9-(1-Phenylpiperidin-4-ylidene)cyclohexanone | 193960-10-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 9-(1-Phenylpiperidin-4-ylidene)cyclohexanone
• 英文别名: 4-(1-Phenylpiperidin-4-ylidene)cyclohexan-1-one；4-(1-phenylpiperidin-4-ylidene)cyclohexan-1-one
• CAS: 193960-10-0
• 化学式: C₁₇H₂₁NO
• 分子量: 255.36
• InChiKey: JOODZCFRHAZGJF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  9-(1-Phenylpiperidin-4-ylidene)cyclohexanone 在 盐酸 、 N,N-二甲基甲酰胺二新戊基乙缩醛 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 乙腈 为溶剂， 反应 8.0h， 生成 4'-(1-phenylpiperidin-4-ylidene)-1,1'-bi(cyclohexyliden)-4-one
  参考文献：
  名称：

  Oligo(Cyclohexylidene)s and Oligo(Cyclohexyl)s as Bridges for Photoinduced Intramolecular Charge Separation and Recombination

  摘要：

  A series of semirigid donor-bridge-acceptor (D-B-A) molecules was synthesized to study the effect of the position and number of nonconjugated olefinic bonds in the bridge on the photoinduced charge-separation and charge-recombination kinetics. The molecules consist of a phenylpiperidine electron donor, an oligo(cyclohexylidene) or oligo(cyclohexyl) bridge, and a dicyanovinyl acceptor. Partly saturated ter(cyclohexylidene) bridges were used as well. The edge-to-edge donor-acceptor separation of the compounds under study varies between 2.89 and 15.4 Angstrom. The replacement of a C-C single bond by an olefinic bond increases the rate of charge separation with a factor of 3.0 +/- 0.8 per replaced bond. For all D-B-A compounds the extended fully charge-separated state folds to a compact charge-transfer (CCT) conformer. The rate of charge recombination (CR) of the CCT state increases with solvent polarity for those compounds having an olefinic bond located three sigma bonds from the acceptor. Thus, while in cyclohexane the CR rate is equal for all compounds, in benzene the CR rate in compounds with an olefinic bond near the acceptor is 10 times larger than in compounds with a single bond instead. It is believed that a (virtual) charge-transfer state involving the radical cation of the olefinic bond and the radical anion of the acceptor (D-B.+-A(.-)) is responsible for the enhanced CR process.

  DOI：

  10.1021/jp0271716
• 作为产物：
  描述：

  3,3-二甲基-1,5-二氧杂螺[5.5]十一烷-9-羧酸 在 盐酸 、 N,N-二甲基甲酰胺二新戊基乙缩醛 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 乙腈 为溶剂， 反应 8.0h， 生成 9-(1-Phenylpiperidin-4-ylidene)cyclohexanone
  参考文献：
  名称：

  Photoinduced Intramolecular Charge Separation in Donor/Acceptor-Substituted Bicyclohexylidene and Bicyclohexyl

  摘要：

  The photophysical properties of a bicyclohexylidene (1DA) and a bicyclohexyl (2DA) substituted with an anilino electron donor and a dicyanoethylene electron acceptor have been studied. Quenching of local donor emission is observed for these compounds as well as quenching of the "pseudo-local" acceptor emission. Transient absorption spectra show dialkylanilino-type radical-cation and dicyanoethylene-type radical-anion absorptions. These results show that intramolecular charge separation takes place in 1DA and 2DA. This was corroborated by time-resolved microwave conductivity measurements from which large excited-state dipole moments were found for both 1DA and 2DA. Time-resolved fluorescence spectroscopy revealed that in the charge-separated state in cyclohexane for 2DA, molecular folding takes place on a nanosecond timescale. For 1DA in cyclohexane, either charge separation takes place in a (fully) folded conformation or very rapid (subnanosecond timescale) folding takes place subsequent to charge separation. In addition to this difference in conformational behavior, the presence of the exocyclic double bond between the cyclohexyl-type rings results in efficient quenching of the anilino donor triplet state and acceleration of the charge recombination rate by a factor of 20.

  DOI：

  10.1002/1521-3765(20000818)6:16<2948::aid-chem2948>3.0.co;2-0

文献信息

• Oligo(Cyclohexylidene)s and Oligo(Cyclohexyl)s as Bridges for Photoinduced Intramolecular Charge Separation and Recombination
  作者：Wibren D. Oosterbaan、Carola Koper、Thijs W. Braam、Frans J. Hoogesteger、Jacob J. Piet、Bart A. J. Jansen、Cornelis A. van Walree、H. Johan van Ramesdonk、Marijn Goes、Jan W. Verhoeven、Wouter Schuddeboom、John M. Warman、Leonardus W. Jenneskens

  DOI：10.1021/jp0271716

  日期：2003.5.1

  A series of semirigid donor-bridge-acceptor (D-B-A) molecules was synthesized to study the effect of the position and number of nonconjugated olefinic bonds in the bridge on the photoinduced charge-separation and charge-recombination kinetics. The molecules consist of a phenylpiperidine electron donor, an oligo(cyclohexylidene) or oligo(cyclohexyl) bridge, and a dicyanovinyl acceptor. Partly saturated ter(cyclohexylidene) bridges were used as well. The edge-to-edge donor-acceptor separation of the compounds under study varies between 2.89 and 15.4 Angstrom. The replacement of a C-C single bond by an olefinic bond increases the rate of charge separation with a factor of 3.0 +/- 0.8 per replaced bond. For all D-B-A compounds the extended fully charge-separated state folds to a compact charge-transfer (CCT) conformer. The rate of charge recombination (CR) of the CCT state increases with solvent polarity for those compounds having an olefinic bond located three sigma bonds from the acceptor. Thus, while in cyclohexane the CR rate is equal for all compounds, in benzene the CR rate in compounds with an olefinic bond near the acceptor is 10 times larger than in compounds with a single bond instead. It is believed that a (virtual) charge-transfer state involving the radical cation of the olefinic bond and the radical anion of the acceptor (D-B.+-A(.-)) is responsible for the enhanced CR process.
• Photoinduced Intramolecular Charge Separation in Donor/Acceptor-Substituted Bicyclohexylidene and Bicyclohexyl
  作者：Frans J. Hoogesteger、Cornelis A. van Walree、Leonardus W. Jenneskens、Martin R. Roest、Jan W. Verhoeven、Wouter Schuddeboom、Jacob J. Piet、John M. Warman

  DOI：10.1002/1521-3765(20000818)6:16<2948::aid-chem2948>3.0.co;2-0

  日期：2000.8.18

  The photophysical properties of a bicyclohexylidene (1DA) and a bicyclohexyl (2DA) substituted with an anilino electron donor and a dicyanoethylene electron acceptor have been studied. Quenching of local donor emission is observed for these compounds as well as quenching of the "pseudo-local" acceptor emission. Transient absorption spectra show dialkylanilino-type radical-cation and dicyanoethylene-type radical-anion absorptions. These results show that intramolecular charge separation takes place in 1DA and 2DA. This was corroborated by time-resolved microwave conductivity measurements from which large excited-state dipole moments were found for both 1DA and 2DA. Time-resolved fluorescence spectroscopy revealed that in the charge-separated state in cyclohexane for 2DA, molecular folding takes place on a nanosecond timescale. For 1DA in cyclohexane, either charge separation takes place in a (fully) folded conformation or very rapid (subnanosecond timescale) folding takes place subsequent to charge separation. In addition to this difference in conformational behavior, the presence of the exocyclic double bond between the cyclohexyl-type rings results in efficient quenching of the anilino donor triplet state and acceleration of the charge recombination rate by a factor of 20.