O-phenyl piperidine-1-carbothioate

• 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-phenyl piperidine-1-carbothioate
• 化学式: C₁₂H₁₅NOS
• 分子量: 221.323
• InChiKey: TVWGACPYJWIWPY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  44.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  N-乙基哌啶 、 硫代氯甲酸苯酯 以 二氯甲烷 为溶剂， 反应 1.0h， 以98%的产率得到O-phenyl piperidine-1-carbothioate
  参考文献：
  名称：

  Phenyl Chloro(thionoformate): a New Dealkylating Agent of Tertiary Amines

  摘要：

  苯基氯代(硫代甲酸酯)在20°下与无障碍的三级脂肪胺迅速反应，生成硫代氨酸酯和烷基氯化物。二烷基环己胺出奇地迅速反应，主要生成环己烯。硫代氨酸酯经过甲基硫酸二甲酯处理后，再用水水解转化为二级胺盐。在氨基中，反应速率和烷基团裂解选择性被发现优于或与以前报道的氯代甲酸酯相媲美。

  DOI：

  10.1071/ch98147

文献信息

• Kinetic Study of the Aminolysis and Pyridinolysis of <i>O-</i>Phenyl and <i>O</i>-Ethyl <i>O</i>-(2,4-Dinitrophenyl) Thiocarbonates. A Remarkable Leaving Group Effect
  作者：Enrique A. Castro、María Cubillos、Margarita Aliaga、Sandra Evangelisti、José G. Santos

  DOI：10.1021/jo035451r

  日期：2004.4.1

  The smaller pKa0 value for the reactions of SA amines with 2 than with O-ethyl S-(2,4-dinitrophenyl) dithiocarbonate (pKa0 = 9.2) is explained by the greater nucleofugality from T⧧ of 2,4-dinitrophenoxide (DNPO-) relative to the thio derivative. The stepwise reactions of SA amines with 1 and 2, in contrast to the concerted mechanisms for the reactions of the same amines with the corresponding carbonates

  一系列仲脂环族（SA）胺与O-苯基和O-乙基O-（2,4-二硝基苯基）硫代碳酸酯（分别为1和2）以及一系列吡啶与前一种底物的反应在25.0°C的水中进行离子动力学研究，离子强度为0.2 M（KCl）。在胺超过底物过量的情况下，所有反应都遵循假一级反应动力学，并且在胺中是一级反应。该布朗斯台德型绘图是双相的，斜率（在高μ ķ一个的β）1 = 0.20为SA胺与反应1和2和β 1 = 0.10的pyridinolysis1，用斜率（在低p- ķ一个）的β 2 = 0.80，SA胺与反应1和2和β 2 = 1.0的pyridinolysis 1。曲率中心处的p K a值（p K a 0）分别为7.7、7.0和7.0。这些结果与两性离子四面体中间体（T⧧）的存在以及速率确定步骤随胺碱性的变化而变化是一致的。较大的p ķ一个0为的pyridinolysis值1相比，对于2（p K a 0 = 6.8）和SA胺与1相对于2的反应中较大的p
• Kinetics and Mechanism of the Aminolysis of Phenyl and 4-Nitrophenyl Chlorothionoformates
  作者：Enrique A. Castro、María Cubillos、José G. Santos

  DOI：10.1021/jo970276y

  日期：1997.6.1

  for the aminolysis of both substrates are linear with the same slope, beta = 0.26. From this value, the kinetic law, and the analysis of products, it is deduced that these reactions proceed through a zwitterionic tetrahedral addition intermediate (T(+/-)) on the reaction path, and its formation is the rate-determining step. From a comparison of the present reactions with the concerted aminolysis of substituted

  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。
• Kinetics and Mechanism of the Aminolysis of Phenyl and Methyl 4-Nitrophenyl Thionocarbonates
  作者：Enrique A. Castro、Claudia Saavedra、José G. Santos、María I. Umaña

  DOI：10.1021/jo990084y

  日期：1999.7.1

  alicyclic amines with the title substrates are subjected to a kinetic study in aqueous solution, 25.0 degrees C, ionic strength 0.2 (KCl), by following spectrophotometrically the release of 4-nitrophenoxide ion. Under amine excess, pseudo-first-order rate coefficients (k(obsd)) are found. For the reactions of phenyl 4-nitrophenyl thionocarbonate (1), linear plots of k(obsd) vs [NH] (NH is the free amine)

  脂环族仲胺与标题底物的反应在25.0摄氏度，离子强度0.2（KCl）的水溶液中进行动力学研究，方法是分光光度法测定4-硝基苯氧根离子的释放。在胺过量下，发现伪一阶速率系数（k（obsd））。对于苯基4-硝基苯基硫代碳酸酯（1）的反应，除了与哌嗪鎓离子的反应外，还获得了k（obsd）对[NH]（NH为游离胺）的线性图，该图显示了非线性的向上图。4-硝基苯基硫代碳酸甲酯（2）的氨解显示k（obsd）对[NH]的非线性图，但哌啶是线性的。1的布朗斯台德型图是线性的，斜率β= 0.25，表明四面体加成中间体（T（+/-））的形成（k（1）步骤）是速率决定的。对于2的氨解（哌啶除外），k（-）（1）大约为k（3）[NH]> k（2），其中k（-）（1），k（3）和k（2）分别是胺驱出，胺去质子化和离开基团从T（+/-）驱出的速率系数。对于2与哌啶的反应，k（-）（1）
• 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.
• Kinetics and mechanism of the aminolysis of O‐phenyl 4‐nitrophenyl dithiocarbonate in aqueous ethanol
  作者：Enrique A. Castro、Leonardo Leandro、José G. Santos

  DOI：10.1002/(sici)1097-4601(1999)31:12<839::aid-kin1>3.0.co;2-#

  日期：1999.1

  The reactions of the title substrate (1) with a series of secondary alicyclic amines are subjected to a kinetic investigation in 44 wt% ethanol-water, at 25.0 degrees C, ionic strength 0.2 M (KCl). Under amine excess over the substrate, pseudo-first-order rate coefficients (k(obs)) are obtained. Plots of k(obs) against [NH], where NH is the free amine, are nonlinear upwards,except the reactions of piperidine, which show linear plots. According to the kinetic results and the analysis of products, a reaction scheme is proposed with two tetrahedral intermediates, one zwitterionic (T+/-) and another anionic (T-), with a kinetically significant proton transfer from T+/- to an amine to yield T- (k(3) step). By nonlinear least-squarer fitting of an equation derived from the scheme to the experimental points, the rate microcoefficients involved in the reactions are determined. Comparison of the kinetics of the title reactions with the linear k(obs) vs. [NH] plots found in the same aminolysis of O-ethyl 4-nitrophenyl dithiocarbonate (2) in the same solvent shows that the rate coefficient for leaving group expulsion from T+/- (k(2)) is larger for 2 due to a stronger push by EtO than Pho. The k(3) value is the same for both reactions since both proton transfers are diffusion controlled. Comparison of the title reactions with the same aminolysis of phenyl 4-nitrophenyl thionocarbonate (3) in water indicates that iii the k(2) value is larger for the aminolysis of 1 due to the less basic nucleofuge involved and the small solvent effect on k(2), (ii) the k(3) value is smaller for the reactions of 1 due to the more viscous solvent, (iii) the rate coefficient for amine expulsion from T+/- (k(-1)) is larger for the aminolysis of 1 than that of 3 due to a solvent effect, and (iv) the value of the rate coefficient for amine attack (k(1)) is smaller for the aminolysis of 1 in aqueous ethanol, which can be explained by a predominant solvent effect relative to the electron-withdrawing effect from the nucleofuge. (C) 1999 John Wiley & Sons, Inc.