tris(6-bromo-1-azulenyl)methane | 241166-19-8

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: tris(6-bromo-1-azulenyl)methane
• 英文别名: 1-[Bis(6-bromoazulen-1-yl)methyl]-6-bromoazulene
• CAS: 241166-19-8
• 化学式: C₃₁H₁₉Br₃
• 分子量: 631.204
• InChiKey: BLMABOZPXJSDDS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.3
• 重原子数：
  34
• 可旋转键数：
  3
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.03
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  tris(6-bromo-1-azulenyl)methane 在 hexafluorophosphoric acid 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 0.25h， 生成 tris[6-(1-morpholino)-1-azulenyl]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：

  6-溴薁 、 6-bromo-1-azulenecarbaldehyde 在 sodium acetate 、 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 40.0 ℃ 、999.99 MPa 条件下， 反应 24.0h， 以18%的产率得到tris(6-bromo-1-azulenyl)methane
  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