5,7-dimethyl-4,8-diphenylpentacyclo[5.4.0.02,5.03,9.04,8]undecan-6-one | 61109-75-9

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 环丁烷木脂素
• 英文名称: 5,7-dimethyl-4,8-diphenylpentacyclo[5.4.0.02,5.03,9.04,8]undecan-6-one
• CAS: 61109-75-9
• 化学式: C₂₅H₂₄O
• 分子量: 340.465
• InChiKey: RBCZFUIFBNJRQN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.48
• 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：

  5,7-dimethyl-4,8-diphenylpentacyclo[5.4.0.02,5.03,9.04,8]undecan-6-one 以 苯 为溶剂， 以77%的产率得到(1R,2R,5S,6S)-3,8-Dimethyl-4,7-diphenyl-tricyclo[4.2.2.02,5]deca-3,7-diene
  参考文献：
  名称：

  Photosensitized [2+2] cycloreversion reactions of arylated cage compounds in nonpolar solvents. Highly efficient adiabatic exciplex isomerization

  摘要：

  Photosensitized [2+2] cycloreversion reactions of arylated cage compounds 1 to dienes 2 using several cyanoaromatics as sensitizers are reported. In acetonitrile, 1a isomerized to 2a via an efficient cation-radical chain process. In contrast, the isomerization of 1a to 2a proceeded via an exciplex in benzene. Interestingly, the exciplex emission maximum observed in the fluorescence quenching by 1a was the same as that by 2a. Such a coincidence was also observed in a series of arylated cage compounds 1a-d and dienes 2a-d in various solvents. These observations together with the results obtained from reaction and exciplex emission quenching experiments clearly demonstrated the occurrence of adiabatic exciplex isomerization of 1 to 2. Efficiencies (A(e)) of the adiabatic process obtained by comparing the intensities of the observed exciplex emissions with those of diene exciplex emissions were quite high and became almost quantitative in some cases. A(e) values were found to increase as (1) the oxidation potentials (E1/2ox) of cage compounds 1a-d decreased, (2) the reduction potentials (E1/2red) of sensitizers increased, and (3) the solvent polarity (E(T)) increased.

  DOI：

  10.1021/jo00006a039
• 作为产物：
  描述：

  2,7a-Dimethyl-3,3a-diphenyl-3a,4,7,7a-tetrahydro-4,7-ethano-inden-1-one 生成 5,7-dimethyl-4,8-diphenylpentacyclo[5.4.0.02,5.03,9.04,8]undecan-6-one
  参考文献：
  名称：

  Thermally induced decarbonylation of cage ketones

  摘要：

  DOI：

  10.1021/ja00435a053

文献信息

• SATO, KATSUHIRO;YAMASHITA, YOSHIRO;MUKAI, TOSHIO, TETRAHEDRON LETT., 1981, 22, N 52, 5303-5306
  作者：SATO, KATSUHIRO、YAMASHITA, YOSHIRO、MUKAI, TOSHIO

  DOI：——

  日期：——
• Photosensitized [2+2] cycloreversion reactions of arylated cage compounds in nonpolar solvents. Highly efficient adiabatic exciplex isomerization
  作者：Eietsu Hasegawa、Keiji Okada、Hiroshi Ikeda、Yoshiro Yamashita、Toshio Mukai

  DOI：10.1021/jo00006a039

  日期：1991.3

  Photosensitized [2+2] cycloreversion reactions of arylated cage compounds 1 to dienes 2 using several cyanoaromatics as sensitizers are reported. In acetonitrile, 1a isomerized to 2a via an efficient cation-radical chain process. In contrast, the isomerization of 1a to 2a proceeded via an exciplex in benzene. Interestingly, the exciplex emission maximum observed in the fluorescence quenching by 1a was the same as that by 2a. Such a coincidence was also observed in a series of arylated cage compounds 1a-d and dienes 2a-d in various solvents. These observations together with the results obtained from reaction and exciplex emission quenching experiments clearly demonstrated the occurrence of adiabatic exciplex isomerization of 1 to 2. Efficiencies (A(e)) of the adiabatic process obtained by comparing the intensities of the observed exciplex emissions with those of diene exciplex emissions were quite high and became almost quantitative in some cases. A(e) values were found to increase as (1) the oxidation potentials (E1/2ox) of cage compounds 1a-d decreased, (2) the reduction potentials (E1/2red) of sensitizers increased, and (3) the solvent polarity (E(T)) increased.
• Thermally induced decarbonylation of cage ketones
  作者：T. Tezuka、Y. Yamashita、T. Mukai

  DOI：10.1021/ja00435a053

  日期：1976.9