11-diazobicyclo<4.4.1>undecane | 230957-92-3

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 炔丙基型1，3-偶极有机化合物
• 英文名称: 11-diazobicyclo<4.4.1>undecane
• 英文别名: 11-Diazobicyclo[4.4.1]undecane
• CAS: 230957-92-3
• 化学式: C₁₁H₁₈N₂
• 分子量: 178.277
• InChiKey: YDBTZSNHLSSKSE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  11-diazobicyclo<4.4.1>undecane 在 三溴化硼 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 48.0h， 生成 11-[bis-(3-tert-butyl-4,5-dihydroxyphenyl)-methylene]-bicyclo-[4.4.1]undecane
  参考文献：
  名称：

  三亚甲基甲烷型双（半醌）双自由基的交换偶联趋势以及交叉共轭体系中磁性交换与混合价的相关性

  摘要：

  介绍了双自由基复合物等结构系列内的磁结构相关性（构象电子自旋交换调制）。X射线晶体结构、变温电子顺磁共振光谱、零场分裂参数和变温磁化率测量被用来评估这一系列分子的分子构象和电子自旋交换耦合。我们的综合结果表明，交换耦合的铁磁部分通过交叉共轭 pi 系统发生，而反铁磁部分通过空间发生，相当于初始键形成。因此，分子构象控制铁磁和反铁磁对交换耦合的贡献的相对量。实际上，交换参数通过 Karplus-Conroy 型关系与平均半醌环扭转角相关。由于电子自旋交换耦合和与电子转移相关的电子耦合之间的自然联系，我们还将双自由基复合物中的交换参数与相应醌-半醌自由基阴离子中的混合价相关联。我们的结果表明，交叉共轭、混合价自由基阴离子的离域与双自由基氧化态中交换耦合的铁磁贡献成正比。我们还将双自由基复合物中的交换参数与相应醌-半醌自由基阴离子中的混合价相关联。我们的结果表明，交叉共轭、混合价自由基阴离子的离

  DOI：

  10.1021/ja0367849
• 作为产物：
  描述：

  bicyclo<4.4.1>undecan-11-one 在 sodium hydroxide 、 乙醇 、 sodium sulfate 、 mercury(II) oxide 作用下， 以 乙醚 为溶剂， 反应 14.0h， 生成 11-diazobicyclo<4.4.1>undecane
  参考文献：
  名称：

  Structure−Property Relationships in Trimethylenemethane-Type Biradicals. 2. Synthesis and EPR Spectral Characterization of Dinitroxide Biradicals

  摘要：

  Several trimethylenemethane-type (TMM-type) dinitroxide biradicals have been prepared that differ in tert-butylaminoxylphenyl ring torsion angles by virtue of different steric demands of their "spin-protecting groups". In addition, the synthesis of a TMM-type dinitroxide having a planar pi-system is reported. The synthetic route employed for the planar TMM-type biradical is general and should therefore expand, the utility of TMM-type biradicals that are susceptible to bond torsions that attenuate exchange coupling. The compounds presented are designed to be effective to map out J-coupling/conformation space in TMM-type biradicals. EPR spectroscopic parameters (hfcc and D-values) were compared to determine if their values reflected differences in conformation in the series of biradicals. Interestingly, neither N- nor H-hfcc varied within our series of biradicals/monoradicals in a regular fashion, indicating that there is no apparent relationship between N- or H-hfcc and conformation (as judged by molecular mechanics calculations). However, D-values, estimated from relative intensities of Delta m(s) = 1 and Delta m(s) = 2 transitions, are consistent with a varied degree of delocalization in the dinitroxides: smaller D-values for biradicals having smaller aryl torsions (and greater delocalization), and larger D-values for dinitroxides having greater aryl torsions (and less delocalization). All the biradicals studied, except 5(..), exhibited linear Curie plots. The linear Curie plots are consistent with both triplet ground-states and singlet-triplet degeneracies. Interestingly, dinitroxide 6(..) exhibited a linear Curie plot, despite the lack of a pi-coupling fragment. Biradical 5(..), however, is a ground-state singlet; species with the triplet lying about 140 cal/mol above the singlet.

  DOI：

  10.1021/jo990061j

文献信息

• Structure−Property Relationships in Trimethylenemethane-Type Biradicals. 2. Synthesis and EPR Spectral Characterization of Dinitroxide Biradicals
  作者：David A. Shultz、Andrew K. Boal、Hyoyoung Lee、Gary T. Farmer

  DOI：10.1021/jo990061j

  日期：1999.6.1

  Several trimethylenemethane-type (TMM-type) dinitroxide biradicals have been prepared that differ in tert-butylaminoxylphenyl ring torsion angles by virtue of different steric demands of their "spin-protecting groups". In addition, the synthesis of a TMM-type dinitroxide having a planar pi-system is reported. The synthetic route employed for the planar TMM-type biradical is general and should therefore expand, the utility of TMM-type biradicals that are susceptible to bond torsions that attenuate exchange coupling. The compounds presented are designed to be effective to map out J-coupling/conformation space in TMM-type biradicals. EPR spectroscopic parameters (hfcc and D-values) were compared to determine if their values reflected differences in conformation in the series of biradicals. Interestingly, neither N- nor H-hfcc varied within our series of biradicals/monoradicals in a regular fashion, indicating that there is no apparent relationship between N- or H-hfcc and conformation (as judged by molecular mechanics calculations). However, D-values, estimated from relative intensities of Delta m(s) = 1 and Delta m(s) = 2 transitions, are consistent with a varied degree of delocalization in the dinitroxides: smaller D-values for biradicals having smaller aryl torsions (and greater delocalization), and larger D-values for dinitroxides having greater aryl torsions (and less delocalization). All the biradicals studied, except 5(..), exhibited linear Curie plots. The linear Curie plots are consistent with both triplet ground-states and singlet-triplet degeneracies. Interestingly, dinitroxide 6(..) exhibited a linear Curie plot, despite the lack of a pi-coupling fragment. Biradical 5(..), however, is a ground-state singlet; species with the triplet lying about 140 cal/mol above the singlet.
• Trends in Exchange Coupling for Trimethylenemethane-Type Bis(semiquinone) Biradicals and Correlation of Magnetic Exchange with Mixed Valency for Cross-Conjugated Systems
  作者：David A. Shultz、Rosario M. Fico,、Scot H. Bodnar、R. Krishna Kumar、Kira E. Vostrikova、Jeff W. Kampf、Paul D. Boyle

  DOI：10.1021/ja0367849

  日期：2003.9.1

  magnetostructural correlation (conformational electron spin exchange modulation) within an isostructural series of biradical complexes is presented. X-ray crystal structures, variable-temperature electron paramagnetic resonance spectroscopy, zero-field splitting parameters, and variable-temperature magnetic susceptibility measurements were used to evaluate molecular conformation and electron spin exchange coupling

  介绍了双自由基复合物等结构系列内的磁结构相关性（构象电子自旋交换调制）。X射线晶体结构、变温电子顺磁共振光谱、零场分裂参数和变温磁化率测量被用来评估这一系列分子的分子构象和电子自旋交换耦合。我们的综合结果表明，交换耦合的铁磁部分通过交叉共轭 pi 系统发生，而反铁磁部分通过空间发生，相当于初始键形成。因此，分子构象控制铁磁和反铁磁对交换耦合的贡献的相对量。实际上，交换参数通过 Karplus-Conroy 型关系与平均半醌环扭转角相关。由于电子自旋交换耦合和与电子转移相关的电子耦合之间的自然联系，我们还将双自由基复合物中的交换参数与相应醌-半醌自由基阴离子中的混合价相关联。我们的结果表明，交叉共轭、混合价自由基阴离子的离域与双自由基氧化态中交换耦合的铁磁贡献成正比。我们还将双自由基复合物中的交换参数与相应醌-半醌自由基阴离子中的混合价相关联。我们的结果表明，交叉共轭、混合价自由基阴离子的离