1-(5-(2-甲氧基-4-硝基苯氧基)戊基)哌啶 | 136616-33-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 1-(5-(2-甲氧基-4-硝基苯氧基)戊基)哌啶
• 英文名称: 1-[5-(2-Methoxy-4-nitrophenoxy)pentyl]piperidine
• CAS: 136616-33-6
• 化学式: C₁₇H₂₆N₂O₄
• 分子量: 322.404
• InChiKey: JOLBPBHAVZKPLY-UHFFFAOYSA-N

物化性质

• 沸点：
  463.1±35.0 °C(Predicted)
• 密度：
  1.116±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  67.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-(5-(2-甲氧基-4-硝基苯氧基)戊基)哌啶 在 sodium hydroxide 作用下， 以 水 、 乙腈 为溶剂， 反应 2.0h， 以88%的产率得到1-Piperidino-5-(2-hydroxy-4-nitrophenoxy)pentane
  参考文献：
  名称：

  Topologically Controlled Coulombic Interactions, a New Tool in the Developing of Novel Reactivity. Photochemical and Electrochemical Cleavage of Phenyl Alkyl Ethers

  摘要：

  The hypothesis that a specific placement of a positive charge would dramatically alter the behavior of a charged intermediate has been tested. Phenyl ethers substituted by electron-attracting groups do not undergo reductive fragmentation. However, related alpha-piperidino-omega-(4-substituted-phenoxy)-alkanes give alkyl ether photocleavage when the linker between the redox centers is short, or the usual substitution-reduction photochemistry when it is long. Mechanistic experiments suggest that the photofragmentation process operates through space intramolecular electron transfer to the triplet aromatic chromophore and that a coplanar relative orientation of the alkyl ether bond and the phenyl ring is compulsory for the photofragmentation to be observed. Configuration interaction AM1 calculations justify the described facts, indicating that the fragmentation process is only operative when a Coulombic stabilization of a sigma* intramolecular electron transfer excited state is produced. Electrochemical studies carried out with the corresponding quaternary salts (intermolecular generation of the phenyl ether radical anion) confirm the conclusions derived from the photochemical experiments.

  DOI：

  10.1021/jo00117a037
• 作为产物：
  描述：

  哌啶 、 α-Bromo-ω-(2-methoxy-4-nitrophenoxy)pentane 在 potassium carbonate 作用下， 以 丙酮 为溶剂， 反应 24.0h， 生成 1-(5-(2-甲氧基-4-硝基苯氧基)戊基)哌啶
  参考文献：
  名称：

  Topologically Controlled Coulombic Interactions, a New Tool in the Developing of Novel Reactivity. Photochemical and Electrochemical Cleavage of Phenyl Alkyl Ethers

  摘要：

  The hypothesis that a specific placement of a positive charge would dramatically alter the behavior of a charged intermediate has been tested. Phenyl ethers substituted by electron-attracting groups do not undergo reductive fragmentation. However, related alpha-piperidino-omega-(4-substituted-phenoxy)-alkanes give alkyl ether photocleavage when the linker between the redox centers is short, or the usual substitution-reduction photochemistry when it is long. Mechanistic experiments suggest that the photofragmentation process operates through space intramolecular electron transfer to the triplet aromatic chromophore and that a coplanar relative orientation of the alkyl ether bond and the phenyl ring is compulsory for the photofragmentation to be observed. Configuration interaction AM1 calculations justify the described facts, indicating that the fragmentation process is only operative when a Coulombic stabilization of a sigma* intramolecular electron transfer excited state is produced. Electrochemical studies carried out with the corresponding quaternary salts (intermolecular generation of the phenyl ether radical anion) confirm the conclusions derived from the photochemical experiments.

  DOI：

  10.1021/jo00117a037

文献信息

• Effect of Topologically Controlled Coulombic Interactions on the Dynamic Behavior of Photoexcited Nitrophenyl Alkyl Ethers in the Presence of Tertiary Amines with Limited Motion Freedom
  作者：Roberto Gonzalez-Blanco、José L. Bourdelande、Jordi Marquet

  DOI：10.1021/jo961821i

  日期：1997.10.1

  Time-resolved electronic absorption spectroscopy has been successfully applied to clarify the mechanism of the ''abnormal'' photochemical cleavage of 4-nitrophenyl piperidinoalkyl ethers induced by controlled Coulombic disturbance of the ''normal'' electronic distribution of the radical anion intermediate. Thus, photolysis of 1-piperidino-2-(2-methoxy-4-nitrophenoxy (a system with an amine with limited freedom of motion) in acetonitrile leads to C-O bond photocleavage in a relatively slow process (k approximate to 4 x 10(5) s(-1)) from intermediate species that show radical-ion pair behavior. Systems with higher freedom of motion of the amine moiety, such as 1-piperidino-5-(2-methoxy-4-nitrophenoxy)pentane or 4-nitroveratrole + triethylamine, show the intermediate radical-ion pairs mainly evolving to reduction products, probably a result of intermediates with geometries not allowed for the system with limited freedom of motion of the amine.
• Topologically Controlled Coulombic Interactions, a New Tool in the Developing of Novel Reactivity. Photochemical and Electrochemical Cleavage of Phenyl Alkyl Ethers
  作者：Jorge Marquet、Eduard Cayon、Xavier Martin、Francisco Casado、Iluminada Gallardo、Miquel Moreno、Jose M. Lluch

  DOI：10.1021/jo00117a037

  日期：1995.6

  The hypothesis that a specific placement of a positive charge would dramatically alter the behavior of a charged intermediate has been tested. Phenyl ethers substituted by electron-attracting groups do not undergo reductive fragmentation. However, related alpha-piperidino-omega-(4-substituted-phenoxy)-alkanes give alkyl ether photocleavage when the linker between the redox centers is short, or the usual substitution-reduction photochemistry when it is long. Mechanistic experiments suggest that the photofragmentation process operates through space intramolecular electron transfer to the triplet aromatic chromophore and that a coplanar relative orientation of the alkyl ether bond and the phenyl ring is compulsory for the photofragmentation to be observed. Configuration interaction AM1 calculations justify the described facts, indicating that the fragmentation process is only operative when a Coulombic stabilization of a sigma* intramolecular electron transfer excited state is produced. Electrochemical studies carried out with the corresponding quaternary salts (intermolecular generation of the phenyl ether radical anion) confirm the conclusions derived from the photochemical experiments.