6-(dimethylamino)azulene | 2048-68-2

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 6-(dimethylamino)azulene
• 英文别名: 6-(Dimethylamino)azulen；6-dimethylaminoazulene；6-N,N-Dimethylaminoazulen；6-Dimethylamino-azulen；N,N-Dimethylazulen-6-amine
• CAS: 2048-68-2
• 化学式: C₁₂H₁₃N
• 分子量: 171.242
• InChiKey: PAPKSPMVQCNFHF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2921499090

反应信息

• 作为反应物：
  描述：

  6-(dimethylamino)azulene 在 hexafluorophosphoric acid 、 溶剂黄146 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 生成 [6-(dimethylamino)-1-azulenyl]bis[4-(dimethylamino)phenyl]methyl hexafluorophosphate
  参考文献：
  名称：

  Tris[6-(dimethylamino)-1-azulenyl]methyl Hexafluorophosphate. Extremely Stable Methyl Cation with the Highest pK_R⁺ Value

  摘要：

  Extremely stable carbocations, tris[6-(dimethylamino)- and 6-morpholino-1-azulenyl]methyl (2e and 2f), bis[6-(dimethylamino)-1-azulenyl][4-(dimethylamino)phenyl]methyl (3e), and [6-(dimethylamino)-1-azulenyl]bis[4-(dimethylamino)phenyl]methyl (4e) cations, were prepared, and their properties were fully characterized. These cations showed extremely high stabilities with high pK(R)(+) values. The values of 2e and 3e were determined spectrophotometrically in DMSO/water as 24.3 +/- 0.3 and 21.5 +/- 0.2, respectively, which are higher than those of tri(1-azulenyl)methyl and di(1-azulenyl)phenylmethyl cations (2a and 3a) by 13.0 and 11.0 pK units. The value of 4e was determined to be 14.0 +/- 0.1 in 50% aqueous acetonitrile and 14.3 +/- 0.2 in DMSO/water, which is higher than that of (1-azulenyl)diphenylmethyl cation (4a) by 11.0-11.3 pK units. The extreme stability of these methyl cations is attributable to the dipolar structure of the azulene rings, in addition to the contribution of the mesomeric effect of three dimethylamino groups. The electrochemical reduction of 2e, 3e, and 4e showed a wave at -1.26, -1.22, and -1.14 V (V vs Ag/Ag+), respectively, upon cyclic voltammetry (CV). The relatively high reduction potentials, compared with those of unsubstituted parent 1-azulenylmethyl cations (2a, -0.78; 3a, -0.66; and 4a, -0.48 V), also exhibited the electrochemical stabilization of these methyl cations by the dimethylamino substituents. The oxidation of 2e, 3e, and 4e exhibited an irreversible, barely separated two-step, one-electron oxidation wave to generate a trication species at a potential range of 0.50-0.75 V upon CV.

  DOI：

  10.1021/jo990029p
• 作为产物：
  描述：

  吡喃-4-酮 在 氟硼酸钠 作用下， 生成 6-(dimethylamino)azulene
  参考文献：
  名称：

  Reactions of 3-substituted pentacyanines with cyclopentadienide and cyclononatetraenide anions

  摘要：

  DOI：

  10.1016/s0040-4039(01)84499-3

文献信息

• First Synthesis of 2-Heteroarylazulenes by the Electrophilic Substitution of Azulene with Triflate of N-Containing Heterocycles
  作者：Taku Shoji、Yuta Inoue、Shunji Ito、Tetsuo Okujima、Noboru Morita

  DOI：10.3987/com-11-12373

  日期：——

  and 5. Electrophilic substitution reactions are a very important and general methodology for the functionalization of aromatic compounds. In azulene derivatives, there are numerous reports for the electrophilic substitution reactions at the 1and 3-positions of the azulene ring. However, there are few reports on the functionalization of azulene derivatives at the 2-position utilizing electrophilic substitution

  通过亲电取代建立了 2-杂芳基天青烯衍生物的有效合成方法。6-二甲基氨基-1,3-二（甲硫基）薁（1a）与含氮杂芳烃的三氟甲磺酸酯在过量杂芳烃存在下进行反应，得到相应的2-二氢杂芳基薁衍生物3-7。除 4 和 5 外，通过在醇中用 KOH 处理，2-二氢杂芳基天青烯衍生物很容易转化为所需的 2-杂芳基天青烯衍生物 8-11。除 4 和 5 外。亲电取代反应是一种非常重要且通用的芳烃官能化方法化合物。在薁衍生物中，有许多关于薁环的 1 位和 3 位发生亲电取代反应的报道。然而，很少有关于利用亲电取代反应在 2 位上对 azulene 衍生物进行官能化的报道，因为 azulene 的 2 位是对亲电试剂的惰性位点。1962 年，Hafner 及其同事报道了 1,3-二烷基取代的 azulene 衍生物使用 DMF 和 POCl3 进行 Vilsmeier 甲酰化反应生成相应的 2-formyllazulenes，但与
• Synthesis and Properties of 6-Methoxy- and 6-Dimethylamino-1-methylthio- and 1,3-Bis(methylthio)azulenes and Triflic Anhydride-Mediated Synthesis of Their Biaryl Derivatives
  作者：Taku Shoji、Akifumi Maruyama、Mitsuhisa Maruyama、Shunji Ito、Tetsuo Okujima、Junya Higashi、Kozo Toyota、Noboru Morita

  DOI：10.1246/bcsj.20130275

  日期：2014.1.15

  6-Methoxy- and 6-dimethylaminoazulenes with methylthio groups at the 1- or 1,3-positions have been prepared by electrophilic substitution of the corresponding azulenes with DMSO in the presence of ...

  在 1- 或 1,3- 位具有甲硫基的 6-甲氧基-和 6-二甲氨基蕈烯已通过在 DMSO 存在下用 DMSO 亲电取代相应的芘烯来制备。
• Synthesis of 1-(pyridyl, quinolyl, and isoquinolyl)azulenes by Reissert–Henze type reaction
  作者：Taku Shoji、Kazuyuki Okada、Shunji Ito、Kozo Toyota、Noboru Morita

  DOI：10.1016/j.tetlet.2010.07.090

  日期：2010.9

  Azulene derivatives reacted with N-oxide of several heterocycles in the presence of trifluoromethanesulfonic anhydride (Tf2O) to afford 1-(pyridyl, quinolyl, and isoquinolyl)azulenes in good yield, respectively. In the case of the reaction with the 1-azulenyl methyl sulfide (12), 1,1′-biazulene derivative 13 was obtained under the similar reaction conditions. The first synthesis of unsymmetrical 1

  在三氟甲磺酸酐（Tf 2 O）存在下，Azulene衍生物与几个杂环的N-氧化物反应，分别以良好的产率得到1-（吡啶基，喹啉基和异喹啉基）azulenes。在与1-氮杂烯基甲基硫化物（12）反应的情况下，在相似的反应条件下获得1,1'-二氮杂烯衍生物13。还通过我们的新制备方法，在Tf 2 O存在下与吡啶反应进行亲电吡啶基化之后，通过我们的新制备方法建立了不对称的1,3-二（吡啶基）ul唑衍生物的第一个合成方法。
• Nonbenzenoid aromatic systems. X. Formation, nuclear magnetic resonance spectral identification, and reactions of both Meisenheimer type and methyleneazulenate anions
  作者：Richard N. McDonald、Herbert E. Petty、N. Lee Wolfe、Joseph V. Paukstelis

  DOI：10.1021/jo00927a020

  日期：1974.6
• Loehr, Hans-Gerd; Voegtle, Fritz, Chemische Berichte, 1985, vol. 118, # 3, p. 905 - 913
  作者：Loehr, Hans-Gerd、Voegtle, Fritz

  DOI：——

  日期：——