endo-2,3-diaza-10,10-dimethoxy-1,4-di(4'-methoxyphenyl)tricyclo[5.2.1.5,9]dec-2-ene | 440085-22-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: endo-2,3-diaza-10,10-dimethoxy-1,4-di(4'-methoxyphenyl)tricyclo[5.2.1.5,9]dec-2-ene
• 英文别名: (1S,2R,6S,7R)-10,10-dimethoxy-1,7-bis(4-methoxyphenyl)-8,9-diazatricyclo[5.2.1.02,6]dec-8-ene
• CAS: 440085-22-3
• 化学式: C₂₄H₂₈N₂O₄
• 分子量: 408.497
• InChiKey: KCUAWDRHFBGHLD-MESAYYPLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  61.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  endo-2,3-diaza-10,10-dimethoxy-1,4-di(4'-methoxyphenyl)tricyclo[5.2.1.5,9]dec-2-ene 以 d6-Benzene 为溶剂， 生成
  参考文献：
  名称：

  取代基对环偶氮烷烃热脱氮速率常数的显着影响：逐步脱氮机理的有力证据

  摘要：

  一系列具有各种芳基的7,7-二甲氧基-1,4-二芳基-2,3-二氮杂双环[2.2.1]庚-2-烯衍生物2（p -CNC ）的热脱氮速率（k）确定6 H 4，C 6 H 5，p -MeC 6 H 4，p -MeOC 6 H 4）以研究脱氮机理。线性相关性（- [R 的相对速率常数（日志之间= 0.988）  ķ相对脱氮反应的）和阿诺德的σ α •观察到苄基型自由基稳定的参数。但是，相对速率常数与取代基对所得单线双基自由基DR2寿命的影响无关。这些结果表明7,7-二甲氧基-2,3-二氮杂双环[2.2.1]庚-2-烯衍生物的脱氮速率决定步骤涉及逐步的CN键断裂。

  DOI：

  10.1071/ch10281
• 作为产物：
  描述：

  1,3-双(4-甲氧基苯基)1,3-丙二酮 在 三氟乙酸 palladium on activated charcoal 、 二苯基二硒醚 、 氢气 、 peroxodisulfate ion 、 肼 作用下， 反应 2.0h， 生成 endo-2,3-diaza-10,10-dimethoxy-1,4-di(4'-methoxyphenyl)tricyclo[5.2.1.5,9]dec-2-ene
  参考文献：
  名称：

  On the Electronic Character of Localized Singlet 2,2-Dimethoxycyclopentane-1,3-diyl Diradicals:  Substituent Effects on the Lifetime

  摘要：

  Photodenitrogenation of the diazenes 4 affords exclusively the housanes 5 through intramolecular cyclization of the spectrally detected and characterized singlet diradicals 3. The lifetime of singlet diradical 3, determined by transient absorption measurements, depends on the Y and Z substituents at the para position of the phenyl ring and has the following order: Y, Z = OMe, OMe > OMe, CN > CN, CN > OMe, H > Cl, Cl approximately CN, H approximately Me, Me > H, H. This unprecedented substituent effect reveals stabilization of the singlet 2,2-dimethoxycyclopentane-1,3-diyl diradicals 3 through radical, zwitterionic, pi-bonding, and hyperconjugative structures.

  DOI：

  10.1021/ja026301l

文献信息

• On the Electronic Character of Localized Singlet 2,2-Dimethoxycyclopentane-1,3-diyl Diradicals:  Substituent Effects on the Lifetime
  作者：Manabu Abe、Waldemar Adam、Michihiro Hara、Masanori Hattori、Tetsuro Majima、Masatomo Nojima、Kei Tachibana、Sachiko Tojo

  DOI：10.1021/ja026301l

  日期：2002.6.1

  Photodenitrogenation of the diazenes 4 affords exclusively the housanes 5 through intramolecular cyclization of the spectrally detected and characterized singlet diradicals 3. The lifetime of singlet diradical 3, determined by transient absorption measurements, depends on the Y and Z substituents at the para position of the phenyl ring and has the following order: Y, Z = OMe, OMe > OMe, CN > CN, CN > OMe, H > Cl, Cl approximately CN, H approximately Me, Me > H, H. This unprecedented substituent effect reveals stabilization of the singlet 2,2-dimethoxycyclopentane-1,3-diyl diradicals 3 through radical, zwitterionic, pi-bonding, and hyperconjugative structures.
• Notable Substituent Effects on the Rate Constant of Thermal Denitrogenation of Cyclic Azoalkanes: Strong Evidence for a Stepwise Denitrogenation Mechanism
  作者：Chizuko Ishihara、Manabu Abe

  DOI：10.1071/ch10281

  日期：——

  thermal denitrogenation rates (k) of a series of 7,7-dimethoxy-1,4-diaryl-2,3-diazabicyclo[2.2.1]hept-2-ene derivatives 2 with a variety of aryl groups (p-CNC6H4, C6H5, p-MeC6H4, p-MeOC6H4) were determined to investigate the denitrogenation mechanism. A linear correlation (r = 0.988) between the relative rate-constant (log krel) of the denitrogenation reaction and Arnold’s σα• parameter for benzylic-type

  一系列具有各种芳基的7,7-二甲氧基-1,4-二芳基-2,3-二氮杂双环[2.2.1]庚-2-烯衍生物2（p -CNC ）的热脱氮速率（k）确定6 H 4，C 6 H 5，p -MeC 6 H 4，p -MeOC 6 H 4）以研究脱氮机理。线性相关性（- [R 的相对速率常数（日志之间= 0.988）  ķ相对脱氮反应的）和阿诺德的σ α •观察到苄基型自由基稳定的参数。但是，相对速率常数与取代基对所得单线双基自由基DR2寿命的影响无关。这些结果表明7,7-二甲氧基-2,3-二氮杂双环[2.2.1]庚-2-烯衍生物的脱氮速率决定步骤涉及逐步的CN键断裂。