9-[1-(4-methoxyphenylpiperidin)-4-ylidene]-3,3-dimethyl-1,5-dioxaspiro[5.5]undecane | 267428-50-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: 9-[1-(4-methoxyphenylpiperidin)-4-ylidene]-3,3-dimethyl-1,5-dioxaspiro[5.5]undecane
• CAS: 267428-50-2
• 化学式: C₂₃H₃₃NO₃
• 分子量: 371.52
• InChiKey: CVGMMGZWDPKFOP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.94
• 重原子数：
  27.0
• 可旋转键数：
  2.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  30.93
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  9-[1-(4-methoxyphenylpiperidin)-4-ylidene]-3,3-dimethyl-1,5-dioxaspiro[5.5]undecane 在 platinum(IV) oxide 氢气 、 溶剂黄146 作用下， 以 乙酸乙酯 为溶剂， 以86%的产率得到9-[1-(4-methoxyphenylpiperidin)-4-yl]-3,3-dimethyl-1,5-dioxaspiro[5.5]undecane
  参考文献：
  名称：

  Stepwise versus Direct Long-Range Charge Separation in Molecular Triads

  摘要：

  Trifunctional electron donor-donor-acceptor molecules are described in which photoinduced charge separation, D-2-D-1-A* --> D-2-D-1(+)-A(-), is followed by a charge migration step D-2-D-1(+)-A(-) (CS1) --> D-2(+)-D-1-A- (CS2), leading to a relatively long-lived charge-separated state. The rate of the charge migration process could be determined in a range of solvents of low polarity. In benzene and dioxane, reversibility of the process allowed the determination of the free energy difference between CS1 and CS2. The relative energy of the CS2 state is much lower than expected from simple electrostatic models. An increase of the charge migration rate was found with increasing solvent polarity within a series of alkyl ethers or alkyl acetates. However, an apparent preferential stabilization of the CS1 state in acetates relative to ethers leads to discontinuities in the solvatochromic shift behavior of the CT fluorescence from the CS1 state, and in the increase of the charge migration rate as a function of dielectric constant. In a reference compound lacking the intermediate redox unit, direct long-range charge separation yielding a D-2(+)-bridge-A(-) charge-separated state can occur, but the yield is significantly lower than in the triads.

  DOI：

  10.1021/ja983716r
• 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 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 2.0h， 生成 9-[1-(4-methoxyphenylpiperidin)-4-ylidene]-3,3-dimethyl-1,5-dioxaspiro[5.5]undecane
  参考文献：
  名称：

  Stepwise versus Direct Long-Range Charge Separation in Molecular Triads

  摘要：

  Trifunctional electron donor-donor-acceptor molecules are described in which photoinduced charge separation, D-2-D-1-A* --> D-2-D-1(+)-A(-), is followed by a charge migration step D-2-D-1(+)-A(-) (CS1) --> D-2(+)-D-1-A- (CS2), leading to a relatively long-lived charge-separated state. The rate of the charge migration process could be determined in a range of solvents of low polarity. In benzene and dioxane, reversibility of the process allowed the determination of the free energy difference between CS1 and CS2. The relative energy of the CS2 state is much lower than expected from simple electrostatic models. An increase of the charge migration rate was found with increasing solvent polarity within a series of alkyl ethers or alkyl acetates. However, an apparent preferential stabilization of the CS1 state in acetates relative to ethers leads to discontinuities in the solvatochromic shift behavior of the CT fluorescence from the CS1 state, and in the increase of the charge migration rate as a function of dielectric constant. In a reference compound lacking the intermediate redox unit, direct long-range charge separation yielding a D-2(+)-bridge-A(-) charge-separated state can occur, but the yield is significantly lower than in the triads.

  DOI：

  10.1021/ja983716r