endo-2,3-diaza-10,10-dimethoxy-1,4-diphenyltricyclo[5.2.1.5,9]dec-2-ene | 440085-24-5

• 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-diphenyltricyclo[5.2.1.5,9]dec-2-ene
• 英文别名: (1R,2S,6R,7S)-10,10-dimethoxy-1,7-diphenyl-8,9-diazatricyclo[5.2.1.02,6]dec-8-ene
• CAS: 440085-24-5
• 化学式: C₂₂H₂₄N₂O₂
• 分子量: 348.445
• InChiKey: YQGZJWBMCFZYQL-FXELSEDVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  43.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  endo-2,3-diaza-10,10-dimethoxy-1,4-diphenyltricyclo[5.2.1.5,9]dec-2-ene 以 d6-Benzene 为溶剂， 生成 5,5-dimethoxy-4,6-diphenyl-2,3,3a,6a-tetrahydro-1H-pentalen-4-ylium-6-ide
  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：

  2,2-dimethoxy-1,3-diphenyl-1,3-propanedione 在 三氟乙酸 palladium on activated charcoal 、 氢气 、 肼 作用下， 反应 2.0h， 生成 endo-2,3-diaza-10,10-dimethoxy-1,4-diphenyltricyclo[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

• Impact of Diradical Spin State (Singlet vs Triplet) and Structure (Puckered vs Planar) on the Photodenitrogenation Stereoselectivity of 2,3-Diazabicyclo[2.2.1]heptanes
  作者：Manabu Abe、Saori Tada、Takemi Mizuno、Katsuyoshi Yamasaki

  DOI：10.1021/acs.jpcb.6b05342

  日期：2016.7.28

  stereoselectivity was observed by low-temperature in situ NMR spectroscopy for the photochemical denitrogenation of a cyclic azoalkane (2,3-diazabicyclo[2.2.1]heptane) derivative. Direct (singlet) photodenitrogenation at 188 K afforded two products, the configurationally retained ring-closed compound (ret-CP) and the inverted compound (inv-CP), in a ratio of 82/18 (±3) (ret-CP/inv-CP), with an overall yield of

  偶氮化合物的多功能转化不仅用于合成有机化学，而且还用于材料科学。在这项研究中，迄今未知的立体选择性是通过低温原位NMR光谱对环状偶氮烷（2,3-二氮杂双环[2.2.1]庚烷）衍生物进行光化学脱氮而观察到的。在188 K进行直接（单次）光脱氮，得到两种产物，构型保留的闭环化合物（ret- CP）和倒置化合物（inv- CP），比率为82/18（±3）（ret- CP / inv- CP），总收率> 95％。使用二苯甲酮（3 BP *）或x吨酮（3Xan *）有选择地产生inv- CP，ret- CP / inv- CP比率为7/93（±3）。INV-的热异构化CP到ret- CP通过低温NMR光谱观察到。瞬态吸收光谱表明，直接光脱氮过程中CP的形成涉及两个不同的单线双自由基，即皱褶的puc- 1 DR和平面pl- 1 DR双自由基。前者产生ret- CP，而后者产生inv- CP。使用综合分
• 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。