O‐(4‐methylphenyl) O‐(4‐nitrophenyl) thiocarbonate | 324047-25-8

• 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: O‐(4‐methylphenyl) O‐(4‐nitrophenyl) thiocarbonate
• 英文别名: 4-nitrophenyl 4-methylphenyl thionocarbonate；(4-Methylphenoxy)-(4-nitrophenoxy)methanethione
• CAS: 324047-25-8
• 化学式: C₁₄H₁₁NO₄S
• 分子量: 289.312
• InChiKey: BIOKPFUXAZFSJT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  96.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  O‐(4‐methylphenyl) O‐(4‐nitrophenyl) thiocarbonate 在 十六烷基三甲基溴化铵 、 sodium hydroxide 作用下， 以 水 为溶剂， 生成 4-nitrophenol sodium salt
  参考文献：
  名称：

  O-芳基O-（4-硝基苯基）硫代碳酸酯与同系碳酸酯的反应性差异：水解反应中的胶束催化

  摘要：

  的碱性水解反应ø - （4-氰基苯基），ø - （4-甲基苯基），和苯基ø - （4-硝基苯基）thionocarbonates（1，2，和3，分别地）和ø - （4-氰基苯基）和苯基O-（4-硝基苯基）碳酸酯（4和5在阳离子表面活性剂CTAB的存在下，已在硼酸水溶液缓冲介质中分光光度法进行了研究。假相模型成功地解释了在该阳离子胶束存在下获得的结果，并确定了各种动力学参数。结果表明，碳酸盐和硫代碳酸盐的催化效率提高。实际上，在硫代碳酸盐1的水解反应中发现485倍的催化效率（ ），而在碳酸盐同系物4的水解反应中，则达到146倍。此外，我们发现在相同的实验条件下（硼酸盐缓冲液pH = 9.0和25°C），缓冲液浓度的增加导致水解速率的降低。

  DOI：

  10.1002/poc.3845
• 作为产物：
  描述：

  对硝基苯酚 、 对甲苯基氯化亚硫代甲酸 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 O‐(4‐methylphenyl) O‐(4‐nitrophenyl) thiocarbonate
  参考文献：
  名称：

  Kinetics and Mechanisms of the Reactions of 4-Nitro- and 3-Nitrophenyl 4-Methylphenyl Thionocarbonates with Alicyclic Amines and Pyridines

  摘要：

  The reactions of the title thionocarbonates (1 and 2, respectively) with a series of secondary alicyclic amines and pyridines are subjected to a kinetic investigation in 44 wt % ethanol-water, 25.0 degreesC, ionic strength 0.2 M (KCl). Under amine excess over the substrates pseudo-first-order rate coefficients (k(obsd)) are obtained for all the reactions. Those of the alicyclic amines with the two substrates show nonlinear upward plots of k(obsd) VS [amine], except the reactions of piperidine, which exhibit linear plots. For these reactions a reaction scheme is proposed with two tetrahedral intermediates, one zwitterionic (T+/-) and the other anionic (T-), with a kinetically significant proton transfer from T+/- to an amine to give T-. From an equation derived from the scheme the rate microcoefficients are obtained through fitting. The rate coefficient for formation of T+/- (k(1)) is larger for 1 compared to 2, which can be explained by a stronger electron-withdrawal of 4-nitro in 1 than 3-nitro in 2, which leaves the thiocarbonyl carbon of 1 more positive and, therefore, more susceptible to nucleophilic attack. For the pyridinolyses of both thionocarbonates the plots of k(obsd) vs [amine] are linear, with the slope (k(N)) independent of pH. The Bronsted plots (log k(N) vs pyridine pK(a)) for these reactions are linear with slopes beta = 0.9 and 1.2 for the pyridinolysis of 1 and 2, respectively. These slopes are consistent with:a mechanism through a T+/- intermediate on the reaction path, whereby decomposition of Ti to products is the rate-determining step. The k(N) values are larger for the reactions of 1 than those of 2. This is attributed to a larger equilibrium formation of T+/- and a larger expulsion rate: of the nucleofuge from T+/- in the reactions of 1 compared to those of 2.

  DOI：

  10.1021/jo005587e

文献信息

• Kinetics and Mechanisms of the Reactions of 4-Nitro- and 3-Nitrophenyl 4-Methylphenyl Thionocarbonates with Alicyclic Amines and Pyridines
  作者：Enrique A. Castro、Paula Garcia、Leonardo Leandro、Nicolas Quesieh、Aquiles Rebolledo、José G. Santos

  DOI：10.1021/jo005587e

  日期：2000.12.1

  The reactions of the title thionocarbonates (1 and 2, respectively) with a series of secondary alicyclic amines and pyridines are subjected to a kinetic investigation in 44 wt % ethanol-water, 25.0 degreesC, ionic strength 0.2 M (KCl). Under amine excess over the substrates pseudo-first-order rate coefficients (k(obsd)) are obtained for all the reactions. Those of the alicyclic amines with the two substrates show nonlinear upward plots of k(obsd) VS [amine], except the reactions of piperidine, which exhibit linear plots. For these reactions a reaction scheme is proposed with two tetrahedral intermediates, one zwitterionic (T+/-) and the other anionic (T-), with a kinetically significant proton transfer from T+/- to an amine to give T-. From an equation derived from the scheme the rate microcoefficients are obtained through fitting. The rate coefficient for formation of T+/- (k(1)) is larger for 1 compared to 2, which can be explained by a stronger electron-withdrawal of 4-nitro in 1 than 3-nitro in 2, which leaves the thiocarbonyl carbon of 1 more positive and, therefore, more susceptible to nucleophilic attack. For the pyridinolyses of both thionocarbonates the plots of k(obsd) vs [amine] are linear, with the slope (k(N)) independent of pH. The Bronsted plots (log k(N) vs pyridine pK(a)) for these reactions are linear with slopes beta = 0.9 and 1.2 for the pyridinolysis of 1 and 2, respectively. These slopes are consistent with:a mechanism through a T+/- intermediate on the reaction path, whereby decomposition of Ti to products is the rate-determining step. The k(N) values are larger for the reactions of 1 than those of 2. This is attributed to a larger equilibrium formation of T+/- and a larger expulsion rate: of the nucleofuge from T+/- in the reactions of 1 compared to those of 2.
• Reactivity differences of <i>O</i> -aryl <i>O</i> -(4-nitrophenyl) thionocarbonates versus their homolog carbonates: Micellar catalysis in hydrolysis reactions
  作者：José G. Santos、Margarita E. Aliaga、Mariana F. Márquez、Mauricio Oyarzún

  DOI：10.1002/poc.3845

  日期：2019.1

  this cationic micelle, and various kinetic parameters were determined. Results show that the catalytic efficiency increases in carbonates and thionocarbonates. In fact, a catalytic efficiency ( ) of 485‐fold was found in the hydrolysis reaction of thionocarbonate 1, while in the carbonate homolog 4, the effect was of 146‐fold. In addition, we found that at the same experimental conditions (Borate buffer

  的碱性水解反应ø - （4-氰基苯基），ø - （4-甲基苯基），和苯基ø - （4-硝基苯基）thionocarbonates（1，2，和3，分别地）和ø - （4-氰基苯基）和苯基O-（4-硝基苯基）碳酸酯（4和5在阳离子表面活性剂CTAB的存在下，已在硼酸水溶液缓冲介质中分光光度法进行了研究。假相模型成功地解释了在该阳离子胶束存在下获得的结果，并确定了各种动力学参数。结果表明，碳酸盐和硫代碳酸盐的催化效率提高。实际上，在硫代碳酸盐1的水解反应中发现485倍的催化效率（ ），而在碳酸盐同系物4的水解反应中，则达到146倍。此外，我们发现在相同的实验条件下（硼酸盐缓冲液pH = 9.0和25°C），缓冲液浓度的增加导致水解速率的降低。