6-methyl-2-(phenylazo)pyridine | 71291-81-1

• 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: 6-methyl-2-(phenylazo)pyridine
• 英文别名: 2-methyl-6-phenylazo-pyridine；6-CH3-2-(phenylazo)pyridine；(6-Methylpyridin-2-yl)-phenyldiazene；(6-methylpyridin-2-yl)-phenyldiazene
• CAS: 71291-81-1
• 化学式: C₁₂H₁₁N₃
• 分子量: 197.239
• InChiKey: PDALBSPENVXVIA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 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：

  6-methyl-2-(phenylazo)pyridine 在 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 作用下， 以 四氯化碳 为溶剂， 反应 12.0h， 以60%的产率得到
  参考文献：
  名称：

  通过Ni（ii）模板上的配体还原，使芳基胺官能化的钳状氮供体氧化还原非纯配体中的胺脱氢。

  摘要：

  我们合成了一系列新的氧化还原非纯偶氮芳族钳状配体：2-（苯基偶氮）-6-（芳基氨基甲基）吡啶（HLa-c：HLa = 2-（苯基偶氮）-6-（2,6-二异丙基苯基氨基甲基）吡啶，HLb = 2-（苯基偶氮）-6-（2,6-二甲基苯基氨基甲基）吡啶，HLc = 2-（苯基偶氮）-6-（苯基氨基甲基）吡啶），其中一个侧臂为芳基氨基甲基部分，另一个臂是2-苯基偶氮部分。通过在甲醇中以1：1摩尔比进行配体：（NiCl 2·6H 2 O）的反应，以良好的产率（约70％）合成了这些配体HLa-c的镍（ii）配合物1-3。每个配体HLa-c中的胺供体均与Ni（ii）中心结合，而没有去质子化。在固态下，配合物3为二聚体；在溶液中它以单体3a的形式存在。分别减少每个配合物1、2和3a的乙腈溶液，用钴（1当量），然后将溶液暴露于空气，分别形成新的配合物7、8和9。除了配合物7和8之外，还分别从配合物1和2的反

  DOI：

  10.1039/d0dt00466a
• 作为产物：
  描述：

  2-氨基-6-甲基吡啶 、 亚硝基苯 在 sodium hydroxide 作用下， 以 苯 为溶剂， 反应 8.0h， 以70%的产率得到6-methyl-2-(phenylazo)pyridine
  参考文献：
  名称：

  通过Ni（ii）模板上的配体还原，使芳基胺官能化的钳状氮供体氧化还原非纯配体中的胺脱氢。

  摘要：

  我们合成了一系列新的氧化还原非纯偶氮芳族钳状配体：2-（苯基偶氮）-6-（芳基氨基甲基）吡啶（HLa-c：HLa = 2-（苯基偶氮）-6-（2,6-二异丙基苯基氨基甲基）吡啶，HLb = 2-（苯基偶氮）-6-（2,6-二甲基苯基氨基甲基）吡啶，HLc = 2-（苯基偶氮）-6-（苯基氨基甲基）吡啶），其中一个侧臂为芳基氨基甲基部分，另一个臂是2-苯基偶氮部分。通过在甲醇中以1：1摩尔比进行配体：（NiCl 2·6H 2 O）的反应，以良好的产率（约70％）合成了这些配体HLa-c的镍（ii）配合物1-3。每个配体HLa-c中的胺供体均与Ni（ii）中心结合，而没有去质子化。在固态下，配合物3为二聚体；在溶液中它以单体3a的形式存在。分别减少每个配合物1、2和3a的乙腈溶液，用钴（1当量），然后将溶液暴露于空气，分别形成新的配合物7、8和9。除了配合物7和8之外，还分别从配合物1和2的反

  DOI：

  10.1039/d0dt00466a

文献信息

• 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
• Hemilabile Amine-Functionalized Efficient Azo-Aromatic Cu-Catalysts Inspired by Galactose Oxidase: Impact of Amine Sidearm on Catalytic Aerobic Oxidation of Alcohols
  作者：Manas Khatua、Bappaditya Goswami、Shivali Hans、Kamal、Shivnath Mazumder、Subhas Samanta

  DOI：10.1021/acs.inorgchem.2c03087

  日期：2022.11.7

  fashion in the catalytic cycle. The amine sidearm in the ligand backbone of the complexes has a significant role in catalytic activity. Complexes with amine sidearms are more effective than complexes without them. Moreover, the aliphatic secondary amine sidearm is more efficient among the amine sidearm than the aromatic secondary amine and tertiary amines. The amine sidearm that remained coordinated

  一系列偶氮芳族铜 (II) 配合物 [ 1a-g ] 和 Cu(I) 配合物 [ 1h ]，具有不同的胺官能化半可比钳状 [ HL 1 – 3 ] 和 [ L 1 , 2 ]、甲基取代的偶氮[ L 3 ]和亚胺[ L 4 ]配体的合成和表征。研究了这些配合物在 2.0 mol% 预催化剂 [ 1a-g ]、二茂钴 (2.0 mol%)、N-甲基咪唑 (NMI) (8.0 mol%) 和 TEMPOH ( 2.0 mol %) 在室温下。Cu(I) 配合物 ( 1h) 在不存在钴茂的情况下充当催化剂。为了理解机理，对代表性配合物 [ 1a ]进行了详细的实验和理论研究，这提出了一种涉及 Cu(II)/Cu(I) 氧化还原对的新机理。Cobaltocene 可作为 [ 1a的还原剂] 生成 Cu(I) 络合物，在 NMI 存在下激活分子氧。TEMPOH 将一个氢原子转移到活化的分子氧上，产生
• Pyrido[1,2-<i>a</i>][1,2,4]triazol-3-ylidenes as a New Family of Stable Annulated <i>N</i>-Heterocyclic Carbenes: Synthesis, Reactivity, and Their Application in Coordination Chemistry and Organocatalysis
  作者：Yajun Ma、Siping Wei、Jingbo Lan、Jingzhi Wang、Rugang Xie、Jingsong You

  DOI：10.1021/jo801349d

  日期：2008.11.7

  General synthetic avenues to the pyrido-annulated triazolium salts with different steric and electronic properties have been developed. This architecture can be readily altered with different N-alkyl or aryl substituents at the N2 position of the triazole ring and modifications to the pyridine backbone. Deprotonation of the triazolium salts 12 with NaH led to formation of stable carbenes 11 at room temperature as clearly demonstrated through ESI mass spectra and by observation of the characteristic C-13 NMR resonance for the carbene carbon at delta = 202-208 ppm. In sharp contrast, treatment of these triazolium salts with K2CO3 led to dimerization of free carbenes 11. The dimeric enetetramine (11b)(2) Could react with elemental sulfur to deliver the corresponding thiourea 16 in toluene at 80 degrees C in good yield. A silver complex with the pyrido[1,2-a][1,2,4]triazol-3-ylidene is described, and the molecular structure of complex 17 was established by X-ray crystallography. The triazolium salts 12 turned out to be powerful catalysts in catalytic benzoin condensations and transesterifications at 25 degrees C. The catalytic activity was largely dependent on the steric and electronic nature of the R-1 and R-2 substituents of the triazolium salt. We rationalized that this type of triazolium-catalyzed benzoin condensations should undergo the "traditional" Breslow mechanism rather than the pathway of the dimer (11)(2) as the real catalytic species.
• 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.