4-methyl-2-(phenylazo)pyridine | 71291-88-8

• 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: 4-methyl-2-(phenylazo)pyridine
• 英文别名: 4-CH3-2-(phenylazo)pyridine；4-Methyl-2-phenylazopyridine；(4-methylpyridin-2-yl)-phenyldiazene
• CAS: 71291-88-8
• 化学式: C₁₂H₁₁N₃
• 分子量: 197.239
• InChiKey: AGRIMFUJVYBAFF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 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：

  4-methyl-2-(phenylazo)pyridine 在 三溴化磷 、 环己烯 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以91%的产率得到3-bromo-7-methyl-2-phenyl-2,3-dihydro-[1,2,4,3]triazaphospholo[4,5-a]pyridine
  参考文献：
  名称：

  环化 1,3,4,2-三氮杂磷烯 - 简单的模块化合成和配体性质的首次探索

  摘要：

  成功使用 1,3,4,2-三氮杂磷 (TAP) 作为有机催化剂强调了对这些分子的有效合成路线的需求。在本研究中，我们建立了 PBr 3的 [1 + 4]-环加成将偶氮吡啶作为一种从容易获得的前体一步制备吡啶并环化的 TAP 的新方法。通过伯胺和亚硝基化合物的缩合实现偶氮组分的模块化组装，以及在杂环结构保守的情况下在 P-Br 键上进行后官能化的可行性，原则上可以解决广泛的目标分子，这是通过原型示例说明的。过渡金属配合物的成功合成首次证实了 TAP 作为 P 供体配体的能力。晶体学研究表明，超共轭效应和分子间相互作用导致 TAP 中 P-Br 键的离子极化在质量上与众所周知的等电子二氮杂磷烯类似。

  DOI：

  10.3390/molecules27154747

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
• Iron carbonyl complexes of 2-(phenylazo)pyridines. First example of a six-electron, bridging 2-(phenylazo)pyridine ligand
  作者：Martin N. Ackermann、Jerome W. Naylor、Eric J. Smith、Gary A. Mines、Neelam S. Amin、Michael L. Kerns、Clifton Woods

  DOI：10.1021/om00041a026

  日期：1992.5

  2-(Phenylazo)pyridines (1a-c) react with Fe2(CO)9 in THF to produce two major products, red brown Fe(CO)3(L-L') (2a-c) and green Fe2(CO)2(L-L')3 (3a-c), where L-L' = 1a-c. A minor product with 3c is the lavender nitrene-capped complex Fe3(CO)9(mu-3-N(C6H5))(mu-3-N(2-(5-CF3C5H4N))) (4c). 3a also is obtained from the reaction of Fe(1a)3(PF6)2 and Na2Fe(CO)4 in THF. Hence, it is proposed that the first step in the formation of 3 from Fe2(CO)9 and 1 involves the disproportionation reaction Fe2(CO)9 + 31 --> Fe(1)3(2+) + Fe(CO)42- + 5CO. When 3c is chromatographed, it decomposes in part to 2-(2-phenylhydrazino)-5-(trifluoromethyl)pyridine, (5-CF3C5H3N)NHNHC6H5, in which the azo bond in 1c has been reduced to a hydrazine. Comparison of the infrared and visible spectra of 2 with those of analogous complexes of alpha-diimines indicates that the 2-PAP ligands are substantially better pi-acceptors than the alpha-diimines and that there is extensive mixing of the metal and ligand orbitals in the LUMO/HOMO orbitals of 2. H-1, C-13, and F-19 NMR data show that the three 2-PAP ligands in 3 are inequivalent. The diiron complex 3b crystallizes in the monoclinic space group P2(1)/n with a = 9.904 (2) angstrom, b = 19.069 (4) angstrom, c = 18.606 (2) angstrom, beta = 101.82 (2)-degrees, V = 3439.4 (15) angstrom3, and Z = 4. The two iron atoms are in different environments. One iron atom occupies an approximate octahedral environment that consists of three pyridine nitrogen atoms and three azo nitrogen atoms from three 4-CH3-2-PAP (1b) ligands. The second iron atom occupies a severely distorted octahedral environment that consists of two carbon monoxide carbon atoms and the four azo nitrogen atoms from two of the 4-CH3-2-PAP ligands. Two of the 4-CH3-2-PAP ligands bridge the two iron atoms with their azo linkages and serve as six-electron donors overall, while the other 4-CH3-2-PAP ligand acts as a conventional nonbridging four-electron donor. The azo bond lengths of the bridging ligands are comparable to those of an N-N single bond.
• 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.
• Annellated 1,3,4,2-Triazaphospholenes-Simple Modular Synthesis and a First Exploration of Ligand Properties
  作者：Ferdinand Richter、Nicholas Birchall、Christoph M. Feil、Martin Nieger、Dietrich Gudat

  DOI：10.3390/molecules27154747

  日期：——

  need for efficient synthetic routes to these molecules. In this study, we establish the [1 + 4]-cycloaddition of PBr3 to azo-pyridines as a new approach to preparing pyrido-annellated TAPs in a single step from easily available precursors. The modular assembly of the azo-component via condensation of primary amines and nitroso compounds along with the feasibility of post-functionalization at the P–Br

  成功使用 1,3,4,2-三氮杂磷 (TAP) 作为有机催化剂强调了对这些分子的有效合成路线的需求。在本研究中，我们建立了 PBr 3的 [1 + 4]-环加成将偶氮吡啶作为一种从容易获得的前体一步制备吡啶并环化的 TAP 的新方法。通过伯胺和亚硝基化合物的缩合实现偶氮组分的模块化组装，以及在杂环结构保守的情况下在 P-Br 键上进行后官能化的可行性，原则上可以解决广泛的目标分子，这是通过原型示例说明的。过渡金属配合物的成功合成首次证实了 TAP 作为 P 供体配体的能力。晶体学研究表明，超共轭效应和分子间相互作用导致 TAP 中 P-Br 键的离子极化在质量上与众所周知的等电子二氮杂磷烯类似。