4-溴苯基二硫代乙酸酯 | 193765-64-9

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 中文名称: 4-溴苯基二硫代乙酸酯
• 英文名称: 4-bromophenyl dithioacetate
• 英文别名: (4-Bromophenyl) ethanedithioate
• CAS: 193765-64-9
• 化学式: C₈H₇BrS₂
• 分子量: 247.18
• InChiKey: OYNPUAUGCFTCBK-UHFFFAOYSA-N

物化性质

• 沸点：
  310.5±44.0 °C(Predicted)
• 密度：
  1.59±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 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-溴苯基二硫代乙酸酯 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：

  4-溴苯基硫代乙酸酯 在 劳森试剂 作用下， 生成 4-溴苯基二硫代乙酸酯
  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

• Substituent effects on the activation parameters of pyridine acylation with esters and thioesters in solution
  作者：V. M. Vlasov

  DOI：10.1134/s1070428013030135

  日期：2013.3

  Variation of the activation parameters in the acylation of pyridine with esters and thioesters may be used as a tool for studying mechanisms of acyl transfer reactions in solution. Here, the effect of substituents in benzene and pyridine derivatives on the activation parameters ΔX ≠ (where X stands for enthalpy H, entropy S, or Gibbs energy G) in terms of an equation analogous to the Hammett equation

  吡啶与酯和硫酯的酰化反应中活化参数的变化可用作研究溶液中酰基转移反应机理的工具。在此，根据类似于哈米特方程的方程，使用苯和吡啶衍生物中的取代基对活化参数ΔX ≠（其中X表示焓H，熵S或吉布斯能量G）的影响。恒δΔ X ≠。反应常数δΔ的线性相关ħ ≠ INT上δΔ ģ ≠ 当该方法的一个步骤是唯一确定速率的步骤时，该方法提供了另一种评估吡啶酰化机理变化的方法。
• 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。
• Kinetics and Mechanism of the Aminolysis of Phenyl Dithioacetates in Acetonitrile
  作者：Hyuck Keun Oh、So Young Woo、Chul Ho Shin、Young Sook Park、Ikchoon Lee

  DOI：10.1021/jo970413r

  日期：1997.8.1

  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.