1-(2-吡啶基)-1-十三烷酮 | 242458-31-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 1-(2-吡啶基)-1-十三烷酮
• 英文名称: Dodecyl pyridin-2-yl ketone
• 英文别名: 2-Tridecanoylpyridine；1-pyridin-2-yltridecan-1-one
• CAS: 242458-31-7
• 化学式: C₁₈H₂₉NO
• 分子量: 275.434
• InChiKey: WULLBZVBTURUNX-UHFFFAOYSA-N

物化性质

• 沸点：
  379.4±15.0 °C(Predicted)
• 密度：
  0.931±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  20
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  30
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2933399090

反应信息

• 作为反应物：
  描述：

  1-(2-吡啶基)-1-十三烷酮 在 正庚烷 、 盐酸羟胺 、 sodium carbonate 、 copper dichloride 作用下， 以 乙醇 、 甲苯 为溶剂， 反应 10.5h， 生成 十三醛
  参考文献：
  名称：

  Photodegradation of Hydrophobic Pyridineketoximes in Toluene and Heptane

  摘要：

  AbstractThe goal of the research was to study the reactivity of the hydrophobic 2‐ and 3‐pyridineketoximes under exposure to UV‐VIS light. The photodegradation was conducted in both toluene and heptane for 10 h under atmosphere of argon. Ten‐hour irradiation experiments demonstrated that the pyridineketoximes underwent the facile E‐Z photoisomerization, photo‐Beckmann rearrangement, and to a lesser extent, the photosubstitution to the pyridine ring. From LC‐MS and NMR analysis of the irradiated solutions, it was found that the photosubstitution proceeded to give the corresponding 6‐substituted 2‐ or 3‐pyridylketoxime via the replacement of the ring hydrogen by the benzyl or heptyl group. The photo‐Beckmann rearrangement led to the formation of the corresponding amides, but also other products formed in the photo‐decomposition reaction.

  DOI：

  10.1111/php.12453
• 作为产物：
  描述：

  2-氰基吡啶 、 magnesium,dodecane,bromide 以 乙醚 为溶剂， 反应 1.0h， 以33%的产率得到1-(2-吡啶基)-1-十三烷酮
  参考文献：
  名称：

  Metal Ion Chelates of Lipophilic Alkyl Diazinyl Ketoximes as Hydrolytic Catalysts

  摘要：

  一系列亲脂性的十二烷基杂环酮肟（杂环 = 吡啶-2-基、吡啶并嗪-3-基、嘧啶-2-基、嘧啶-4-基、吡嗪-2-基以及它们的甲基杂环同系物）被合成，并研究了它们与十六烷基三甲基溴化铵的胶束基质或均相水溶液中的Co²⁺、Ni²⁺、Cu²⁺和Zn²⁺螯合物的水解活性，使用4-硝基苯乙酸酯、4-硝基己酸酯和4-硝基二苯酚磷酸酯作为模型底物。虽然Co²⁺和Cu²⁺螯合物几乎无活性，但Ni²⁺和Zn²⁺的螯合物表现出相当的活性。研究的螯合物均不促进所使用磷酸酯的水解。当酯裂解在胶束基质中进行时，有效的物种是Ni²⁺和Zn²⁺的金属：配体化学计量比为1：3和1：1的螯合物，而在水溶液中发现了Ni²⁺和Zn²⁺的甲基酮肟螯合物的1：2化学计量比。

  DOI：

  10.1135/cccc19991159

文献信息

• Metal Ion Chelates of Lipophilic Alkyl Diazinyl Ketoximes as Hydrolytic Catalysts
  作者：Radek Cibulka、František Hampl、Tomáš Martinů、Jiří Mazáč、Sonja Totevová、František Liška

  DOI：10.1135/cccc19991159

  日期：——

  A series of lipophilic dodecyl hetaryl ketoximes (hetaryl = pyridin-2-yl, pyridazin-3-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrazin-2-yl as well as their methyl hetaryl homologues was synthesized and hydrolytic activity of their chelates with Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺ in a micellar matrix of hexadecyltrimethylammonium bromide or in homogeneous aqueous solutions was investigated using 4-nitrophenyl acetate, 4-nitrophenyl hexanoate and 4-nitrophenyl diphenyl phosphate as model substrates. While Co²⁺ and Cu²⁺ chelates are almost inactive, those of Ni²⁺ and Zn²⁺ exhibit considerable activity. None of the studied chelates promotes hydrolysis of the used phosphate. The effective species are chelates of the metal : ligand stoichiometry 1 : 3 and 1 : 1 with Ni²⁺ and Zn²⁺, respectively, when the ester cleavage proceeds in the micellar matrix. The 1 : 2 stoichiometry was found in aqueous solutions of Ni²⁺ and Zn²⁺ chelates of methyl ketoximes.

  一系列亲脂性的十二烷基杂环酮肟（杂环 = 吡啶-2-基、吡啶并嗪-3-基、嘧啶-2-基、嘧啶-4-基、吡嗪-2-基以及它们的甲基杂环同系物）被合成，并研究了它们与十六烷基三甲基溴化铵的胶束基质或均相水溶液中的Co²⁺、Ni²⁺、Cu²⁺和Zn²⁺螯合物的水解活性，使用4-硝基苯乙酸酯、4-硝基己酸酯和4-硝基二苯酚磷酸酯作为模型底物。虽然Co²⁺和Cu²⁺螯合物几乎无活性，但Ni²⁺和Zn²⁺的螯合物表现出相当的活性。研究的螯合物均不促进所使用磷酸酯的水解。当酯裂解在胶束基质中进行时，有效的物种是Ni²⁺和Zn²⁺的金属：配体化学计量比为1：3和1：1的螯合物，而在水溶液中发现了Ni²⁺和Zn²⁺的甲基酮肟螯合物的1：2化学计量比。
• Quaternary Pyridinium Ketoximes - New Efficient Micellar Hydrolytic Catalysts
  作者：Radek Cibulka、František Hampl、Hana Kotoučová、Jiří Mazáč、František Liška

  DOI：10.1135/cccc20000227

  日期：——

  A series of quaternized alkyl pyridyl ketoximes was synthesized and tested as micellar hydrolytic catalysts. 2- And 4-[1-(hydroxyimino)tridecyl]-1-methylpyridinium bromides were surprisingly efficient, most probably due to the location of their nucleophilic hydroxyimino group below the micellar surface. Absorbance of the reaction mixture vs time plots exhibited remarkable positive deviation from the first-order kinetics when hydrolysis of 4-nitrophenyl phosphates was catalyzed by 1-dodecyl-3-[1-(hydroxyimino)ethyl]- or 3-[1-(hydroxyimino)tridecyl]-1-methylpyridinium bromide.

  一系列季铵化烷基吡啶酮肟化合物被合成并作为胶束水解催化剂进行测试。2-和4-[1-(羟基亚胺)十三烷基]-1-甲基吡啶溴化物表现出出乎意料的高效，很可能是因为它们的亲核羟基亚胺基团位于胶束表面以下。当1-十二烷基-3-[1-(羟基亚胺)乙基]-或3-[1-(羟基亚胺)十三烷基]-1-甲基吡啶溴化物催化4-硝基苯磷酸酯水解时，反应混合物的吸光度与时间的关系图表现出与一阶动力学明显不同的正偏离。
• Metal Ion Transport Through Bulk Liquid Membrane Mediated by Cationic Ligand Surfactants
  作者：Eva Svobodová、Radek Cibulka、František Hampl、Jan Šmidrkal、František Liška

  DOI：10.1135/cccc20050441

  日期：——

  A series of N,N,N-trialkyl-2-(hydroxyimino)-2-(pyridin-2-yl)ethan-1-aminium nitrates 3a-3h and N,N,N-trialkyl-4-(hydroxyimino)-4-(pyridin-2-yl)butan-1-aminium nitrates 3i-3l representing cationic surfactants with a powerful 1-(hydroxyimino)-1-(pyridin-2-yl)alkyl chelating subunit were prepared as potential selective metal ion extractants. Their extraction ability was tested in transport of Cu²⁺, Ni²⁺, Co²⁺, and Pd²⁺ through a bulk liquid membrane. The introduction of the cationic group into the extractant molecule increases the selectivity and facilitates the metal ion transport as shown by comparing the transports carried out with ligand surfactants 3 and lipophilic alkyl pyridin-2-yl ketoximes 2. The efficiency and selectivity of the metal ion transport mediated by ligand surfactants 3 depends predominantly on their structure and lipophilicity, i.e. on the number and length of hydrophobic alkyl chains and on the length of the spacer connecting the chelating moiety with the cationic head group of the surfactant.

  一系列N,N,N-三烷基-2-(羟基亚胺基)-2-(吡啶-2-基)乙基-1-胺盐3a-3h和N,N,N-三烷基-4-(羟基亚胺基)-4-(吡啶-2-基)丁基-1-胺盐3i-3l代表具有强大1-(羟基亚胺基)-1-(吡啶-2-基)烷基螯合亚基的阳离子表面活性剂，作为潜在的选择性金属离子萃取剂进行制备。它们的萃取能力在通过大量液膜传输Cu2+、Ni2+、Co2+和Pd2+时进行了测试。将阳离子基团引入萃取剂分子中增加了选择性，并促进了金属离子的传输，通过比较使用配体表面活性剂3和亲脂性烷基吡啶-2-基酮肟2进行的传输可以看出。由配体表面活性剂3介导的金属离子传输的效率和选择性主要取决于它们的结构和亲脂性，即疏水烷基链的数量和长度，以及连接螯合基团与表面活性剂阳离子头基的间隔长度。
• Photodegradation of Hydrophobic Pyridineketoximes in Toluene and Heptane
  作者：Karolina Wieszczycka、Joanna Zembrzuska

  DOI：10.1111/php.12453

  日期：2015.7

  AbstractThe goal of the research was to study the reactivity of the hydrophobic 2‐ and 3‐pyridineketoximes under exposure to UV‐VIS light. The photodegradation was conducted in both toluene and heptane for 10 h under atmosphere of argon. Ten‐hour irradiation experiments demonstrated that the pyridineketoximes underwent the facile E‐Z photoisomerization, photo‐Beckmann rearrangement, and to a lesser extent, the photosubstitution to the pyridine ring. From LC‐MS and NMR analysis of the irradiated solutions, it was found that the photosubstitution proceeded to give the corresponding 6‐substituted 2‐ or 3‐pyridylketoxime via the replacement of the ring hydrogen by the benzyl or heptyl group. The photo‐Beckmann rearrangement led to the formation of the corresponding amides, but also other products formed in the photo‐decomposition reaction.