2,3-二氮杂双环[2.2.2]辛-2-烯 2,3-二氧化物 | 36479-80-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪烷类
• 中文名称: 2,3-二氮杂双环[2.2.2]辛-2-烯 2,3-二氧化物
• 中文别名: 2,3-二氮杂双环[2.2.2]辛-2-烯2,3-二氧化物
• 英文名称: N,N'-dioxo-2,3-diazabicyclo<2.2.2>oct-2-ene
• 英文别名: 2,3-diazabicyclo<2.2.2>oct-2-ene dioxide；2,3-diaza-bicyclo[2.2.2]oct-2-ene 2,3-dioxide；Bicyclo[2,2,2]-2,3-diazaoct-2-en-2,3-dioxide；2,3-Diazabicyclo-<2.2.2>-oct-2-en-2,3-dioxid；2,3-Diazabicyclo(2.2.2)oct-2-ene 2,3-dioxide；3-oxido-3-aza-2-azoniabicyclo[2.2.2]octane 2-oxide
• CAS: 36479-80-8
• 化学式: C₆H₁₀N₂O₂
• 分子量: 142.158
• InChiKey: KQTDJBAPOKEJFF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  46.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  7,8-二氮杂双环[2.2.2]辛-7-烯 在 Oxone 作用下， 以 水 为溶剂， 反应 168.0h， 以35%的产率得到2,3-二氮杂双环[2.2.2]辛-2-烯 2,3-二氧化物
  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

• Pericyclic Arrays in the Solid State. Azooxide and Azodioxide Donor-Acceptor Complexes with Tetracyanoethylene
  作者：Silas C. Blackstock、Kathy Poehling、Melinda L. Greer

  DOI：10.1021/ja00129a036

  日期：1995.6
• SINGH P., J. ORG. CHEM. <JOCE-AH>, 1975, 40, NO 10, 1405-1408
  作者：SINGH P.

  DOI：——

  日期：——
• 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.