1-piperidinecarbothioic acid O-ethyl ester | 56525-81-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 1-piperidinecarbothioic acid O-ethyl ester
• 英文别名: O-ethyl 1-piperidinecarbothioate；piperidinyl thiocarbamate；O-ethyl piperidine-1-carbothioate；piperidine；piperidine-1-carbothioic acid O-ethyl ester；Piperidin-1-thiocarbonsaeure-O-aethylester；O-ethyl N,N-pentamethylene-thiocarbamate
• CAS: 56525-81-6
• 化学式: C₈H₁₅NOS
• 分子量: 173.279
• InChiKey: YCXOMQXFITYRQP-UHFFFAOYSA-N

物化性质

• 沸点：
  92 °C(Press: 1 Torr)
• 密度：
  1.086±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  44.6
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335
• 储存条件：
  室温

反应信息

• 作为反应物：
  描述：

  1-piperidinecarbothioic acid O-ethyl ester 、 硫酸二乙酯 生成 piperidine-1-carbothioic acid S-ethyl ester
  参考文献：
  名称：

  Process for the preparation of substituted S-alkyl thio-carbamates

  摘要：

  该发明涉及一种新的和有利的过程，用于制备具有通式（I）的取代S-烷基硫代氨基甲酸酯，其中R.sup.1代表C.sub.1-4烷基基团，R.sup.2代表C.sub.1-4烷基或环己基团，或R.sup.1和R.sup.2可以一起形成C.sub.4-6聚亚甲基基团，而R.sup.3代表C.sub.2-3烷基基团。根据该发明，通式（II）的取代O-烷基硫代氨基甲酸酯，在存在二甲基硫酸酯或乙基硫酸酯的情况下，通过加热它们在130°C至180°C的温度下进行异构化，从而得到相应的S-烷基酯。

  公开号：

  US03953427A1
• 作为产物：
  描述：

  S-ethoxycarbonyl O-ethyl dithiocarbonate 生成 1-piperidinecarbothioic acid O-ethyl ester
  参考文献：
  名称：

  HERRERA, M.;RUIZ, V. M.;TAPIA, R.;VALDERRAMA, J.;VEGA, J. C., AN. QUIM. PUBL. REAL SOC. ESP. FIS. Y QUIM., 1980, 76, N 2, 183-186

  摘要：

  DOI：

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
• Syntheses of N-alkyl, N,N-dialkyl, and N-(4-substituted phenyl) O-ethyl thioncarbamates: a kinetic study
  作者：Milutin M. Milosavljević、Aleksandar D. Marinković、Vlada B. Veljković、Dragan D. Milenković

  DOI：10.1007/s00706-011-0596-1

  日期：2012.1

  AbstractThe kinetics of the syntheses of N-alkyl, N,N-dialkyl, and N-(4-substituted phenyl) O-ethyl thioncarbamates from sodium ethyl xanthogenacetate, ten alkylamines, and eight substituted anilines were studied at 25, 30, 35, and 40 °C. The reactions were found to follow second-order kinetics. The kinetic (Arrhenius) parameters, such as the activation energy and the frequency factor, as well as the

  摘要N-烷基，N，N-二烷基和N-（4-取代的苯基）O的合成动力学在25、30、35和40°C下研究了由黄原酸乙酯钠，十个烷基胺和八个取代的苯胺生成的亚乙基乙基氨基甲酸酯。发现反应遵循二级动力学。由二阶速率计算出动力学（Arrhenius）参数，例如活化能和频率因子，以及Eyring参数，例如标准熵，标准吉布斯能量和标准活化焓。常数。根据提出的动力学研究和使用MOPAC PM6半经验方法对反应机理进行了优化，推测了反应机理。 图形概要
• Iodine mediated direct coupling of benzylic alcohols with dithiocarbamate anions: An easy access of S-benzyl dithiocarbamate esters under neat reaction condition
  作者：Soumya Dutta、Amit Saha

  DOI：10.1016/j.tetlet.2020.152382

  日期：2020.10

  solvent free synthesis of S-benzylic dithiocarbamate esters has been demonstrated via the iodine mediated direct C-S coupling of benzylic alcohols with dithiocarbamate anions generated in-situ by the reactions of amines and carbon disulphide. All the reactions were very fast (15–30 min) and performed under open air atmosphere. Cyclic and acyclic secondary amines, primary amine, aromatic amine actively

  通过碘介导的苄醇与由胺和二硫化碳反应原位产生的二硫代氨基甲酸酯阴离子的直接介导的CS偶联，已经证明了S-苄基的二硫代氨基甲酸酯的有效，无金属和溶剂的合成。所有反应都非常快（15-30分钟），并且在露天气氛下进行。环状和无环仲胺，伯胺，芳族胺积极参与与不同苯甲醇的一锅偶联反应。非苄醇在相同的反应条件下提供邻硫代氨基甲酸酯化合物的合成。
• Structure-reactivity relationships in the aminolysis of O-ethyl S-aryl dithiocarbonates in aqueous solution
  作者：Enrique A. Castro、Maria Cubillos、Fernando Ibanez、Inge Moraga、Jose G. Santos

  DOI：10.1021/jo00072a022

  日期：1993.9

  The reactions of O-ethyl S-(X-phenyl) dithiocarbonates (X = p-Cl, p-Me, and p-MeO) with a series of secondary alicyclic amines and those of the same substrates and analogous derivatives (X = H, p-NO2, and 2,4-(NO2)2) with pyrrolidine are subjected to a kinetic study in water, 25.0-degrees-C, ionic strength 0.2 M (KCl). The reactions of piperidine and pyrrolidine show second-order kinetics (first order in amine) with the formation of a zwitterionic tetrahedral intermediate (T+/-) as the rate-determining step, The reactions of the other amines exhibit orders in amine different from one, compatible with the presence of an anionic intermediate (T-), resulting from a kinetically important proton transfer from T+/- to the amine. The rate of this proton transfer is faster than that of expulsion of arylthiolate from T+/- (k2) as evidenced by the estimation of these rate coefficients. The rate constants for formation of T+/- (k1) are obtained experimentally, and those for amine expulsion from T+/- (k-1) are estimated. Equations for k1 and k-1 are derived as functions of the basicity of the amine and leaving (aryl thiolate) groups. Comparison of the k-1 and k2 values found in the present reactions with those obtained in the aminolysis of aryl dithioacetates shows that substitution of Me by EtO as the ''acyl'' group of the zwitterionic tetrahedral intermediate destabilizes this species.
• Structure−Reactivity Correlations in the Aminolysis of Ethyl <i>S</i>-Aryl Thiolcarbonates
  作者：Enrique A. Castro、María Cubillos、José G. Santos

  DOI：10.1021/jo990531+

  日期：1999.8.1

  The reactions of secondary alicyclic amines (saa) with ethyl S-4-X-phenyl thiolcarbonates (X = Cl, H, Me, and MeO) are subjected to a kinetic analysis in water, 25.0 degrees C, ionic strength 0.2 (KCI). By following the leaving groups spectrophotometrically (260-270 nm), under amine excess, pseudo first-order rate coefficients (K-obsd) are obtained. Plots of k(obsd) against free-amine concentration at constant, pH are linear, with slope (k(N)) independent of pH. The Bronsted-type plots (log k(N) against amine pK(a)) are linear for the aminolysis of the four substrates, with slopes beta(N) = 0.7-0.8. The magnitudes of the slopes are consistent with a stepwise mechanism through a zwitterionic tetrahedral intermediate (T+/-) whose breakdown to products is rate-determining (k(2) step). This mechanism is simpler than that for the same aminolysis of the corresponding ethyl S-aryl dithiocarbonates, which includes proton transfer from T+/- to the amine (k(3) step), due to the fact that for the title reactions k(2) > k(3)[amine]. With the results of the present work and those for the reactions of saa with ethyl S-4-nitrophenyl thiolcarbonate, a dual parametric equation is deduced for kN as a function of amine and leaving group basicity, with both beta(N) and -beta(lg) = 0.8. Another dual parametric equation is deduced from literature data for the pyridinolysis of ethyl S-aryl thiolcarbonates, Comparison of both multiparametric expressions shows that pyridines are more reactive than isobasic saa toward thiolcarbonates when breakdown of T+ to products is rate-limiting.