N-methyl-3-nitro-N-(phenylsulfanylmethyl)aniline | 166986-06-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-methyl-3-nitro-N-(phenylsulfanylmethyl)aniline
• CAS: 166986-06-7
• 化学式: C₁₄H₁₄N₂O₂S
• 分子量: 274.343
• InChiKey: WAICJFDUUJSPBJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  74.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-methyl-3-nitro-N-(phenylsulfanylmethyl)aniline 在 水 、 二甲基亚砜 、 sodium chloride 作用下， 生成 thiophenolate 、
  参考文献：
  名称：

  Lifetimes of Iminium Ions in Aqueous Solution

  摘要：

  Iminium cations have been generated in aqueous solution from the solvolysis of anilinothioethers ArN(CH3)CH(2)SR at 25 degrees C. Common ion inhibition of the solvolysis of anilinothioethers was observed when the thiolate anion leaving group was added to the reaction mixture. This inhibition results from trapping of the iminium ion by RS(-) to regenerate the anilinothioether. Rate constants, k(H2O), for hydration of the iminium ions were determined from common ion inhibition of the solvolysis of anilinothioethers in the presence of added thiolate ions and a rate constant of 5 x 10(9) M(-1) s(-1) for diffusion-controlled trapping of the iminium ions by RS(-), which regenerates the starting material. The values of k(H2O) for H2C=N+(CH3)C(6)H(4)X are 1.0 x 10(8), 3.1 x 10(7), 3.0 x 10(7), 5.5 x 10(6), 4.5 x 10(6), and 3.1 x 10(6) s(-1) for X = 4-NO2, 4-CN, 3-NO2, 3-Cl, 4-COO-, and 4-Cl, respectively. Rate constants for the solvolysis of anilinothioethers, k(solv) depend on the pK(a) of the thiolate leaving group with beta(1g) = -0.93 +/- 0.09, which shows that the dissociation reaction has a very late transition state. This result is consistent with rate-limiting diffusion-controlled encounter of RS(-) with H2C=N+(CH3)Ar in the reverse direction. The value of beta(nuc) = 1.00-0.93 = 0.07 +/- 0.09 approximate to 0 is expected for a diffusion-controlled addition reaction. The solvolysis reaction is sensitive to the basicity of the electron-donating nitrogen atom of the aniline with a value of beta(dg) = 0.79 +/- 0.06; i.e., there is a large amount of electron donation from the nitrogen atom that provides the driving force for cleavage of the CH2-S bond in the late transition state. Hammett correlations of the rate constants for the solvolysis reaction, k(solv), show a better correlation with sigma(-) than with sigma for substituents on the aniline and follow rho(-) = -3.3 +/- 0.3. This also indicates a large amount of electron donation and an important contribution of resonance in the transition state of the solvolysis reaction. Reaction of the iminium ions with water is accelerated by electron-withdrawing substituents on the aniline ring and follows rho(-) = 1.5 +/- 0.2 and beta(dg) = -0.35 +/- 0.03; i.e., the rate of reaction of the iminium cation with water is approximately half as sensitive to polar substituents as the solvolysis reaction.

  DOI：

  10.1021/ja00122a015
• 作为产物：
  描述：

  聚合甲醛 、 3-硝基-N-甲基苯胺 、 苯硫酚 以 乙醇 为溶剂， 生成 N-methyl-3-nitro-N-(phenylsulfanylmethyl)aniline
  参考文献：
  名称：

  苯胺基硫醚与苯胺在甲醇中的亲核取代反应

  摘要：

  已经对苯胺硫醚，N-甲基-N -[[（Z-苯硫基）甲基] -Y-苯胺，YC 6 H 4 N（CH 3）CH 2 SC 6 H的苯胺的溶剂分解和氨解反应进行了动力学研究。 4 Z，I在45.0°C的甲醇中。与在水中产生大量寿命的亚胺阳离子相反，溶剂分解是通过在甲醇中的直接置换（S N 2）机理进行的。在氨解，无论键的形成和裂解的井下，在后期小号方式Ñ具有高2过渡状态ρ X（β X）和ρ Ž（β Ž）值。然而，亲核试剂和离去基团之间的交叉相互作用广泛与大的负常数（ρ XZ = -1.7，β XZ = -0.27），这是暗示一个S的Ñ与前侧攻击2反应。氘代苯胺（k H / k D = 0.84-0.88）以及较低的ΔH ≠ （4.2-5.2 kcal mol -1）和ΔS ≠（-46--59 eu）值的逆次要动力学同位素效应是一致的提出的机制。

  DOI：

  10.1039/a909541a

文献信息

• Lifetimes of Iminium Ions in Aqueous Solution
  作者：Sherif Eldin、William P. Jencks

  DOI：10.1021/ja00122a015

  日期：1995.5

  Iminium cations have been generated in aqueous solution from the solvolysis of anilinothioethers ArN(CH3)CH(2)SR at 25 degrees C. Common ion inhibition of the solvolysis of anilinothioethers was observed when the thiolate anion leaving group was added to the reaction mixture. This inhibition results from trapping of the iminium ion by RS(-) to regenerate the anilinothioether. Rate constants, k(H2O), for hydration of the iminium ions were determined from common ion inhibition of the solvolysis of anilinothioethers in the presence of added thiolate ions and a rate constant of 5 x 10(9) M(-1) s(-1) for diffusion-controlled trapping of the iminium ions by RS(-), which regenerates the starting material. The values of k(H2O) for H2C=N+(CH3)C(6)H(4)X are 1.0 x 10(8), 3.1 x 10(7), 3.0 x 10(7), 5.5 x 10(6), 4.5 x 10(6), and 3.1 x 10(6) s(-1) for X = 4-NO2, 4-CN, 3-NO2, 3-Cl, 4-COO-, and 4-Cl, respectively. Rate constants for the solvolysis of anilinothioethers, k(solv) depend on the pK(a) of the thiolate leaving group with beta(1g) = -0.93 +/- 0.09, which shows that the dissociation reaction has a very late transition state. This result is consistent with rate-limiting diffusion-controlled encounter of RS(-) with H2C=N+(CH3)Ar in the reverse direction. The value of beta(nuc) = 1.00-0.93 = 0.07 +/- 0.09 approximate to 0 is expected for a diffusion-controlled addition reaction. The solvolysis reaction is sensitive to the basicity of the electron-donating nitrogen atom of the aniline with a value of beta(dg) = 0.79 +/- 0.06; i.e., there is a large amount of electron donation from the nitrogen atom that provides the driving force for cleavage of the CH2-S bond in the late transition state. Hammett correlations of the rate constants for the solvolysis reaction, k(solv), show a better correlation with sigma(-) than with sigma for substituents on the aniline and follow rho(-) = -3.3 +/- 0.3. This also indicates a large amount of electron donation and an important contribution of resonance in the transition state of the solvolysis reaction. Reaction of the iminium ions with water is accelerated by electron-withdrawing substituents on the aniline ring and follows rho(-) = 1.5 +/- 0.2 and beta(dg) = -0.35 +/- 0.03; i.e., the rate of reaction of the iminium cation with water is approximately half as sensitive to polar substituents as the solvolysis reaction.
• Nucleophilic substitution reactions of anilino thioethers with anilines in methanol
  作者：Huck Keun Oh、Jin Hee Yang、Hai Whang Lee、Ikchoon Lee

  DOI：10.1039/a909541a

  日期：——

  state with high ρX (βX) and ρZ (βZ) values. However, cross interactions between the nucleophile and leaving group are extensive with large negative constants (ρXZ=−1.7, βXZ=−0.27), which are suggestive of an SN2 reaction with frontside attack. The inverse secondary kinetic isotope effects involving deuterated anilines (kH/kD=0.84–0.88) along with low ΔH≠ (4.2–5.2 kcal mol−1) and ΔS≠ (−46–−59 e.u.) values

  已经对苯胺硫醚，N-甲基-N -[[（Z-苯硫基）甲基] -Y-苯胺，YC 6 H 4 N（CH 3）CH 2 SC 6 H的苯胺的溶剂分解和氨解反应进行了动力学研究。 4 Z，I在45.0°C的甲醇中。与在水中产生大量寿命的亚胺阳离子相反，溶剂分解是通过在甲醇中的直接置换（S N 2）机理进行的。在氨解，无论键的形成和裂解的井下，在后期小号方式Ñ具有高2过渡状态ρ X（β X）和ρ Ž（β Ž）值。然而，亲核试剂和离去基团之间的交叉相互作用广泛与大的负常数（ρ XZ = -1.7，β XZ = -0.27），这是暗示一个S的Ñ与前侧攻击2反应。氘代苯胺（k H / k D = 0.84-0.88）以及较低的ΔH ≠ （4.2-5.2 kcal mol -1）和ΔS ≠（-46--59 eu）值的逆次要动力学同位素效应是一致的提出的机制。