6,9-dihydro-7-pyrrolidino-5H-benzocycloheptene | 123792-58-5

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 6,9-dihydro-7-pyrrolidino-5H-benzocycloheptene
• 英文别名: 1-(8,9-dihydro-5H-benzo[7]annulen-7-yl)pyrrolidine
• CAS: 123792-58-5
• 化学式: C₁₅H₁₉N
• 分子量: 213.323
• InChiKey: MOGFOMLMUAKMAF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  6,9-dihydro-7-pyrrolidino-5H-benzocycloheptene 、 5-硝基嘧啶 以 乙醇 为溶剂， 反应 24.0h， 以80%的产率得到10,11-dihydro-3-nitro-5H-benzo<4,5>cyclohepta<1,2-b>pyridine
  参考文献：
  名称：

  5-硝基嘧啶与烯胺的电子反需求狄尔斯-阿尔德反应。3-硝基吡啶衍生物的合成

  摘要：

  已经研究了环状和非环状烯胺与5-硝基嘧啶的反应。许多烯胺以反电子需求的狄尔斯-阿尔德反应进行反应，导致形成3-硝基吡啶。还发现N，S-乙烯酮缩醛与5-硝基嘧啶反应。将讨论该反应的机理。

  DOI：

  10.1016/s0040-4020(01)80099-5
• 作为产物：
  描述：

  四氢吡咯 、 5,6,8,9-四氢-苯并环庚烯-7-酮 在 对甲苯磺酸 作用下， 以 甲苯 为溶剂， 反应 7.0h， 生成 6,9-dihydro-7-pyrrolidino-5H-benzocycloheptene
  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

• MARCELIS, A. T. M.;VAN, DER PLAS H. C., TETRAHEDRON, 45,(1989) N, C. 2693-2702
  作者：MARCELIS, A. T. M.、VAN, DER PLAS H. C.

  DOI：——

  日期：——
• Inverse electron demand diels-alder reactions of 5-nitropyrimidine with enamines. synthesis of 3-nitropyridine derivatives
  作者：Antonius T.M. Marcelis、Henk C. Van Der Plas

  DOI：10.1016/s0040-4020(01)80099-5

  日期：1989.1

  The reaction of cyclic and non-cyclic enamines with 5-nitropyrimidine has been studied. Many enamines react in an inverse electron-demand Diels-Alder reaction, leading to the formation of 3-nitropyridines. N,S-ketene acetals were also found to react with 5-nitropyrimidine. The mechanism of the reaction will be discussed.

  已经研究了环状和非环状烯胺与5-硝基嘧啶的反应。许多烯胺以反电子需求的狄尔斯-阿尔德反应进行反应，导致形成3-硝基吡啶。还发现N，S-乙烯酮缩醛与5-硝基嘧啶反应。将讨论该反应的机理。
• 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.