O‐(4‐cyanophenyl) O‐(4‐nitrophenyl) thiocarbonate | 370104-80-6

• 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‐cyanophenyl) O‐(4‐nitrophenyl) thiocarbonate
• 英文别名: 4-nitrophenyl 4-cyanophenyl thionocarbonate；4-cyanophenyl 4-nitrophenyl thiocarbonate；4-(4-Nitrophenoxy)carbothioyloxybenzonitrile
• CAS: 370104-80-6
• 化学式: C₁₄H₈N₂O₄S
• 分子量: 300.295
• InChiKey: LPVPYLRPNYRFHU-UHFFFAOYSA-N

物化性质

• 沸点：
  467.7±55.0 °C(Predicted)
• 密度：
  1.46±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  120
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  O‐(4‐cyanophenyl) 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 、 4-cyanophenyl chlorothionoformate 生成 O‐(4‐cyanophenyl) O‐(4‐nitrophenyl) thiocarbonate
  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

• Kinetic Study of the Phenolysis of Bis(4-nitrophenyl) Carbonate, Bis(4-nitrophenyl) Thionocarbonate, and Methyl 4-Nitrophenyl Thionocarbonate
  作者：Enrique A. Castro、Mauricio Angel、David Arellano、José G. Santos

  DOI：10.1021/jo0101252

  日期：2001.10.1

  The reactions of a homogeneous series of phenols with bis(4-nitrophenyl) carbonate (BNPC), bis(4-nitrophenyl) thionocarbonate (BNPTOC), and methyl 4-nitrophenyl thionocarbonate (MNPTOC) are subjected to a kinetic investigation in water, at 25.0 degrees C and ionic strength of 0.2 M (KCl). Under excess of phenol over the substrate, all the reactions obey pseudo-first-order kinetics and are first order

  均相系列苯酚与碳酸双（4-硝基苯酯），双（4-硝基苯基）硫代碳酸酯（BNPTOC）和4-硝基苯基硫代碳酸甲酯（MNPTOC）的反应在水中进行25.0摄氏度，离子强度为0.2 M（KCl）。在底物上过量的苯酚下，所有反应均遵循拟一级反应动力学，并且在酚盐阴离子中为一级反应。BNPC的反应显示出线性的Bönsted型图，斜率β= 0.66，与一致的机理一致（一个步骤）。相比之下，BNPTOC和MNPTOC的双相布朗斯台德图在高pK（a）时斜率分别为β= 0.30和0.44，在低pK（a）时斜率分别为β= 1.25和1.60，与逐步一致机制。对于两种硫代碳酸酯的反应，布朗斯台德图中心（pK（a）（0））的pK（a）值为7.1，它对应于4-硝基苯酚的pK（a）。这证实了硫代碳酸酯的酚类是逐步过程，形成了阴离子四面体中间体。通过比较标题反应和相似反应的动力学和机理，可以得出以下结论：（i）在阴离子四
• Kinetic and theoretical study on nucleofugality in the phenolysis of 3-nitrophenyl and 4-nitrophenyl 4-cyanophenyl thionocarbonates
  作者：Enrique A. Castro、Alvaro Cañete、Paola R. Campodónico、Marjorie Cepeda、Paulina Pavez、Renato Contreras、José G. Santos

  DOI：10.1016/j.cplett.2013.04.002

  日期：2013.5

  evaluate the nucleofugality of the corresponding leaving groups. For the reaction of 2 only 4-nitrophenoxide is obtained as leaving group. For the reaction of 1 the nucleofugality ratio 3-nitrophenoxide/4-cyanophenoxide is 1/3 from the corresponding T− intermediate. Theoretical calculations confirm the experimental results. From these results it can be concluded that the non-leaving group affects the

  对3-硝基苯基4-氰基苯基硫代碳酸酯（1）和4-硝基苯基4-氰基苯基硫代碳酸酯（2）的酚醛化进行动力学研究，以评估相应离去基团的核键性。对于2的反应，仅获得4-硝基苯氧基作为离去基团。对于反应1的nucleofugality比率3-硝基苯酚/ 4- cyanophenoxide是从相应的T 1/3 -中间体。理论计算证实了实验结果。从这些结果可以得出结论，非离去基团影响核不纯率。
• Nucleofugality hierarchy, in the aminolysis reaction of 4-cyanophenyl 4-nitrophenyl carbonate and thionocarbonate. Experimental and theoretical study
  作者：Rodrigo Montecinos、Margarita E. Aliaga、Paulina Pavez、Patricio Cornejo、José G. Santos

  DOI：10.1039/d0nj05837h

  日期：——

  Nucleophilic substitution reactions of the title compounds have been investigated with a series of secondary alicyclic amines in several solvents. The solvent, amine, and electrophilic group effects on kinetics, mechanism and nucleofugality hierarchy are discussed from experimental and theoretical studies. These studies show the mechanistic dependence on the solvent polarity; the theoretical results

  已经在几种溶剂中用一系列脂环仲胺研究了标题化合物的亲核取代反应。从实验和理论研究中讨论了溶剂、胺和亲电子基团对动力学、机理和核疏散等级的影响。这些研究显示了对溶剂极性的机械依赖性；理论结果表明，反应中心（C O 和C S ）的相对极化和离核剂的稳定性是控制产物分布的主要因素。
• Kinetics and Mechanisms of the Reactions of 3-Methoxyphenyl, 3-Chlorophenyl, and 4-Cyanophenyl 4-Nitrophenyl Thionocarbonates with Alicyclic Amines
  作者：Enrique A. Castro、Leonardo Leandro、Nicolas Quesieh、José G. Santos

  DOI：10.1021/jo0157371

  日期：2001.9.1

  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.
• 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。