3-nitrophenyl 4-methylphenyl thionocarbonate | 324047-26-9

• 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: 3-nitrophenyl 4-methylphenyl thionocarbonate
• 英文别名: (4-Methylphenoxy)-(3-nitrophenoxy)methanethione
• CAS: 324047-26-9
• 化学式: C₁₄H₁₁NO₄S
• 分子量: 289.312
• InChiKey: YYCLHKZLJBKEBB-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：

  4-甲基吡啶 、 3-nitrophenyl 4-methylphenyl thionocarbonate 在 potassium chloride 作用下， 以 乙醇 、 水 为溶剂， 生成 3-Nitro-phenolate4-methyl-1-p-tolyloxythiocarbonyl-pyridinium;
  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
• 作为产物：
  描述：

  对甲苯基氯化亚硫代甲酸 、 间硝基苯酚 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 3-nitrophenyl 4-methylphenyl thionocarbonate
  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.