[12-(4-Nitro-phenoxy)-dodecyl]-phenyl-amine | 99610-61-4

• 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: [12-(4-Nitro-phenoxy)-dodecyl]-phenyl-amine
• 英文别名: N-[12-(4-nitrophenoxy)dodecyl]aniline
• CAS: 99610-61-4
• 化学式: C₂₄H₃₄N₂O₃
• 分子量: 398.546
• InChiKey: WOXAQICJYXRTHA-UHFFFAOYSA-N

物化性质

• 沸点：
  552.3±20.0 °C(Predicted)
• 密度：
  1.075±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.1
• 重原子数：
  29
• 可旋转键数：
  15
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  67.1
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [12-(4-Nitro-phenoxy)-dodecyl]-phenyl-amine 以 乙腈 为溶剂， 生成 12-(4-Nitroso-phenoxy)-dodecanal 、 苯胺
  参考文献：
  名称：

  Bifunctional reactivity of the nitrophenoxyl group in intramolecular photoreactions

  摘要：

  The photochemical behavior of a homologous series of compounds, p-O2NC6H4O(CH2)(n)NHPh (n = 2-10, 12, and 16) in acetonitrile is reported. The lower (n = 2-6) homologues undergo an apparently nucleophilic type rearrangement to give omega-((p-nitrophenyl)amino)alkanol, while the higher homologues (n greater-than-or-equal-to 8) undergo an intramolecular photoredox reaction accompanied by C-N bond cleavage to give omega-(p-nitrosophenoxy)alkanal and aniline. The n = 7 homologue is situated at the switching point of these two reaction pathways, exhibiting neither type of photoreactions. Photoinduced intramolecular electron transfer to generate a radical ion pair is observed for all homologues, and the quantum yield decreases with increasing chain length. This species is the intermediate in the photorearrangement, for which the effect of base-catalysis is discussed in connection with the reaction mechanism. Comparison of the quantum yield for the electron transfer in 1 with that in 1-(anilinomethyl)-4-((p-nitrophenoxy)methyl)cyclohexane reveals the dominance of through-bond electron-transfer mechanism in the higher (n greater-than-or-equal-to 6) homologues. The reaction quantum yield vs chain length profile is discussed in terms of the relative quantum yield of the radical ion pair, the chain conformation, and the photoredox reaction mechanism.

  DOI：

  10.1021/jo00016a017
• 作为产物：
  描述：

  对硝基苯酚 在 四丁基溴化铵 、 potassium carbonate 作用下， 以 水 为溶剂， 反应 4.5h， 生成 [12-(4-Nitro-phenoxy)-dodecyl]-phenyl-amine
  参考文献：
  名称：

  Bifunctional reactivity of the nitrophenoxyl group in intramolecular photoreactions

  摘要：

  The photochemical behavior of a homologous series of compounds, p-O2NC6H4O(CH2)(n)NHPh (n = 2-10, 12, and 16) in acetonitrile is reported. The lower (n = 2-6) homologues undergo an apparently nucleophilic type rearrangement to give omega-((p-nitrophenyl)amino)alkanol, while the higher homologues (n greater-than-or-equal-to 8) undergo an intramolecular photoredox reaction accompanied by C-N bond cleavage to give omega-(p-nitrosophenoxy)alkanal and aniline. The n = 7 homologue is situated at the switching point of these two reaction pathways, exhibiting neither type of photoreactions. Photoinduced intramolecular electron transfer to generate a radical ion pair is observed for all homologues, and the quantum yield decreases with increasing chain length. This species is the intermediate in the photorearrangement, for which the effect of base-catalysis is discussed in connection with the reaction mechanism. Comparison of the quantum yield for the electron transfer in 1 with that in 1-(anilinomethyl)-4-((p-nitrophenoxy)methyl)cyclohexane reveals the dominance of through-bond electron-transfer mechanism in the higher (n greater-than-or-equal-to 6) homologues. The reaction quantum yield vs chain length profile is discussed in terms of the relative quantum yield of the radical ion pair, the chain conformation, and the photoredox reaction mechanism.

  DOI：

  10.1021/jo00016a017

文献信息

• Magnetic field effects on end product yields observed for photochemistry involving biradical intermediates
  作者：Ryoichi Nakagaki、Yasuhiro Tsujimoto、Kiyoshi Mutai

  DOI：10.1016/0009-2614(95)00943-x

  日期：1995.10

  reactions of the chain molecules (4-nitrophenoxyl)-(methylene spacer)- (reductant) when the intersystem crossing rate between the singlet and triplet biradicals depends upon the magnetic field and the escape process involving the biradical intermediates and the starting species is relatively efficient. The magnitude of the magnetic field effects can be determined by the competition between the spin-lattice

  当单线态和三线态双自由基之间的系统穿越速率取决于磁场和涉及的逸出过程时，对于链分子（4-硝基苯氧基）-（亚甲基间隔基）-（还原剂）的光氧化还原反应，可以检测到磁场对产物收率的影响。双自由基中间体和起始物种是相对有效的。磁场效应的大小可以通过自旋晶格弛豫和双分子逸出过程之间的竞争来确定。
• Magnetic Field Effects on and Mechanism of Photoredox Reaction of Aromatic Nitro Group
  作者：Kiyoshi Mutai、Ryoichi Nakagaki、Hideyuki Tukada

  DOI：10.1246/bcsj.66.920

  日期：1993.3

  Photoredox reaction mechanism of a homologous series p-O2NC6H4O(CH2)nNHPh (1) in acetonitrile and benzene is studied. The major products are p-ONC6H4O(CH2)n−1CHO (3) and aniline derived from intramolecular reaction, but the presence of minor amounts of intermolecular reaction products, p-O2NC6H4O(CH2)n−1CHO (4) and p-ONC6H4O(CH2)nNHPh (5) is confirmed in the reaction mixture. In the presence of an external magnetic field, the yield of 3 is suppressed and those of 4 and 5 are correspondingly increased, while the rates of the disappearance of 1 and of the formation of aniline remain unchanged, suggesting the presencer of biradical recombination process accompanied by intersystem crossing in a rate-determining step. On the basis of these observations, two reaction schemes are proposed. The magnetic field effects provide strong evidence for the presence of a transient species with (nitro)N(OH)–O–CHN< group generally supposed for nitro oxygen transfer process in this type photoreaction.

  研究了同族系列 p-O2NC6H4O(CH2)nNHPh (1) 在乙腈和苯中的光氧化反应机理。主要产物是分子内反应生成的 p-ONC6H4O( )n-1CHO (3) 和苯胺，但证实反应混合物中存在少量分子间反应产物 p-O2NC6H4O( )n-1CHO (4) 和 p-ONC6H4O( )nNHPh (5)。在外加磁场的作用下，3 的产率被抑制，4 和 5 的产率相应增加，而 1 的消失速率和苯胺的生成速率保持不变，这表明在速率决定步骤中存在双辐射重组过程，同时伴有体系间的交叉。根据这些观察结果，提出了两种反应方案。磁场效应提供了强有力的证据，证明在这类光反应中存在一种带有（硝基）N(OH)-O-CHN<基团的瞬态物种，一般认为这种物种存在于硝基氧转移过程中。