5-diazotricyclo[4.1.0.0^1,3]heptane-4-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-diazotricyclo[4.1.0.0^1,3]heptane-4-one
• 英文别名: (3R,6R)-5-diazotricyclo[4.1.0.01,3]heptan-4-one
• 化学式: C₇H₆N₂O
• 分子量: 134.137
• InChiKey: RUJZVVDVMUFCTC-HMFOOQLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  5-diazotricyclo[4.1.0.0^1,3]heptane-4-one 以 solid matrix 为溶剂， 生成 (3S,5S)-1-Tricyclo[3.1.0.0^1,3]hex-4-ylidene-methanone
  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
• 作为产物：
  描述：

  1,5-己二烯醇 在 sodium hydroxide 、 二甲基硫 、 苄基三乙基氯化铵 、 甲基锂 、 臭氧 、 甲烷磺酰基叠氮化物 作用下， 以 二氯甲烷 为溶剂， 反应 145.0h， 生成 5-diazotricyclo[4.1.0.0^1,3]heptane-4-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

• Synthesis, Reactions, and Structural Studies of Two-Carbon Bridged Spiropentanes
  作者：Kenneth B. Wiberg、John R. Snoonian

  DOI：10.1021/jo970972y

  日期：1998.3.1

  The syntheses of three 4,5-disubstituted derivatives of tricyclo[4.1.0.0(1,3)]heptane (3) are reported. The relative stereochemistry of the oxygen substituents in these compounds was deduced by C-13 NMR spectroscopy and unequivocally confirmed by single-crystal X-ray analysis of the thiocarbonate derivative 15, The experimental results obtained from reaction of the 2,4-diol 6 under Swern conditions and with TPAP were explained by the results of ab initio calculations at the MP2/6-31G* level of theory.
• 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.