Bis(p-chlorphenylthio)malononitril | 67973-16-4

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: Bis(p-chlorphenylthio)malononitril
• 英文别名: 2,2-bis[(4-chlorophenyl)sulfanyl]propanedinitrile
• CAS: 67973-16-4
• 化学式: C₁₅H₈Cl₂N₂S₂
• 分子量: 351.28
• InChiKey: FEWXWODCPSJUMH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.62
• 重原子数：
  21.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  47.58
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  2-(4-chlorophenyl)sulfanylpropanedinitrile 在 chloramine-B 作用下， 生成 Bis(p-chlorphenylthio)malononitril
  参考文献：
  名称：

  Markovskii,L.N. et al., Journal of Organic Chemistry USSR (English Translation), 1978, vol. 14, p. 1548 - 1553

  摘要：

  DOI：

文献信息

• Pyrolysis of (2-Phenylethyl)phenylsulfonium Ylides.
  作者：Toshiaki Yoshimura、Atsushi Motoyama、Akiko Morishige、Eiichi Tsukurimichi、Choichiro Shimasaki、Kiyoshi Hasegawa

  DOI：10.1246/bcsj.66.174

  日期：——

  In order to obtain information concerning the reaction mechanism of the pyrolysis of sulfonium ylides bearing a substituted phenyl group on the 2-position in the S-ethyl group of ethylphenylsulfonium ylide, (2-phenylethyl)phenylsulfonium bis(methoxycarbonyl)methylide (1) and dicyanomethylide (2) were subjected to pyrolysis in benzene. The reaction rates of 1 and 2 at 140 °C were 6.0- and 3.2-times faster than those of ethylphenylsulfonium bis(methoxycarbonyl)methylide and dicyanomethylide, respectively. The activation parameters for 1 were ΔH‡ = 125 kJ mol−1 and ΔS‡ = −3.8 J K−1 mol−1, while those for 2 were ΔH‡ = 124 kJ mol−1 and ΔS‡ = −2.5 J K−1 mol−1. Substituent effects on the β-phenyl groups in 1 and 2 afforded positive Hammett ρ-values: ρ = 0.49 (γ = 0.997) and ρ = 0.26 (γ = 0.993), respectively.From the obtained results, it was suggested that the pyrolysis proceeds through essentially a concerted intramolecular cis-elimination inclined toward a slightly carbanion-like type from an E1-like type by introducing a phenyl substituent at the 2-position of the ethyl group in the ethylphenylsulfonium ylide.

  为了获取有关乙基苯基亚磺酸乙酯中乙基的2-位上带有取代苯基的磺酸亚磺酸分解反应机理的信息，将（2-苯乙基）苯基亚磺酸双（甲氧基羰基）甲亚基（1）和双氰基甲亚基（2）在苯中进行分解。在140°C时，1和2的反应速率分别比乙基苯基亚磺酸双（甲氧基羰基）甲亚基和双氰基甲亚基快6.0倍和3.2倍。1的活化参数为ΔH‡ = 125 kJ mol−1，ΔS‡ = -3.8 J K−1 mol−1，而2的活化参数为ΔH‡ = 124 kJ mol−1，ΔS‡ = -2.5 J K−1 mol−1。1和2中β-苯基的取代效应提供了正的Hammett ρ值：ρ = 0.49（γ = 0.997）和ρ = 0.26（γ = 0.993）。从得到的结果可以看出，通过在乙基苯基亚磺酸乙的乙基的2-位引入苯基取代基，基本上是通过倾向于稍微类似于碳负离子的顺式消除过程，从而类似于E1型反应。