4-chlorophenyl dithioacetate | 193765-63-8

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 4-chlorophenyl dithioacetate
• 英文别名: (4-Chlorophenyl) ethanedithioate
• CAS: 193765-63-8
• 化学式: C₈H₇ClS₂
• 分子量: 202.729
• InChiKey: LHRNZEOMNAELEG-UHFFFAOYSA-N

物化性质

• 沸点：
  292.8±42.0 °C(Predicted)
• 密度：
  1.32±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  57.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  苯胺 、 4-chlorophenyl dithioacetate 以 乙腈 为溶剂， 生成 硫代乙酰苯胺
  参考文献：
  名称：

  Kinetics and Mechanism of the Aminolysis of Phenyl Dithioacetates in Acetonitrile

  摘要：

  The aminolysis reactions of phenyl dithioacetates with anilines (AN), N,N-dimethylanilines (DMA), and benzylamines (BA) in acetonitrile are investigated. The mechanism is relatively simple, involving a zwitterionic tetrahedral intermediate, T+/-, and is uncomplicated by the fast proton transfer step which may become rate limiting in the aminolysis of thiono and dithio esters and carbonates with poor leaving groups in water. The mechanism changes from rate-limiting expulsion of the leaving group with beta(X) = 0.80-0.86 and beta(Z) = -0.71 to -0.84 for ANs and DMAs to rate-limiting attack by the nucleophile with much smaller magnitudes of beta(X) and beta(Z) for BAs. The relatively large beta(XZ) values for the former series and a smaller beta(XZ) for the latter series support the proposed mechanistic change.

  DOI：

  10.1021/jo970413r
• 作为产物：
  描述：

  S-acetyl-4-chlorothiophenol 在 劳森试剂 作用下， 生成 4-chlorophenyl dithioacetate
  参考文献：
  名称：

  Kinetics and Mechanism of the Aminolysis of Phenyl Dithioacetates in Acetonitrile

  摘要：

  The aminolysis reactions of phenyl dithioacetates with anilines (AN), N,N-dimethylanilines (DMA), and benzylamines (BA) in acetonitrile are investigated. The mechanism is relatively simple, involving a zwitterionic tetrahedral intermediate, T+/-, and is uncomplicated by the fast proton transfer step which may become rate limiting in the aminolysis of thiono and dithio esters and carbonates with poor leaving groups in water. The mechanism changes from rate-limiting expulsion of the leaving group with beta(X) = 0.80-0.86 and beta(Z) = -0.71 to -0.84 for ANs and DMAs to rate-limiting attack by the nucleophile with much smaller magnitudes of beta(X) and beta(Z) for BAs. The relatively large beta(XZ) values for the former series and a smaller beta(XZ) for the latter series support the proposed mechanistic change.

  DOI：

  10.1021/jo970413r

文献信息

• Nucleophilic Substitution Reactions of Aryl Dithioacetates with Pyridines in Acetonitrile
  作者：Hyuck Keun Oh、Myoung Hwa Ku、Hai Whang Lee、Ikchoon Lee

  DOI：10.1021/jo025637a

  日期：2002.5.1

  are carried out in acetonitrile at 60.0 degrees C. A biphasic Brönsted plot is obtained with a change in slope from a large value (beta(X) congruent with 0.9) to a small value (beta(X) congruent with 0.4) at pK(a) degrees = 5.2, which is attributed to a change in the rate-limiting step from breakdown to formation of a zwitterionic tetrahedral intermediate, T(+/-), in the reaction path as the basicity

  芳基二硫代乙酸酯（CH（3）C（= S）SC（6）H（4）Z）的吡啶分解反应（XC（5）H（4）N）的动力学研究在60.0摄氏度的乙腈中进行。在pK（a）度= 5.2时，斜率从大值（β（X）等于0.9）变小值（β（X）等于0.4）获得斜率双相图。随着吡啶亲核试剂的碱度增加，反应路径中的限速步骤从分解到两性离子四面体中间体T（+/-）的变化。交叉相互作用常数rho（XZ）从大的正值（rho（XZ）= +1.34）到小的负值（rho（XZ）= -0.15）的清晰变化可以支持所提出的机械变化。