5H-benzocyclohepta[6,5-a]azulene | 477760-74-0

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 5H-benzocyclohepta[6,5-a]azulene
• 英文别名: Tetracyclo[9.8.0.02,7.012,18]nonadeca-1(19),2,4,6,9,11,13,15,17-nonaene
• CAS: 477760-74-0
• 化学式: C₁₉H₁₄
• 分子量: 242.32
• InChiKey: PTYAKKSGAPUZFT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 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：

  5H-benzocyclohepta[6,5-a]azulene 在 TrBF₄ 作用下， 以 二氯甲烷 为溶剂， 反应 27.0h， 以96%的产率得到
  参考文献：
  名称：

  Synthesis, Stability, and Spectroscopic and Electronic Properties of Three Benzocyclohepta[a]azulenylium Ions¹

  摘要：

  Novel pi-systems, three benzocyclohepta[a]azulenylium ions, 7a-c, are synthesized, and their stability and properties have been characterized in terms of the position of the benzo-annulation and compared with those of the parent cyclohepta[a]azulenylium ion 4. Benzocyclohepta[6,7-a]azulenylium ion (7a) (pK(R+) = 7.3,E-red = -0.567 V vs Ag/Ag+) and benzocyclohepta[6,5-a]azulenylium ion (7b) ( pK(R+) = 5.1, E-red = - 0.482 V vs Ag/Ag+), which are annulated with benzene on the position having a high bond order of 4, are not appreciably destabilized compared with cyclohepta[a]azulenylium ion (4) (pK(R+) = 7.3, E-red = -0.458 V vs Ag/Ag+). On the other hand, benzocyclohepta[7,6-a]azulenylium ion (7c) (pK(R+) = 1.6, E-red = -0.197 V vs Ag/Ag+) is considerably destabilized, probably due to enhanced contribution of the quinoid structure of the benzene ring, which is annulated on the position having a low bond order of the cyclohepta[a]azulenylium ion moiety. Furthermore, the cations 7a and 7b are more stable than 12,13-dihydrobenzocyclohepta[7,6-a]azulenylium ion (25) (pK(R+) = 4.8, E-red = -0.513 V vs Ag/Ag+), which is a dihydrogenated compound of 7a, while 7c is less stable than 25. These features are reflected in the considerable red shift of the longest absorption maximum of the electronic spectrum of 7c, as compared with those of 4, 7a, and 7b, and in the chemical shifts of the protons and their coupling constants of the H-1 NMR spectra. Furthermore, the H-1 NMR spectra and electronic spectra of 5H-benzocyclohepta[6,7-a]azulen-5-one (8a) and 7H-benzocyclohepta[6,5-a]azulen-7-one (8b) in acidic media have also been studied to clarify the spectral characteristics similar to those of 7a and 7b.

  DOI：

  10.1021/jo020136a
• 作为产物：
  描述：

  12,13-dihydro-5H-benzocyclohepta[6,5-a]azulene 在 吡啶 、 sodium tetrahydroborate 、 cerium(III) chloride 、 对甲苯磺酰氯 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 乙醇 、 水 、 丙酮 为溶剂， 反应 46.25h， 生成 5H-benzocyclohepta[6,5-a]azulene
  参考文献：
  名称：

  Synthesis, Stability, and Spectroscopic and Electronic Properties of Three Benzocyclohepta[a]azulenylium Ions¹

  摘要：

  Novel pi-systems, three benzocyclohepta[a]azulenylium ions, 7a-c, are synthesized, and their stability and properties have been characterized in terms of the position of the benzo-annulation and compared with those of the parent cyclohepta[a]azulenylium ion 4. Benzocyclohepta[6,7-a]azulenylium ion (7a) (pK(R+) = 7.3,E-red = -0.567 V vs Ag/Ag+) and benzocyclohepta[6,5-a]azulenylium ion (7b) ( pK(R+) = 5.1, E-red = - 0.482 V vs Ag/Ag+), which are annulated with benzene on the position having a high bond order of 4, are not appreciably destabilized compared with cyclohepta[a]azulenylium ion (4) (pK(R+) = 7.3, E-red = -0.458 V vs Ag/Ag+). On the other hand, benzocyclohepta[7,6-a]azulenylium ion (7c) (pK(R+) = 1.6, E-red = -0.197 V vs Ag/Ag+) is considerably destabilized, probably due to enhanced contribution of the quinoid structure of the benzene ring, which is annulated on the position having a low bond order of the cyclohepta[a]azulenylium ion moiety. Furthermore, the cations 7a and 7b are more stable than 12,13-dihydrobenzocyclohepta[7,6-a]azulenylium ion (25) (pK(R+) = 4.8, E-red = -0.513 V vs Ag/Ag+), which is a dihydrogenated compound of 7a, while 7c is less stable than 25. These features are reflected in the considerable red shift of the longest absorption maximum of the electronic spectrum of 7c, as compared with those of 4, 7a, and 7b, and in the chemical shifts of the protons and their coupling constants of the H-1 NMR spectra. Furthermore, the H-1 NMR spectra and electronic spectra of 5H-benzocyclohepta[6,7-a]azulen-5-one (8a) and 7H-benzocyclohepta[6,5-a]azulen-7-one (8b) in acidic media have also been studied to clarify the spectral characteristics similar to those of 7a and 7b.

  DOI：

  10.1021/jo020136a

文献信息

• Synthesis, Stability, and Spectroscopic and Electronic Properties of Three Benzocyclohepta[<i>a</i>]azulenylium Ions¹
  作者：Kazuo Yamane、Hiroyuki Yamamoto、Makoto Nitta

  DOI：10.1021/jo020136a

  日期：2002.11.1

  Novel pi-systems, three benzocyclohepta[a]azulenylium ions, 7a-c, are synthesized, and their stability and properties have been characterized in terms of the position of the benzo-annulation and compared with those of the parent cyclohepta[a]azulenylium ion 4. Benzocyclohepta[6,7-a]azulenylium ion (7a) (pK(R+) = 7.3,E-red = -0.567 V vs Ag/Ag+) and benzocyclohepta[6,5-a]azulenylium ion (7b) ( pK(R+) = 5.1, E-red = - 0.482 V vs Ag/Ag+), which are annulated with benzene on the position having a high bond order of 4, are not appreciably destabilized compared with cyclohepta[a]azulenylium ion (4) (pK(R+) = 7.3, E-red = -0.458 V vs Ag/Ag+). On the other hand, benzocyclohepta[7,6-a]azulenylium ion (7c) (pK(R+) = 1.6, E-red = -0.197 V vs Ag/Ag+) is considerably destabilized, probably due to enhanced contribution of the quinoid structure of the benzene ring, which is annulated on the position having a low bond order of the cyclohepta[a]azulenylium ion moiety. Furthermore, the cations 7a and 7b are more stable than 12,13-dihydrobenzocyclohepta[7,6-a]azulenylium ion (25) (pK(R+) = 4.8, E-red = -0.513 V vs Ag/Ag+), which is a dihydrogenated compound of 7a, while 7c is less stable than 25. These features are reflected in the considerable red shift of the longest absorption maximum of the electronic spectrum of 7c, as compared with those of 4, 7a, and 7b, and in the chemical shifts of the protons and their coupling constants of the H-1 NMR spectra. Furthermore, the H-1 NMR spectra and electronic spectra of 5H-benzocyclohepta[6,7-a]azulen-5-one (8a) and 7H-benzocyclohepta[6,5-a]azulen-7-one (8b) in acidic media have also been studied to clarify the spectral characteristics similar to those of 7a and 7b.