(1S,2R,5S,6R)-3,4-Diaza-tricyclo[4.3.2.0^2,5]undeca-3,10-diene | 625454-55-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (1S,2R,5S,6R)-3,4-Diaza-tricyclo[4.3.2.0^2,5]undeca-3,10-diene
• 英文别名: (1R,2S,5R,6S)-3,4-diazatricyclo[4.3.2.02,5]undeca-3,10-diene
• CAS: 625454-55-9
• 化学式: C₉H₁₂N₂
• 分子量: 148.208
• InChiKey: PYKDNOBPQFUBFF-OJOKCITNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S,2R,5S,6R)-3,4-Diaza-tricyclo[4.3.2.0^2,5]undeca-3,10-diene 以 various solvent(s) 为溶剂， 生成 bicyclo[3.2.2]nona-6,8-diene
  参考文献：
  名称：

  Thermal Decomposition of a Series of 1,2-Diazetines

  摘要：

  A homologous series of tricyclic diazetines (6a-c), differing by the number of methylene groups in the saturated bridges of the fused carbon bicycles, was synthesized. The DeltaH(not equal) of decomposition for each of the diazetines to afford N-2 and the corresponding alkene was determined experimentally: 6a, 31.7; 6b, 39.3; 6c, 38.8 kcal/mol. The ground-state strain energy of each diazetine was estimated utilizing computationally obtained DeltaH(f)'s for each of the experimentally investigated diazetines as well as several other diazetines whose DeltaHs(not equal,) had been previously reported in the literature. The sum of the ground-state strain energies and DeltaHs(not equal,) of decomposition for all of the diazetines was nearly constant, with an average value of 59 kcal/mol, suggesting that all of the diazetines decompose via the same mechanism. Generally, the higher the ground-state strain energy of the diazetine, the less the DeltaH(not equal) for decomposition. The decomposition transition states for 6a-c and 7 were modeled computationally at the RB3LYP/6-311+G(3df,2p)//UB3LYP/6-31+G(d,p) level. The agreement of the experimentally determined DeltaH(not equal) values with transition-state energies obtained computationally supports the reaction mechanism originally proposed by Yamabe that the elimination process occurs by an unsymmetrical, yet concerted, transition state with strong biradical character.

  DOI：

  10.1021/jo0351926
• 作为产物：
  描述：

  1,3-环庚二烯 在 氢氧化钾 作用下， 以 氯苯 、 异丙醇 为溶剂， 反应 50.0h， 生成 (1S,2R,5S,6R)-3,4-Diaza-tricyclo[4.3.2.0^2,5]undeca-3,10-diene
  参考文献：
  名称：

  Thermal Decomposition of a Series of 1,2-Diazetines

  摘要：

  A homologous series of tricyclic diazetines (6a-c), differing by the number of methylene groups in the saturated bridges of the fused carbon bicycles, was synthesized. The DeltaH(not equal) of decomposition for each of the diazetines to afford N-2 and the corresponding alkene was determined experimentally: 6a, 31.7; 6b, 39.3; 6c, 38.8 kcal/mol. The ground-state strain energy of each diazetine was estimated utilizing computationally obtained DeltaH(f)'s for each of the experimentally investigated diazetines as well as several other diazetines whose DeltaHs(not equal,) had been previously reported in the literature. The sum of the ground-state strain energies and DeltaHs(not equal,) of decomposition for all of the diazetines was nearly constant, with an average value of 59 kcal/mol, suggesting that all of the diazetines decompose via the same mechanism. Generally, the higher the ground-state strain energy of the diazetine, the less the DeltaH(not equal) for decomposition. The decomposition transition states for 6a-c and 7 were modeled computationally at the RB3LYP/6-311+G(3df,2p)//UB3LYP/6-31+G(d,p) level. The agreement of the experimentally determined DeltaH(not equal) values with transition-state energies obtained computationally supports the reaction mechanism originally proposed by Yamabe that the elimination process occurs by an unsymmetrical, yet concerted, transition state with strong biradical character.

  DOI：

  10.1021/jo0351926

文献信息

• Thermal Decomposition of a Series of 1,2-Diazetines
  作者：Gary W. Breton、John H. Shugart

  DOI：10.1021/jo0351926

  日期：2003.10.1

  A homologous series of tricyclic diazetines (6a-c), differing by the number of methylene groups in the saturated bridges of the fused carbon bicycles, was synthesized. The DeltaH(not equal) of decomposition for each of the diazetines to afford N-2 and the corresponding alkene was determined experimentally: 6a, 31.7; 6b, 39.3; 6c, 38.8 kcal/mol. The ground-state strain energy of each diazetine was estimated utilizing computationally obtained DeltaH(f)'s for each of the experimentally investigated diazetines as well as several other diazetines whose DeltaHs(not equal,) had been previously reported in the literature. The sum of the ground-state strain energies and DeltaHs(not equal,) of decomposition for all of the diazetines was nearly constant, with an average value of 59 kcal/mol, suggesting that all of the diazetines decompose via the same mechanism. Generally, the higher the ground-state strain energy of the diazetine, the less the DeltaH(not equal) for decomposition. The decomposition transition states for 6a-c and 7 were modeled computationally at the RB3LYP/6-311+G(3df,2p)//UB3LYP/6-31+G(d,p) level. The agreement of the experimentally determined DeltaH(not equal) values with transition-state energies obtained computationally supports the reaction mechanism originally proposed by Yamabe that the elimination process occurs by an unsymmetrical, yet concerted, transition state with strong biradical character.