4-Chlorbornanon | 55784-69-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 4-Chlorbornanon
• 英文别名: 4-Chloro-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one
• CAS: 55784-69-5
• 化学式: C₁₀H₁₅ClO
• 分子量: 186.681
• InChiKey: CVWPMLBZPBDOGG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 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：

  4-Chlorbornanon 、 sodium diphenylphosphide 在 氨 、 双氧水 作用下， 生成 樟脑 、 (1,7,7-Trimethyl-2-oxobicyclo<2.2.1>hept-4-yl)diphenylphosphine oxide
  参考文献：
  名称：

  Intramolecular Electron Transfer Reactions Catalyzed by .alpha.-Oxo and .beta.-Oxo Substituents in the 1-Chlorobicyclo[2.2.1]heptane System

  摘要：

  Efficient intramolecular ET catalysis in S(RN)1 reactions was observed when a carbonyl group is present in 1-chlorobicyclo[2.2.1]heptane in the alpha or beta position. 1-Chloro-3,3-dimethyl-2-oxobicyclo[2.2.1]heptane (1) and 4-chloro-1,7,7-trimethyl-2-oxobicyclo[2.2.1]heptane (4) reacted with diphenylphosphide ion (Ph(2)P(-)) as nucleophile in liquid ammonia under photostimulation to give the substitution products in good yields, together with very small amounts of the reduction product. The substitution products were not observed in dark conditions, and the photostimulated reactions were inhibited by p-dinitrobenzene. These reactions are proposed to proceed via the S(RN)1 mechanism. In competition experiments, the reactivity ratio of 1 to 4 was 2.8, whereas the ratio of 1-chloro-3,3-dimethyl-2-oxobicyclo[2.2.2]octane (8) to 4 was 1.1. On the other hand, 1-chloro-2-methylene-3, 3-dimethylbicyclo[2.2.1]heptane (7) was unreactive under these experimental conditions. It then seems to follow that when there is a carbonyl group in these bicyclic compounds, in the a or beta position, they react by the S(RN)1 mechanism, and the overall reactivity is similar, but when the C=O is replaced by a C=C, the substrate did not react in these experimental conditions. These results are in agreement with MO calculations, in which the LUMO of compounds 1, 4, and 8 belongs to the pi* MO of the C=O group, with similar energies, and is lower than the pi* MO of 7.

  DOI：

  10.1021/jo00109a035

文献信息

• Intramolecular Electron Transfer Reactions Catalyzed by .alpha.-Oxo and .beta.-Oxo Substituents in the 1-Chlorobicyclo[2.2.1]heptane System
  作者：Andres E. Lukach、David G. Morris、Ana N. Santiago、Roberto A. Rossi

  DOI：10.1021/jo00109a035

  日期：1995.2

  Efficient intramolecular ET catalysis in S(RN)1 reactions was observed when a carbonyl group is present in 1-chlorobicyclo[2.2.1]heptane in the alpha or beta position. 1-Chloro-3,3-dimethyl-2-oxobicyclo[2.2.1]heptane (1) and 4-chloro-1,7,7-trimethyl-2-oxobicyclo[2.2.1]heptane (4) reacted with diphenylphosphide ion (Ph(2)P(-)) as nucleophile in liquid ammonia under photostimulation to give the substitution products in good yields, together with very small amounts of the reduction product. The substitution products were not observed in dark conditions, and the photostimulated reactions were inhibited by p-dinitrobenzene. These reactions are proposed to proceed via the S(RN)1 mechanism. In competition experiments, the reactivity ratio of 1 to 4 was 2.8, whereas the ratio of 1-chloro-3,3-dimethyl-2-oxobicyclo[2.2.2]octane (8) to 4 was 1.1. On the other hand, 1-chloro-2-methylene-3, 3-dimethylbicyclo[2.2.1]heptane (7) was unreactive under these experimental conditions. It then seems to follow that when there is a carbonyl group in these bicyclic compounds, in the a or beta position, they react by the S(RN)1 mechanism, and the overall reactivity is similar, but when the C=O is replaced by a C=C, the substrate did not react in these experimental conditions. These results are in agreement with MO calculations, in which the LUMO of compounds 1, 4, and 8 belongs to the pi* MO of the C=O group, with similar energies, and is lower than the pi* MO of 7.

表征谱图