5-benzoylbicyclo<2.1.0>pentane | 335203-05-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-benzoylbicyclo<2.1.0>pentane
• 英文别名: 5-Bicyclo[2.1.0]pentanyl(phenyl)methanone
• CAS: 335203-05-9
• 化学式: C₁₂H₁₂O
• 分子量: 172.227
• InChiKey: PXWJVFOYBBTPKH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  5-benzoylbicyclo<2.1.0>pentane 在 氘代甲醇-d 、 sodium methylate 、 sodium amide 作用下， 以 甲苯 为溶剂， 反应 11.0h， 生成 endo-5-bicyclo<2.1.0>pentane-5-d
  参考文献：
  名称：

  Dynamic models for the thermal deazetization of 2,3-diazabicyclo[2.2.1]hept-2-ene

  摘要：

  Kinetic studies on the thermal nitrogen extrusion from 2,3-diazabicyclo[2.2.1]hept-2-ene-exo,exo-5,6-d2 are reported. The ratio of rate constants for formation of the label-isomeric products (bicyclo[2.1.0]pentane-exo,exo-2,3-d2 and -endo,endo-2,3-d2) is found to exhibit no statistically significant temperature dependence. A comparison of gas-phase and solution-phase results is presented. The results are interpreted in terms of two complementary dynamic models. In the first,classical trajectory calculations are run on a three-dimensional projection (two geometric coordinates) of the potential energy hypersurface. These calculations correctly identify the major product, and reproduce the near temperature-independence of the rate-constant ratio, but do not match the ratio quantitatively. Modification of the trajectory calculations to simulate the effect of collisions with solvent molecules also qualitatively matches the observed difference between gas-phase and solution-phase behavior. In the second model, the vector of atomic displacements corresponding to the reaction coordinate at the transition state for nitrogen loss is identified by both semiempirical and ab initio calculations. The components of this vector pointing along the paths to the post-transition-state minima are computed and are shown to lead to a prediction of the product ratio that is in good (if partly fortuitous) agreement with the experimental result. The vector model is used to predict isotope effects on the product ratio, which are then investigated experimentally with 2,3-diazabicyclo[2.2.1]hept-2-ene-endo,endo-1,4,5,6,7,7-d6 and -endo-7-d.

  DOI：

  10.1021/ja00059a043
• 作为产物：
  描述：

  bicyclo<2.1.0>pentane-5-carboxylic acid 、 苯基锂 以 乙醚 、 正己烷 为溶剂， 反应 1.0h， 生成 5-benzoylbicyclo<2.1.0>pentane
  参考文献：
  名称：

  Dynamic models for the thermal deazetization of 2,3-diazabicyclo[2.2.1]hept-2-ene

  摘要：

  Kinetic studies on the thermal nitrogen extrusion from 2,3-diazabicyclo[2.2.1]hept-2-ene-exo,exo-5,6-d2 are reported. The ratio of rate constants for formation of the label-isomeric products (bicyclo[2.1.0]pentane-exo,exo-2,3-d2 and -endo,endo-2,3-d2) is found to exhibit no statistically significant temperature dependence. A comparison of gas-phase and solution-phase results is presented. The results are interpreted in terms of two complementary dynamic models. In the first,classical trajectory calculations are run on a three-dimensional projection (two geometric coordinates) of the potential energy hypersurface. These calculations correctly identify the major product, and reproduce the near temperature-independence of the rate-constant ratio, but do not match the ratio quantitatively. Modification of the trajectory calculations to simulate the effect of collisions with solvent molecules also qualitatively matches the observed difference between gas-phase and solution-phase behavior. In the second model, the vector of atomic displacements corresponding to the reaction coordinate at the transition state for nitrogen loss is identified by both semiempirical and ab initio calculations. The components of this vector pointing along the paths to the post-transition-state minima are computed and are shown to lead to a prediction of the product ratio that is in good (if partly fortuitous) agreement with the experimental result. The vector model is used to predict isotope effects on the product ratio, which are then investigated experimentally with 2,3-diazabicyclo[2.2.1]hept-2-ene-endo,endo-1,4,5,6,7,7-d6 and -endo-7-d.

  DOI：

  10.1021/ja00059a043