3-methoxyphenyl 4-nitrophenyl thionocarbonate | 370104-78-2

• 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-methoxyphenyl 4-nitrophenyl thionocarbonate
• 英文别名: 3-methoxyphenyl 4-nitrophenyl thiocarbonate；(3-Methoxyphenoxy)-(4-nitrophenoxy)methanethione
• CAS: 370104-78-2
• 化学式: C₁₄H₁₁NO₅S
• 分子量: 305.311
• InChiKey: SNLVNHRGTUBKKK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  106
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  吗啉 、 3-methoxyphenyl 4-nitrophenyl thionocarbonate 以 乙醇 、 水 为溶剂， 生成 对硝基苯酚 、
  参考文献：
  名称：

  Kinetics and Mechanisms of the Reactions of 3-Methoxyphenyl, 3-Chlorophenyl, and 4-Cyanophenyl 4-Nitrophenyl Thionocarbonates with Alicyclic Amines

  摘要：

  The reactions of 3-methoxyphenyl, 3-chlorophenyl, and 4-cyanophenyl 4-nitrophenyl thionocarbonates (1, 2, and 3, respectively) with a series of secondary alicyclic amines are studied kinetically in 44 wt % ethanol-water at 25.0 degreesC and an ionic strength of 0.2 M (KCl). Pseudo-first-order rate coefficients (k(obsd)) are obtained for all reactions (amine excess was used). The reactions of compound 1 with piperidine, piperazine, and 1-(2-hydroxyethyl)piperazine and of compounds 2 and 3 with these amines and morpholine exhibit linear k(obsd) versus amine concentration plots with slopes (k(1)) independent of pH. In contrast, the plots are nonlinear upward for the reactions of substrate I with morpholine, 1-formylpiperazine, and piperazinium ion and of substrates 2 and 3 with the two latter amines. For all these reactions, a reaction scheme is proposed with a zwitterionic tetrahedral intermediate (T +/-), which can be deprotonated by an amine to yield an anionic intermediate (T-). When the nonlinear plots are fit through an equation derived from the scheme, rate and equilibrium microcoefficients are obtained. The Bronsted-type plots for k(1) are linear with slopes of beta (1) = 0.22, 0.20, and 0.24 for the aminolysis of 1, 2, and 3, respectively, indicating that the formation of T+/- (k(1) step) is rate-determining. The k(1) values for these reactions follow the sequence 3 > 2 > 1, which can be explained by the sequence of the electron-withdrawing effects from the substituents on the nonleaving group of the substrates.

  DOI：

  10.1021/jo0157371
• 作为产物：
  描述：

  对硝基苯酚 、 3-methoxyphenyl thiochloroformate 生成 3-methoxyphenyl 4-nitrophenyl thionocarbonate
  参考文献：
  名称：

  Kinetics and Mechanisms of the Reactions of 3-Methoxyphenyl, 3-Chlorophenyl, and 4-Cyanophenyl 4-Nitrophenyl Thionocarbonates with Alicyclic Amines

  摘要：

  The reactions of 3-methoxyphenyl, 3-chlorophenyl, and 4-cyanophenyl 4-nitrophenyl thionocarbonates (1, 2, and 3, respectively) with a series of secondary alicyclic amines are studied kinetically in 44 wt % ethanol-water at 25.0 degreesC and an ionic strength of 0.2 M (KCl). Pseudo-first-order rate coefficients (k(obsd)) are obtained for all reactions (amine excess was used). The reactions of compound 1 with piperidine, piperazine, and 1-(2-hydroxyethyl)piperazine and of compounds 2 and 3 with these amines and morpholine exhibit linear k(obsd) versus amine concentration plots with slopes (k(1)) independent of pH. In contrast, the plots are nonlinear upward for the reactions of substrate I with morpholine, 1-formylpiperazine, and piperazinium ion and of substrates 2 and 3 with the two latter amines. For all these reactions, a reaction scheme is proposed with a zwitterionic tetrahedral intermediate (T +/-), which can be deprotonated by an amine to yield an anionic intermediate (T-). When the nonlinear plots are fit through an equation derived from the scheme, rate and equilibrium microcoefficients are obtained. The Bronsted-type plots for k(1) are linear with slopes of beta (1) = 0.22, 0.20, and 0.24 for the aminolysis of 1, 2, and 3, respectively, indicating that the formation of T+/- (k(1) step) is rate-determining. The k(1) values for these reactions follow the sequence 3 > 2 > 1, which can be explained by the sequence of the electron-withdrawing effects from the substituents on the nonleaving group of the substrates.

  DOI：

  10.1021/jo0157371

文献信息

• Kinetics and mechanism of the anilinolysis of aryl 4-nitrophenyl thionocarbonates in aqueous ethanol
  作者：Enrique A. Castro、Rayen Acevedo、José G. Santos

  DOI：10.1002/poc.1814

  日期：2011.7

  aniline concentration are linear, with the slopes (kN) pH independent, kN being the rate coefficient for the anilinolysis of the thionocarbonates. The Brønsted plot (log kN vs. pKa of anilinium ions) for thionocarbonate 1 is linear, with slope (β) 0.62, which is consistent with a concerted mechanism. The Brønsted plots for thionocarbonates 2 and 3 are curved, with slopes 0.1 at high pKa for both reaction

  双（4-硝基苯基），3-氯苯基4-硝基苯基，和3-甲氧基苯基4-硝基苯基thionocarbonates（的反应1，2，和3，分别地）与一系列苯胺经受在44重量动力学调查。 ％乙醇-水，在25.0°C，离子强度为0.2M。在苯胺过量的情况下，发现拟一级反应速率系数（k obs）。k obs对苯胺浓度的曲线是线性的，其斜率（k N）与pH无关，k N是硫代碳酸盐的苯胺分解的速率系数。布朗斯台德图（log  k N vs. p K一苯胺离子）为硫羰碳酸酯1是直链的，具有斜率（β）0.62，这与协同机制是一致的。所述布朗斯台德地块为thionocarbonates 2和3是弯曲的，与高磷斜坡0.1 ķ一个用于两个反应系列和斜坡0.84和0.79，在低p- ķ一个用于反应2和3分别。后者图是根据到一个步进机制，通过两性离子的四面体中间体（T ±）及其阴离子类似物（T - ），后者是用T的去质子化形成±通过缓冲区的基本形式（HPO