2-methyl-3-(4',4'-diphenylcyclohex-2'-en-1'-ylidene)prop-2-ene | 145237-54-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-methyl-3-(4',4'-diphenylcyclohex-2'-en-1'-ylidene)prop-2-ene
• CAS: 145237-54-3
• 化学式: C₂₂H₂₂
• 分子量: 286.417
• InChiKey: RFMTVLXORPXTRZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.81
• 重原子数：
  22.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  2-methyl-3-(4',4'-diphenylcyclohex-2'-en-1'-ylidene)prop-2-ene 以 叔丁醇 为溶剂， 反应 4.0h， 以61%的产率得到2-methyl-3-(5',6'-trans-diphenylbicyclo<3.1.0>hexylidene)prop-2-ene
  参考文献：
  名称：

  Photochemistry of some allenic counterparts of cyclohexenones and 2,5-cyclohexadienones

  摘要：

  Allenic analogs of 4,4-diphenylcyclohexenone and a similar counterpart of 4,4-diphenyl-2,5-cyclohexadienone were synthesized. These molecules have a 2-electron pi-MO perpendicular to the six-ring pi-system. This perpendicular pi-orbital is analogous to the oxygen p(y) orbital which is orthogonal to the carbonyl pi-bond. The photochemistry of the allenic systems was explored with the finding that the triplets were unreactive and the singlets underwent a phenyl migration to form bicyclic photoproducts whose structures were established by spectral means, degradation, and independent synthesis. Excited states involving appreciable out-of-plane to pi or pi to out-of-plane excitations are defined as pi-perpendicular-to* and perpendicular-to-pi*, respectively. MNDO-CI level and CASSCF ab initio computations with geometry optimization were carried out with the objective of determining the role of perpendicular-to-pi* and pi-perpendicular-to* transitions and for comparison with the experimental results.

  DOI：

  10.1021/ja00055a014
• 作为产物：
  描述：

  4,4-二苯基-2-环己烯-1-酮 在 4-二甲氨基吡啶 、 copper(l) iodide 、 正丁基锂 、 三乙胺 作用下， 反应 18.5h， 生成 2-methyl-3-(4',4'-diphenylcyclohex-2'-en-1'-ylidene)prop-2-ene
  参考文献：
  名称：

  Photochemistry of some allenic counterparts of cyclohexenones and 2,5-cyclohexadienones

  摘要：

  Allenic analogs of 4,4-diphenylcyclohexenone and a similar counterpart of 4,4-diphenyl-2,5-cyclohexadienone were synthesized. These molecules have a 2-electron pi-MO perpendicular to the six-ring pi-system. This perpendicular pi-orbital is analogous to the oxygen p(y) orbital which is orthogonal to the carbonyl pi-bond. The photochemistry of the allenic systems was explored with the finding that the triplets were unreactive and the singlets underwent a phenyl migration to form bicyclic photoproducts whose structures were established by spectral means, degradation, and independent synthesis. Excited states involving appreciable out-of-plane to pi or pi to out-of-plane excitations are defined as pi-perpendicular-to* and perpendicular-to-pi*, respectively. MNDO-CI level and CASSCF ab initio computations with geometry optimization were carried out with the objective of determining the role of perpendicular-to-pi* and pi-perpendicular-to* transitions and for comparison with the experimental results.

  DOI：

  10.1021/ja00055a014