3-diazobicyclo-[3.1.0]hexan-2-one | 24810-45-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-diazobicyclo-[3.1.0]hexan-2-one
• 英文别名: 3-Diazobicyclo[3.1.0]hexan-2-one
• CAS: 24810-45-5
• 化学式: C₆H₆N₂O
• 分子量: 122.126
• InChiKey: QWMOKSOFGNVFPD-UHFFFAOYSA-N

物化性质

• 沸点：
  69-72 °C(Press: 0.02 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  19.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-diazobicyclo-[3.1.0]hexan-2-one 在 2,3,5-三甲基吡啶 、 sodium hydroxide 作用下， 以 水 为溶剂， 反应 3.0h， 生成 bicyclo<2.1.0>pentane-2-carboxylic acid
  参考文献：
  名称：

  Brook, Peter R.; Brophy, Bernard V., Journal of the Chemical Society. Perkin transactions I, 1985, p. 2509 - 2514

  摘要：

  DOI：
• 作为产物：
  描述：

  3-[1-Dimethylamino-meth-(E)-ylidene]-bicyclo[3.1.0]hexan-2-one 在 对甲苯磺酰叠氮 作用下， 以 二氯甲烷 为溶剂， 反应 72.0h， 以0.40 g的产率得到3-diazobicyclo-[3.1.0]hexan-2-one
  参考文献：
  名称：

  Ring Expansion and Contraction of a Two-Carbon Bridged Spiropentane

  摘要：

  The reactions of tricyclo[4.1.0.0(1,3)]heptan-4-one (5) and two related systems with diazomethane and m-CPBA were examined in order to determine the relative reactivity and migratory aptitudes for the three compounds. The reactions of 5 with diazomethane and m-CPBA yielded new derivatives of the tricyclo[5.1.0.0(1,3)]octane ring system that showed that migration of cyclopropylcarbinyl is favored over cyclopropyl migration in this system. Photolysis of 5-diazotricyclo[4.1.0.0(1,3)]heptan-4-one (23) in methanol and dimethylamine did not lead to ring contraction to the tricyclo[3.1.0.0(1,3)]hexane ring system, but an interesting product was derived from an unusual rearrangement process in the photolysis in dimethylamine. Matrix photolysis of 23 at 15 K gave a decrease in the diazo band at 2085 cm(-1) and the appearance of a new band at 2117 cm(-1), which is a normal position expected for a small-ring ketene such as cyclopropylketene. Thus, matrix photolysis appears to have yielded a derivative of the previously unknown tricyclo[3.1.0.0(1,3)]hexane ring system. The lithium enolate of 5 was characterized by NMR spectroscopy at -80 degrees C and was found to rearrange to m-cresol at -65 degrees C. The geometries of the bridged spiropentanes of this work were optimized at the MP2(frozen core)/6-31G* level of theory, and group equivalent values were derived in order to calculate the heats of formation for these compounds using the calculated energies.

  DOI：

  10.1021/jo970980e

文献信息

• BROOK, P. R.;BROPHY, B. V., J. CHEM. SOC. PERKIN TRANS., 1985, N 12, 2509-2513
  作者：BROOK, P. R.、BROPHY, B. V.

  DOI：——

  日期：——
• Brook, Peter R.; Brophy, Bernard V., Journal of the Chemical Society. Perkin transactions I, 1985, p. 2509 - 2514
  作者：Brook, Peter R.、Brophy, Bernard V.

  DOI：——

  日期：——
• Ring Expansion and Contraction of a Two-Carbon Bridged Spiropentane
  作者：Kenneth B. Wiberg、John R. Snoonian

  DOI：10.1021/jo970980e

  日期：1998.3.1

  The reactions of tricyclo[4.1.0.0(1,3)]heptan-4-one (5) and two related systems with diazomethane and m-CPBA were examined in order to determine the relative reactivity and migratory aptitudes for the three compounds. The reactions of 5 with diazomethane and m-CPBA yielded new derivatives of the tricyclo[5.1.0.0(1,3)]octane ring system that showed that migration of cyclopropylcarbinyl is favored over cyclopropyl migration in this system. Photolysis of 5-diazotricyclo[4.1.0.0(1,3)]heptan-4-one (23) in methanol and dimethylamine did not lead to ring contraction to the tricyclo[3.1.0.0(1,3)]hexane ring system, but an interesting product was derived from an unusual rearrangement process in the photolysis in dimethylamine. Matrix photolysis of 23 at 15 K gave a decrease in the diazo band at 2085 cm(-1) and the appearance of a new band at 2117 cm(-1), which is a normal position expected for a small-ring ketene such as cyclopropylketene. Thus, matrix photolysis appears to have yielded a derivative of the previously unknown tricyclo[3.1.0.0(1,3)]hexane ring system. The lithium enolate of 5 was characterized by NMR spectroscopy at -80 degrees C and was found to rearrange to m-cresol at -65 degrees C. The geometries of the bridged spiropentanes of this work were optimized at the MP2(frozen core)/6-31G* level of theory, and group equivalent values were derived in order to calculate the heats of formation for these compounds using the calculated energies.