N-<(phenylthio)methyl>pyridinium chloride

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: N-<(phenylthio)methyl>pyridinium chloride
• 英文别名: pyridiniummethyl phenyl sulfide chloride；N-[(phenylthio)methyl]pyridinium chloride；1-((Phenylthio)methyl)pyridin-1-ium chloride；1-(phenylsulfanylmethyl)pyridin-1-ium;chloride
• 化学式: C₁₂H₁₂NS*Cl
• 分子量: 237.753
• InChiKey: AYOAABZGKLPFCA-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -0.27
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  29.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  吡啶 、 氯甲基苯硫醚 以 苯 为溶剂， 反应 12.0h， 生成 N-<(phenylthio)methyl>pyridinium chloride
  参考文献：
  名称：

  硫化物单线态氧反应表面上中间体的取代基指示分配。α-氢过氧硫化物氧化 C-S 键断裂的新机制

  摘要：

  报道了单线态氧与 17 个带有阴离子或自由基稳定取代基的硫化物的反应。根据氢过氧锍叶立德中间体的分配，分析了取代基在氧化裂解和硫化物氧化途径中改变产物组成的能力。有证据表明氢过氧锍叶立德以双自由基和两性离子形式存在。此外，建议分解 α-氢过氧硫化物的分子间和分子内途径使氧化 C-S 键裂解产物的取代基依赖性形成合理化。

  DOI：

  10.1021/ja004188y

文献信息

• Equilibrium acidities and homolytic bond dissociation energies of the acidic carbon-hydrogen bonds in N-substituted trimethylammonium and pyridinium cations
  作者：Xian Man Zhang、Frederick G. Bordwell、Michael Van Der Puy、Herbert E. Fried

  DOI：10.1021/jo00063a026

  日期：1993.5

  Equilibrium acidities (pK(HA)s) of the cations in sixteen N-substituted trimethylammonium salts, one N-phenacylquinuclidinium salt, eight N-substituted pyridinium salts, and N-(ethoxycarbonyl)isoquinolinium bromide, together with the oxidation potentials of their conjugate bases, have been determined in dimethyl sulfoxide (DMSO) solution. The acidifying effects of the alpha-trimethylammonium groups (alpha-Me3N+) and the alpha-pyridinium groups (alpha-PyN+) on the adjacent acidic C-H bonds in these cations were found to average about 10 and 18 pK(HA) units, respectively, in DMSO. The homolytic bond dissociation energies of the acidic C-H bonds in these cations, estimated by the combination of the equilibrium acidities with the oxidation potentials of their corresponding conjugate bases (ylides), show that the alpha-trimethylammonium groups destabilize adjacent radicals by 2-6 kcal/mol, whereas alpha-pyridinium groups stabilize adjacent radicals by 3-6 kcal/mol. The effects of alpha-pyridinium groups on the stabilization energies of the radicals derived from these cations were found to be ca. 4-10 kcal/mol smaller than those of the corresponding phenyl groups, whereas their effects on the equilibrium acidities of the cations were 5.4-13.1 pK(HA) units larger. The pK(HA) value of tetramethylammonium cation (Me4N+) was estimated by extrapolation to be about 42 in DMSO.
• Substituent-Dictated Partitioning of Intermediates on the Sulfide Singlet Oxygen Reaction Surface. A New Mechanism for Oxidative C−S Bond Cleavage in α-Hydroperoxy Sulfides
  作者：Alexei Toutchkine、David Aebisher、Edward L. Clennan

  DOI：10.1021/ja004188y

  日期：2001.5.1

  singlet oxygen with 17 sulfides bearing either anion or radical stabilizing substituents are reported. The abilities of substituents to modify product compositions in both the oxidative cleavage and sulfide oxidation pathways are analyzed in terms of partitioning of the hydroperoxy sulfonium ylide intermediate. Evidence is presented that suggests that the hydroperoxy sulfonium ylide exists in both diradical

  报道了单线态氧与 17 个带有阴离子或自由基稳定取代基的硫化物的反应。根据氢过氧锍叶立德中间体的分配，分析了取代基在氧化裂解和硫化物氧化途径中改变产物组成的能力。有证据表明氢过氧锍叶立德以双自由基和两性离子形式存在。此外，建议分解 α-氢过氧硫化物的分子间和分子内途径使氧化 C-S 键裂解产物的取代基依赖性形成合理化。