O-Ethyl S-(2,4,6-trinitrophenyl) thiocarbonate | 153621-93-3

• 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-Ethyl S-(2,4,6-trinitrophenyl) thiocarbonate
• 英文别名: ethyl S-(2,4,6-trinitrophenyl) thiolcarbonate；S-(2,4,6-trinitrophenyl) ethyl thiocarbonate；ethyl S-(2,4,6-trinitrophenyl) thiocarbonate；S-(2,4,6-trinitrophenyl) thiocarbonate；Ethyl (2,4,6-trinitrophenyl)sulfanylformate
• CAS: 153621-93-3
• 化学式: C₉H₇N₃O₈S
• 分子量: 317.236
• InChiKey: NWNIPRPUOPSAFE-UHFFFAOYSA-N

物化性质

• 沸点：
  434.3±55.0 °C(Predicted)
• 密度：
  1.65±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  189
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  O-Ethyl S-(2,4,6-trinitrophenyl) thiocarbonate 在 citrate buffer 、 potassium chloride 、 thiobenzoate anion 作用下， 以 水 为溶剂， 生成 2,4,6-trinitrobenzenethiolate anion
  参考文献：
  名称：

  2,4-二硝基苯基和2,4,6-三硝基苯基甲基碳酸酯和S-（2,4-二硝基苯基）和S-（2,4,6-三硝基苯基）硫代碳酸乙酯的苯硫解动力学和机理。

  摘要：

  碳酸2,4-二硝基苯基和2,4,6-三硝基苯基甲基碳酸酯（分别为DNPC和TNPC）与S-（2,4-二硝基苯基）和S-（2,4,6-三硝基苯基）硫代碳酸乙酯的反应（ DNPTC和TNPTC）分别与一系列苯硫醇盐阴离子在水中进行动力学研究，温度为25.0摄氏度，离子强度为0.2 M（KCl）。这些反应在过量的苯硫醇盐下服从拟一级反应动力学，在后一种反应物中是一级反应。但是，在4-硝基苯硫代酸根阴离子与TNPC和TNPTC的反应中使用了可比的反应物浓度，显示了二级动力学。亲核速率常数与pH无关，但TNPC与4-甲氧基和五氟苯硫醇酯的反应除外。TNPTC与苯硫醇盐，4-氯-和3-氯苯硫醇盐，表现出对酸的依赖性。对于DNPC，TNPC，DNPTC和TNPTC的反应，亲核速率常数的布朗斯台德图呈线性，斜率分别为β= 0.9、1.0、0.9和0.9。在DNPC和DNPTC在pK（a）处的反应中，在布朗斯台德图中没有发现断裂。4

  DOI：

  10.1021/jo034082w
• 作为产物：
  描述：

  在 氢氧化钾 、 potassium chloride 作用下， 以 1,4-二氧六环 、 水 为溶剂， 生成 O-Ethyl S-(2,4,6-trinitrophenyl) thiocarbonate
  参考文献：
  名称：

  O-乙基S-（2,4,6-三硝基苯基）硫代和二硫代碳酸酯的碱解机理

  摘要：

  在25.0°C和5％的二恶烷水溶液中，分别于5％的二恶烷中动力学研究了O-乙基S-（2,4,6-三硝基苯基）硫代碳酸氢盐和二硫代碳酸氢盐的碱性水解，分别为1和2。–3（KCl）。检测到两个动力学过程，它们在时间上间隔得很好。快速过程涉及通过添加HO –形成σ络合物。到芳环的未取代位置之一上，然后使该络合物快速电离。缓慢的过程导致在2的反应中分别以10∶1的比例形成2,4,6-三硝基苯氧基和2,4,6-三硝基苯硫基离子的混合物，并在2：的混合物中形成混合物。反应中1的比例为1，与KOH浓度无关。尽管底物在KOH浓度下表现出不同的动力学行为，但可以基于常见的反应机理来讨论结果。

  DOI：

  10.1039/a903143j

文献信息

• Kinetics and Mechanism of the Reactions of Anilines with Ethyl <i>S</i>-Aryl Thiocarbonates
  作者：Enrique A. Castro、Leonardo Leandro、Pablo Millán、José G. Santos

  DOI：10.1021/jo982063u

  日期：1999.3.1

  pK(a) of anilinium ions) are linear, with slopes beta = 0.9 for DNPTC, in agreement with a stepwise mechanism where the breakdown of a tetrahedral addition intermediate (T(+/-)) is rate determining, and beta = 0.54 for TNPTC, consistent with a concerted mechanism. Consideration of the results for aminolysis from the present work and those from previous studies leads to the following conclusions. (i) The

  苯胺与S-（2,4-二硝基苯基）硫代碳酸乙酯（DNPTC）和S-（2,4,6-三硝基苯基）硫代碳酸乙酯（TNPTC）的反应在水溶液中于25.0℃下进行动力学研究。离子强度0.2（KCl）。通过分光光度法（400 nm）释放相应的取代苯硫醇根阴离子来研究反应。在苯胺过量的情况下，找到伪一阶速率系数（k（obsd））。k（obsd）与[N]（N为游离取代的苯胺）的关系呈线性且与pH无关，斜率为k（N）。Brönsted型图（苯胺离子的log k（N）vs pK（a））是线性的，DNPTC的斜率β= 0.9，这与逐步机理有关，其中四面体加成中间体（T（+ / -））是速率确定的，对于TNPTC，β= 0.54，与协调机制一致。考虑目前工作和以前研究得出的氨解结果，得出以下结论。（i）具有2，4-二硝基苯硫基的四面体中间体比包括2，4，6-三硝基苯硫基的中间体更稳定。（ii）具有2,4,6-三硝基
• Kinetics and Mechanism of the Reactions of Quinuclidines with Ethyl <i>S</i>-Aryl Thiolcarbonates
  作者：Enrique A. Castro、Patricio Muñoz、José G. Santos

  DOI：10.1021/jo991036g

  日期：1999.10.1

  with slope beta = 0.85 for NPTC, in agreement with a stepwise mechanism where the breakdown of a tetrahedral addition intermediate (T(+/-)) is rate determining, and beta = 0.54 and 0.47 for DNPTC and TNPTC, respectively, consistent with a concerted mechanism. By comparison of the reactions under investigation among them and with similar aminolyses, the following conclusions can be drawn: (i) Substitution

  奎宁烷与S-（4-硝基苯基）硫代碳酸乙酯（NPTC），S-（2,4-二硝基苯基）硫代碳酸乙酯（DNPTC）和S-（2,4,6-三硝基苯基）硫代碳酸乙酯（TNPTC）的反应在25.0摄氏度，离子强度0.2（KCl）的水溶液中进行动力学研究。通过分光光度法（400 nm）释放相应的取代苯硫醇根阴离子来研究反应。在奎尼丁过量下，发现伪一阶速率系数（k（obsd））。k（obsd）对[N]（N为游离取代的奎尼丁）的图是线性的，且与pH无关，斜率为k（N）。布朗斯台德型图（对数喹喔啉离子的对数k（N）与pK（a））是线性的，对于NPTC，斜率β= 0.85，与分步机制一致，其中确定速率的是四面体加成中间体（T（+/-））的分解，DNPTC和TNPTC的beta分别为0.54和0.47，与一致的机制一致。通过比较所研究的反应和相似的氨基酸水解反应，可以得出以下结论：（i）用2,4-二硝基苯硫基或2,4
• Kinetics and Mechanism of the Pyridinolysis of <i>O</i>-Ethyl <i>S</i>-Aryl Thiocarbonates in Aqueous Solution
  作者：Enrique A. Castro、María I. Pizarro、José G. Santos

  DOI：10.1021/jo960781f

  日期：1996.1.1

  The reactions of a series of 3- and 4-substituted pyridines with S-(4-nitrophenyl), S-(2,4-dinitrophenyl), and S-(2,4,6-trinitrophenyl) O-ethyl thiocarbonates (NPTC, DNPTC, and TNPTC, respectively) are subjected to a kinetic investigation in aqueous solution, 25.0 degrees C, ionic strength 0.2 M (KCl). Pseudo-first-order rate coefficients (K-obsd) are found under amine excess. Plots of k(obsd) vs free amine concentration are linear and pH independent. The Bronsted-type plot for NPTC is linear whereas those for DNPTC and TNPTC are biphasic with slopes beta(1) = 0.2 (high pK(a)) for both, and beta(2) = 0.9 and 0.8 (low pK(a)) for DNPTC and TNPTC, respectively. The curvature center on the PKa axis is pK(a)(o) = 8.6 (DNPTC) and 7.3 (TNPTC). The Bronsted plots are consistent with the presence of a zwitterionic tetrahedral intermediate on the reaction path where its breakdown is rate determining for NPTC and there isa change in the rate-limiting step for the reactions of the other two substrates. Comparison of the stepwise reactions of the present work with the concerted ones of DNPTC and TNPTC with secondary alicyclic amines shows that the latter amines greatly destabilize T-+/- relative to isobasic pyridines. Comparison of the present reactions with other pyridinolysis indicates that substitution of the oxygen phenoxy atom by sulfur increases pK(a)(o) and the change of methyl to ethoxy as the remaining group also enlarges the pK(a)(o) and besides destabilizes T-+/-.
• Concerted mechanism of the reactions of secondary alicyclic amines with O-ethyl S-(2,4,6-trinitrophenyl) thiocarbonate
  作者：Enrique A. Castro、Mirtha Salas、Jose G. Santos

  DOI：10.1021/jo00080a008

  日期：1994.1

  The title reactions are subjected to a kinetic study in water, 25.0 degrees C, ionic strength 0.2 M (KCl). Under amine excess, pseudo-first-order coefficients (k(obsd)) are obtained. Plots of k(obsd) vs free amine concentration at constant pH are linear, with the slope (k(N)) independent of pH. The Bronsted-type plot (log k(N) vs pK(a) of the amine) found is linear, with slope beta=0.48, indicating a concerted mechanism. If the present reactions were stepwise, the hypothetical pK(a) value at the Bronsted break (pK(a)(0)) would be 7;9, which is within the pK(a) range of the amines (6.4-11.5). The fact that the Bronsted break is not observed confirms that the present reactions are concerted. With the data for the present reactions together with those for the same aminolysis of O-ethyl S-(2,4-dinitrophenyl) thiocarbonate, an equation relating log k(N) with the pK(a) of both the amine and the leaving group of the substrate is deduced. Comparison of the present reactions with similar aminolyses show that a tetrahedral addition intermediate is kinetically destabilized by the changes of the following groups attached to its central carbon: ii) methyl by ethoxy, (ii) S- by O-, and (iii) pyridino by an isobasic secondary alicyclic amino group.
• Concerted Mechanisms of the Reactions of Ethyl <i>S</i>-Aryl Thiocarbonates with Substituted Phenoxide Ions
  作者：Enrique A. Castro、Paulina Pavez、José G. Santos

  DOI：10.1021/jo981956j

  日期：1999.4.1

  The reactions of 4-nitrophenyl, 2,4-dinitrophenyl, and 2,4,6-trinitrophenyl O-ethyl thiolcarbonates with substituted phenoxide ions are subjected to a kinetic study in water, 25.0 degrees C, ionic strength 0.2 M (KCl). By following the reactions spectrophotometrically, pseudo-first-order rate coefficients (k(obsd)) are found under excess of the nucleophile. Plots of k(obsd) VS phenoxide anion concentration at constant pH are linear, with the slope (k(N)) independent of pH. The Bronsted-type plots (log kN vs pK(a) of the phenols) are linear with slopes beta = 0.92, 0.77, and 0.61 for the reactions of the 4-nitrophenyl, 2,4-dinitrophenyl, and 2,4,6-trinitrophenyl derivatives, respectively. For these reactions, a concerted mechanism is proposed since the slope values are similar to those found in the concerted phenolysis of aryl acetates; the slope magnitudes are not consistent with a stepwise mechanism where the formation of a tetrahedral intermediate is rate limiting. Our results are in line with the finding that the reactions of the 2,4-dinitrophenyl and 2,4,6-trinitrophenyl derivatives with secondary alicyclic amines in water are concerted. In contrast, the reactions of the same substrates with pyridines are stepwise, which means that substitution of a pyridine moiety in a tetrahedral intermediate with a benzenethio group by a phenoxy group destabilizes the intermediate.