1-methyl-2-(naphthyl-α-azo)imidazole | 356522-75-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1-methyl-2-(naphthyl-α-azo)imidazole
• 英文别名: 1H-Imidazole, 1-methyl-2-(1-naphthalenylazo)-；(1-methylimidazol-2-yl)-naphthalen-1-yldiazene
• CAS: 356522-75-3
• 化学式: C₁₄H₁₂N₄
• 分子量: 236.276
• InChiKey: QGYBVVUDSGGXRP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  dicarbonyldichlororuthenium 、 1-methyl-2-(naphthyl-α-azo)imidazole 以 乙腈 为溶剂， 反应 6.0h， 以72%的产率得到
  参考文献：
  名称：

  Ru(II)–halide–carbonyl complexes of naphthylazoimidazoles: Synthesis, spectra, electrochemistry, catalytic activity and electronic structure

  摘要：

  [Ru(CO)(2)Cl-2(alpha/beta-NaiR)] (1, 2) and [Ru(CO)(2)I-2(alpha/beta-NaiR)] (3, 4) are synthesized by the reaction of [Ru(CO)(2)Cl-2](n) or [Ru(CO)(4)I-2] with alpha/beta-NaiR (1-alkyl-2-(naphthyl-alpha/beta-azo)imidazole (alpha-NaiR/beta-NaiR, where, R = Me, CH2CH3 and CH2Ph)) and have been characterized by spectroscopic data. The geometry of the representative complexes [Ru(CO)(2)Cl-2(beta-NaiMe)] (2a) and [Ru(CO)(2)I-2(beta-NaiEt)] (4b) have been structurally confirmed by X-ray diffraction study. The redox property is examined by electrochemistry. Catalytic activity of these compounds is investigated to the oxidation of PhCH2OH to PhCHO, 2-butanol (C4H9OH) to 2-butanone, 1-phenylethanol (PhC2H4OH) to acetophenone, cyclopentanol (C5H9OH) to cyclopentanone and cyclohexanol to cyclohexanone by N-methylmorpholine-N-oxide (NMO), H2O2 or (BuOOH)-O-t in CH2Cl2 and NMO shows highest yield. The catalytic efficiency is again dependent on Ru-X (X = Cl or I) bond and higher yield is observed for [Ru(CO)(2)Cl-2(alpha/beta-NaiR)] (1, 2). Electronic structure, spectral and redox properties are explained based on DFT and TD-DFT calculations on the representative complexes. (C) 2012 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2012.06.009

文献信息

• Rhodium(III) supported amination reaction of a pendant naphthyl group: Structure, electrochemistry and theoretical interpretation
  作者：Dibakar Sardar、Papia Datta、Rajat Saha、Raghavaiah Pallepogu、Chittaranjan Sinha

  DOI：10.1016/j.poly.2019.07.045

  日期：2019.10

  Abstract [Rh(α-NaiR)2Cl2]ClO4 (2) (α-NaiR (1), 1-alkyl-2-(naphthyl-α-azo)imidazoles, R = Me (a), Et (b)) complexes react with ArNH2 (where Ar = X C6H4 , X = H (3), Me (4), Cl (5)) to synthesize the naphthyl appended C N fused bis-[1-alkyl-2-(7-imidoaryl)naphthyl-α-azo}imidazole-N,N′,N″]rhodium(III)perchlorate complexes [Rh(α-NaiR N Ar)2]ClO4 (3–5). The single crystal X-ray diffraction measurements

  摘要[Rh（α-NaiR）2Cl2] ClO4（2）（α-NaiR（1），1-烷基-2-（萘基-α-偶氮）咪唑，R = Me（a），Et（b））配合物与ArNH2反应（其中Ar = X C6H4，X = H（3），Me（4），Cl（5））合成萘基附加的CN稠合双-[1-烷基-2-（7-亚氨基芳基）萘基-α-偶氮}咪唑-N，N'，N'']高氯酸铑（III）络合物[Rh（α-NaiRN Ar）2] ClO4（3-5）。配合物之一[Rh（α-NaiEtN C6H5）2] ClO4（3b）的单晶X射线衍射测量证实了结构。与前体2在500 nm处的跃迁相比，配合物3-5的吸收光谱在650-800 nm处显示出高强度的宽广多重跃迁，DFT计算已将该跃迁归为LLCT的混合物（配体-配体电荷转移，亚氨基芳基→氮杂萘基）和LMCT过渡。
• Ru(II)–halide–carbonyl complexes of naphthylazoimidazoles: Synthesis, spectra, electrochemistry, catalytic activity and electronic structure
  作者：Shyamal Kumar Sarkar、Mahendra Sekhar Jana、Tapan Kumar Mondal、Chittaranjan Sinha

  DOI：10.1016/j.jorganchem.2012.06.009

  日期：2012.10

  [Ru(CO)(2)Cl-2(alpha/beta-NaiR)] (1, 2) and [Ru(CO)(2)I-2(alpha/beta-NaiR)] (3, 4) are synthesized by the reaction of [Ru(CO)(2)Cl-2](n) or [Ru(CO)(4)I-2] with alpha/beta-NaiR (1-alkyl-2-(naphthyl-alpha/beta-azo)imidazole (alpha-NaiR/beta-NaiR, where, R = Me, CH2CH3 and CH2Ph)) and have been characterized by spectroscopic data. The geometry of the representative complexes [Ru(CO)(2)Cl-2(beta-NaiMe)] (2a) and [Ru(CO)(2)I-2(beta-NaiEt)] (4b) have been structurally confirmed by X-ray diffraction study. The redox property is examined by electrochemistry. Catalytic activity of these compounds is investigated to the oxidation of PhCH2OH to PhCHO, 2-butanol (C4H9OH) to 2-butanone, 1-phenylethanol (PhC2H4OH) to acetophenone, cyclopentanol (C5H9OH) to cyclopentanone and cyclohexanol to cyclohexanone by N-methylmorpholine-N-oxide (NMO), H2O2 or (BuOOH)-O-t in CH2Cl2 and NMO shows highest yield. The catalytic efficiency is again dependent on Ru-X (X = Cl or I) bond and higher yield is observed for [Ru(CO)(2)Cl-2(alpha/beta-NaiR)] (1, 2). Electronic structure, spectral and redox properties are explained based on DFT and TD-DFT calculations on the representative complexes. (C) 2012 Elsevier B.V. All rights reserved.
• The C–H activation of pendant naphthyl group of 1-alkyl-2-(naphthyl-α-azo)imidazole by rhodium(III). Spectral, structural characterization and, DFT computation
  作者：Dibakar Sardar、Papia Datta、Rajat Saha、Pallepogu Raghavaiah、Chittaranjan Sinha

  DOI：10.1016/j.jorganchem.2013.02.013

  日期：2013.5

  The reaction of RhCl3 with 1-alkyl-2-(naphthyl-alpha-azo)imidazole (alpha-NaiR, N, N'chelator) (R = CH3, CH2 -CH3, CH2-Ph) has synthesized a coordination compound, [Rh(alpha-NaiR-N, N')(PPh3)Cl-3] (2) from boiling methanol in the presence of PPh3 while the reaction under similar condition in the presence of Et3N has synthesized cyclometallated complex, [Rh(alpha-NaiR-N, N', C)(PPh3)Cl-2] (3). The structures of both types of complexes are confirmed by single crystal X-ray diffraction study in representative cases. All the complexes have been characterized by spectral data (FT-IR, UV-VIS, MS, H-1-NMR) and elemental analyses. Density functional theory calculation has also been performed to rationalize the electronic structures and their spectral properties. (C) 2013 Elsevier B.V. All rights reserved.