morpholine 4-nitrophenyl thionocarbamate | 5292-87-5

• 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: morpholine 4-nitrophenyl thionocarbamate
• 英文别名: morpholine-4-carbothioic acid O-(4-nitro-phenyl) ester；Morpholin-4-YL-(4-nitrophenoxy)methanethione；O-(4-nitrophenyl) morpholine-4-carbothioate
• CAS: 5292-87-5
• 化学式: C₁₁H₁₂N₂O₄S
• 分子量: 268.293
• InChiKey: IVZZYAQWPUGSQX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  99.6
• 氢给体数：
  0
• 氢受体数：
  5

安全信息

• 海关编码：
  2934999090

反应信息

• 作为产物：
  描述：

  吗啉 、 对硝基苯基硫代氯甲酸酯 以 水 为溶剂， 生成 morpholine 4-nitrophenyl thionocarbamate
  参考文献：
  名称：

  苯基和4-硝基苯基氯噻吩甲酸酯氨基分解的动力学和机理。

  摘要：

  一系列仲脂环族胺与标题底物的反应在25°C的离子强度0.2 M（用KCl维持）的水溶液中进行动力学研究。在胺下，发现过量的伪一阶速率系数（k（obsd））。在恒定pH下，k（obsd）对游离胺浓度的曲线是线性的，其斜率（k（N））与pH无关。获得的两种底物的氨解布朗斯台德型图（log k（N）与胺pK（a））呈线性，斜率相同，β= 0.26。根据该值，动力学定律和产物分析，可以推断这些反应在反应路径上通过两性离子四面体加成中间体（T（+/-））进行，其形成是决定速率的步骤。

  DOI：

  10.1021/jo970276y

文献信息

• 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。
• Structure−Reactivity Correlations in the Aminolysis and Pyridinolysis of Bis(phenyl) and Bis(4-nitrophenyl) Thionocarbonates
  作者：Enrique A. Castro、José G. Santos、Jimena Téllez、María I. Umaña

  DOI：10.1021/jo970624w

  日期：1997.9.1

  The reactions of a series of secondary alicyclic amines with bis(phenyl) and bis(4-nitrophenyl) thionocarbonates (BPTOC and BNPTOC, respectively), and a series of pyridines with the latter substrate, are subjected to a kinetic investigation in water, 25.0 degrees C, ionic strength 0.2 M (KCl). All the reactions obey pseudo-first-order kinetics under amine excess over the substrate. The reactions of piperidine with BPTOC are first order in amine, but those of the same substrate with the other secondary alicyclic amines exhibit a complex order, consistent with the existence of both a zwitterionic (T+/-) and an anionic (T-) tetrahedral intermediates on the reaction pathway. Deprotonation of T+/- by a secondary amine to give T- (rate coefficient k(3)) competes with expulsion of the amine moiety from T+/- (k(-1)), except in the reactions of 1-formylpiperazine whereby k(-1) much greater than k(3) [1-formylpiperazine], and a kinetics second order in amine is observed. The reactions of secondary alicyclic amines with BNPTOC are all first order in amine and show a nonlinear Bronsted-type plot with limiting slopes beta = 0.1 (high amine pK(a)) and beta = 0.5 (low amine pK(a)). This slight curvature is consistent with a concerted mechanism (one step). The intermediate T+/- is not formed because of its high kinetic instability due to a large k(-1) value. The pyridinolysis of BNPTOC exhibits a first order in amine kinetics and a linear Bronsted-type plot of slope beta = 1.0, which is consistent with the existence of T+/- whereby the expulsion of the leaving group from T+/- is the rate-determining step. This intermediate is less unstable than that with a secondary amine due to the fact that k(-1) is smaller for a pyridine compared to an isobasic secondary alicyclic amine.