6-CH3} and cis-Mo(CO)4(2-(2-CH3-phenylazo)pyridine) have been synthesized and characterized by cyclic voltammetry, by visible and infrared spectroscopy, and by 1H, 13C, and 95Mo NMR spectroscopy. The 95Mo chemical shift correlates with the lowest energy electronic transition, with the sum of the carbonyl stretching

  配合物顺式-Mo（CO）4（X-2-（苯基偶氮）吡啶）（X = 4-CH 3 O，4-CH 3，4 -Cl，5-Br，5-CF 3，6-CH合成了3 }和顺式-Mo（CO）4（2-（2-CH 3-苯基偶氮）吡啶），并通过循环伏安法，可见光和红外光谱以及1 H，13 C和95 Mo NMR进行了表征光谱学。95Mo化学位移与最低能量的电子跃迁，羰基拉伸频率的总和，第一氧化电位以及吡啶基取代基的Hammettσ参数相关。的复合物的失败顺-Mo（CO）4（6-CH 3 -2-（苯基偶氮）吡啶）和顺式-Mo（CO）4（2-（2--CH 3-苯基偶氮）吡啶）来拟合某些相关性归因于空间或电子效应。取代基对2-（苯基偶氮）吡啶的吡啶基环的作用似乎完全是通过σ键起作用的感应性基团。建议将2-（苯基偶氮）吡啶适当地视为偶氮基团具有较强的π-受体能力的配体，而吡啶基主要起吡啶的作用，其碱度因强吸电子而降低2
• [EN] OSMIUM (II) ARENE AZO ANTI-CANCER COMPLEXES<br/>[FR] COMPLEXES ANTICANCÉREUX D'OSMIUM(II)ARÈNE AZO
  申请人：UNIV WARWICK

  公开号：WO2011131925A3

  公开（公告）日：2012-03-29
• Synthesis and studies of cis-Mo(CO)2(L–L′)2 and Mo(L–L′)3 complexes of 2-(phenylazo)pyridines (L–L′) and the crystal structures of Mo(CO)2(4-methyl-2-(phenylazo)pyridine)2 and Mo(4-methyl-2-(phenylazo)pyridine)3
  作者：Martin N. Ackermann、Suzanne R. Kiihne、Patricia A. Saunders、Craig E. Barnes、Sarah C. Stallings、Hidong Kim、Clifton Woods、Michael Lagunoff

  DOI：10.1016/s0020-1693(02)00851-4

  日期：2002.5

  The complexes cis-Mo(CO)(2)(X-2-(phenylazo)pyridine)(2) (III) and Mo(X-2-(phenylazo)pyridine)(3) (IV) (X = 4-CH3O (a), 4-CH3 (b), H (c), 4-Cl (d), 5-Br (e), 5-CF3 (f), 6-CH3 (g)), cis-Mo(CO)(2)(2-(2-CH3-phenylazo)pyridine)(2) (IIIh), and Mo(2-(2-CH3-phenylazo)pyridine)(3) (IVh) have been synthesized and characterized by cyclic voltammetry, by visible and infrared spectroscopy, and by H-1, C-13, and Mo-95 NMR spectroscopy. Correlations among these data and correlations of the data with the Hammett sigma parameter within each series of complexes were investigated. Initially, correlations were found only for the Hammett sigma parameter with the first oxidation potential and with the first reduction potential for both the type III and type IV complexes and with the sum of the carbonyl stretching frequencies for the type III complexes. However, combining Mo-95 NMR linewidth and chemical shift data for this quadrupolar metal allowed separation of the nephelauxetic and spectrochemical effects and revealed a number of additional correlations. The X-ray crystal structures of cis-Mo(CO)(2)(4-CH3-2-(phenylazo)pyridine)(2) (IIIb) and Mo(4-CH3-2-(phenylazo)pyridine)(3) (IVb) also have been determined. In IIIb each CO is trans to a pyridyl nitrogen of a 2-(phenylazo)pyridine ligand. In IVb each pyridyl nitrogen is trans to an azo nitrogen, yielding the facial isomer of the complex. (C) 2002 Elsevier Science B.V. All rights reserved.
• Structure–activity relationships for organometallic osmium arene phenylazopyridine complexes with potent anticancer activity
  作者：Ying Fu、Abraha Habtemariam、Aida M. B. H. Basri、Darren Braddick、Guy J. Clarkson、Peter J. Sadler

  DOI：10.1039/c1dt10937e

  日期：——

  We report the synthesis and characterisation of 32 half sandwich phenylazopyridine OsII arene complexes [Os(η6-arene)(phenylazopyridine)X]+ in which X is chloride or iodide, the arene is p-cymene or biphenyl and the pyridine and phenyl rings contain a variety of substituents (F, Cl, Br, I, CF3, OH or NO2). Ten X-ray crystal structures have been determined. Cytotoxicity towards A2780 human ovarian cancer cells ranges from high potency at nanomolar concentrations to inactivity. In general the introduction of an electron-withdrawing group (e.g. F, Cl, Br or I) at specific positions on the pyridine ring significantly increases cytotoxic activity and aqueous solubility. Changing the arene from p-cymene to biphenyl and the monodentate ligand X from chloride to iodide also increases the activity significantly. Activation by hydrolysis and DNA binding appears not to be the major mechanism of action since both the highly active complex [Os(η6-bip)(2-F-azpy)I]PF6 (9) and the moderately active complex [Os(η6-bip)(3-Cl-azpy)I]PF6 (23) are very stable and inert towards aquation. Studies of octanol–water partition coefficients (log P) and subcellular distributions of osmium in A2780 human ovarian cancer cells suggested that cell uptake and targeting to cellular organelles play important roles in determining activity. Although complex 9 induced the production of reactive oxygen species (ROS) in A2780 cells, the ROS level did not appear to play a role in the mechanism of anticancer activity. This class of organometallic osmium complexes has new and unusual features worthy of further exploration for the design of novel anticancer drugs.

  我们报告了 32 个半夹心苯并吡啶 OsII 炔配合物 [Os(δ-6-烯)(苯并吡啶)X]+ 的合成和表征，其中 X 是氯化物或碘化物，炔是对伞花烃或联苯，吡啶和苯基环含有各种取代基（F、Cl、Br、I、CF3、OH 或 NO2）。已测定了十种 X 射线晶体结构。对 A2780 人卵巢癌细胞的细胞毒性从纳摩尔浓度的高效力到无活性不等。一般来说，在吡啶环上的特定位置引入一个抽电子基团（如 F、Cl、Br 或 I）可显著提高细胞毒性活性和水溶性。将对伞花烃改为联苯，将单齿配体 X 从氯化物改为碘化物，也会显著提高活性。水解和 DNA 结合活化似乎不是主要的作用机制，因为高活性复合物 [Os(δ-6-bip)(2-F-azpy)I]PF6 (9) 和中度活性复合物 [Os(δ-6-bip)(3-Cl-azpy)I]PF6 (23) 都非常稳定，而且不溶于水。对锇在 A2780 人卵巢癌细胞中的辛醇-水分配系数（log P）和亚细胞分布的研究表明，细胞摄取和细胞器靶向在决定活性方面起着重要作用。虽然复合物 9 能诱导 A2780 细胞产生活性氧（ROS），但 ROS 水平在抗癌活性机制中似乎并不起作用。这一类有机金属锇配合物具有新颖而不寻常的特点，值得在设计新型抗癌药物方面进一步探索。