trans-1,1'-azonorbornane N,N'-dioxide | 172017-23-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: trans-1,1'-azonorbornane N,N'-dioxide
• 英文别名: N,N'-dioxo-1,1'-azobis(norbornane)
• CAS: 172017-23-1
• 化学式: C₁₄H₂₂N₂O₂
• 分子量: 250.341
• InChiKey: VZSDDEXWWDANJW-FOCLMDBBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.12
• 重原子数：
  18.0
• 可旋转键数：
  2.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  52.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  trans-1,1'-azonorbornane N,N'-dioxide 在 六氯乙硅烷 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 生成 N,N'-Bis-bicyclo[2.2.1]hept-1-yl-diazene N-oxide
  参考文献：
  名称：

  氧化的反式偶氮烷与四氰基氨基乙烯的配合物。π氧偶极子与电子贫烯烃的相互作用。

  摘要：

  反式1,1'-偶氮降冰片烷（1）的N-氧化物和N，N'-二氧化物（1ao和1ado）与TCNE在溶液和固态下缔合。溶液配合物的特征是分别在1ao / TCNE和1ado / TCNE的CH（2）Cl（2）中在lambda（m）364和540 nm处进行电荷转移光学吸收。这些复合物是弱结合的，K（f）值为0.5-3.0 M（-）（1）。（1ao）（2）/ TCNE和1ado / TCNE的晶体是可分离的，其结构已通过X射线衍射确定。发现π偶极子供体与电子贫乏的TCNE之间存在局部供体-受体（DA）相互作用。（1ao）（2）/ TCNE的晶体由离散的DAD三元组组成，其中1ao氧比另一个（C（2），C）更接近TCNE的一个烯烃C原子（C（1），2.86Å）。 3.07Å）。OC（1）-C（2）角为87度，偶氮氧化物分子平面垂直于TCNE的分子平面。1ado / TCNE晶体由延伸的-DADA-

  DOI：

  10.1021/jo960998+
• 作为产物：
  描述：

  双环[2.2.1]庚烷-1-胺 在 sodium carbonate 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 以77%的产率得到trans-1,1'-azonorbornane N,N'-dioxide
  参考文献：
  名称：

  Azodioxide Radical Cations

  摘要：

  This report provides the first examples of solution-stable azodioxide radical cations and describes their direct spectroscopic observation and, in one case, their thermal chemistry. The formal oxidation potentials, Eo', for N,N*-dioxo-2,3-diazabicyclo[2.2.2]oct-2-ene (3), N,N'-dioxo-2,3-diazabicyclo[2.2.1]hept-2-ene (4), and N,N-dioxo-1,1'-azobis(norbornane) (5) are 1.65, 1.68, and 1.54 V vs SCE, respectively. ESR spectroscopy shows the intermediate cations to be pi radicals. Radical cation 5(.+) (red, lambda(m), 510 nm) has a five-line ESR spectrum of a(2N) 1.1 G, while 3(.+) (bronze) has a nine-line ESR spectrum simulated as a(4H) 0.86 and a(2N) 1.22 G. Both 3(.+) and 5(.+) decay in seconds to minutes at room temperature. Thermal decomposition of 5(.+) results in C,N and N,N bond cleavage, yielding 1-norbornyl cation (trapped by solvent) and NO+ (trapped in low yield by the oxidant under chemical oxidation conditions). Two viable mechanisms are presented for 5(.+)'s thermal decay, both of which invoke nitrosoalkane monomer 5m as an intermediate. In a related study, oxidation of nitrosoalkane 2m is found to mediate its facile denitrosation. This work affords the first examples of electron-transfer-mediated C,N band cleavage of azodioxides and of nitrosoalkanes. Substantial bond weakening is shown to accompany electron loss from these substrates. For 5, pi oxidation leads ultimately to a C,N bond activation.

  DOI：

  10.1021/ja00147a007

文献信息

• Azodioxide Radical Cations
  作者：Melinda L. Greer、Haripada Sarker、Maria E. Mendicino、Silas C. Blackstock

  DOI：10.1021/ja00147a007

  日期：1995.10

  This report provides the first examples of solution-stable azodioxide radical cations and describes their direct spectroscopic observation and, in one case, their thermal chemistry. The formal oxidation potentials, Eo', for N,N*-dioxo-2,3-diazabicyclo[2.2.2]oct-2-ene (3), N,N'-dioxo-2,3-diazabicyclo[2.2.1]hept-2-ene (4), and N,N-dioxo-1,1'-azobis(norbornane) (5) are 1.65, 1.68, and 1.54 V vs SCE, respectively. ESR spectroscopy shows the intermediate cations to be pi radicals. Radical cation 5(.+) (red, lambda(m), 510 nm) has a five-line ESR spectrum of a(2N) 1.1 G, while 3(.+) (bronze) has a nine-line ESR spectrum simulated as a(4H) 0.86 and a(2N) 1.22 G. Both 3(.+) and 5(.+) decay in seconds to minutes at room temperature. Thermal decomposition of 5(.+) results in C,N and N,N bond cleavage, yielding 1-norbornyl cation (trapped by solvent) and NO+ (trapped in low yield by the oxidant under chemical oxidation conditions). Two viable mechanisms are presented for 5(.+)'s thermal decay, both of which invoke nitrosoalkane monomer 5m as an intermediate. In a related study, oxidation of nitrosoalkane 2m is found to mediate its facile denitrosation. This work affords the first examples of electron-transfer-mediated C,N band cleavage of azodioxides and of nitrosoalkanes. Substantial bond weakening is shown to accompany electron loss from these substrates. For 5, pi oxidation leads ultimately to a C,N bond activation.
• Complexes of Oxygenated <i>trans</i>-Azoalkanes and Tetracyanoethylene. The Interaction of π Oxygen Dipoles with an Electron Poor Alkene
  作者：Melinda L. Greer、Silas C. Blackstock

  DOI：10.1021/jo960998+

  日期：1996.1.1

  state. The solution complexes are characterized by charge-transfer optical absorptions at lambda(m) 364 and 540 nm in CH(2)Cl(2) for 1ao/TCNE and 1ado/TCNE, respectively. These complexes are weakly bound, with K(f) values of 0.5-3.0 M(-)(1). Crystals of (1ao)(2)/TCNE and 1ado/TCNE are isolable, and their structures have been determined by X-ray diffraction. Local donor-acceptor (DA) interactions between

  反式1,1'-偶氮降冰片烷（1）的N-氧化物和N，N'-二氧化物（1ao和1ado）与TCNE在溶液和固态下缔合。溶液配合物的特征是分别在1ao / TCNE和1ado / TCNE的CH（2）Cl（2）中在lambda（m）364和540 nm处进行电荷转移光学吸收。这些复合物是弱结合的，K（f）值为0.5-3.0 M（-）（1）。（1ao）（2）/ TCNE和1ado / TCNE的晶体是可分离的，其结构已通过X射线衍射确定。发现π偶极子供体与电子贫乏的TCNE之间存在局部供体-受体（DA）相互作用。（1ao）（2）/ TCNE的晶体由离散的DAD三元组组成，其中1ao氧比另一个（C（2），C）更接近TCNE的一个烯烃C原子（C（1），2.86Å）。 3.07Å）。OC（1）-C（2）角为87度，偶氮氧化物分子平面垂直于TCNE的分子平面。1ado / TCNE晶体由延伸的-DADA-