1-pyrrolidinecarbothioic acid O-ethyl ester | 56525-82-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: 1-pyrrolidinecarbothioic acid O-ethyl ester
• 英文别名: O-ethyl pyrrolidine-1-carbothioate；pyrrolidine；pyrrolidine-1-carbothioic acid O-ethyl ester；Pyrrolidin-1-thiocarbonsaeure-O-aethylester
• CAS: 56525-82-7
• 化学式: C₇H₁₃NOS
• 分子量: 159.252
• InChiKey: FXNRCZNZONGZMF-UHFFFAOYSA-N

物化性质

• 沸点：
  201.5±23.0 °C(Predicted)
• 密度：
  1.123±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 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：

  O-乙基-S-羧基甲基二硫代碳酸 在 氢氧化钾 作用下， 生成 1-pyrrolidinecarbothioic acid O-ethyl ester
  参考文献：
  名称：

  D'Angeli, 1957, vol. 116, p. 9

  摘要：

  DOI：

文献信息

• Synthesis of novel dithiocarbamates and xanthates using dialkyl azodicarboxylates: S N bond formation
  作者：Azim Ziyaei Halimehjani、Blanka Klepetářová、Petr Beier

  DOI：10.1016/j.tet.2018.02.049

  日期：2018.4

  characterized by a wide scope, high efficiency and straightforward isolation protocol. The synthetic utility of the dithiocarbamates and xanthates was demonstrated on the preparation of symmetrical and unsymmetrical thioureas, isothiocyanates, and thiocarbamates.

  通过在温和且无催化剂的条件下原位生成的二硫代氨基甲酸或黄原酸酯与偶氮二羧酸二烷基酯的反应，开发了一种用于合成一类新型二硫代氨基甲酸酯或黄原酸酯的单锅三组分途径。该反应的特点是范围广，效率高和直接的分离方案。在制备对称和不对称的硫脲，异硫氰酸酯和硫代氨基甲酸酯时，证明了二硫代氨基甲酸酯和黄原酸酯的合成效用。
• 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
• 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 correlation in the reactions of pyrrolidine with O-ethyl S-aryl dithiocarbonates in aqueous ethanol
  作者：Enrique A. Castro、Mauricio Cabrera、Jose G. Santos

  DOI：10.1002/(sici)1097-4601(1997)29:2<113::aid-kin4>3.0.co;2-x

  日期：——

  The reactions of pyrrolidine with O-ethyl S-(X-phenyl) dithiocarbonates (X = 4-methyl, 4-methoxy, H, 4-chloro, 4-nitro, 2,4-dinitro, and 2,4,6-trinitro) are subjected to a kinetic study in 44 wt% aqueous ethanol, 25.0 degrees C, and ionic strength 0.2 M (maintained with KCl). Pseudo-first-order kinetics are found under amine excess. Linear plots of the pseudo-first-order rate coefficient against concentration of free-base pyrrolidine are obtained for all the reactions, the nucleophilic rate coefficient (it,) being the slope of such plots. The Bronsted-type plot (log k(N) vs. pK(a) for the leaving group) is linear with slope beta(lg) = -0.2, which is consistent with a mechanism through a tetrahedral intermediate (T-+/-) where its formation is rate determining. The beta(lg) Value is very similar to that found in the same reactions in water. There is a great difference in the mechanism of the reactions of O-ethyl S-phenyl dithiocarbonate with pyrrolidine (order one in amine) and piperidine (complex order in amine) in aqueous ethanol, and this is attributed to a greater nucleofugality from T-+/- of piperidine rather than pyrrolidine. (C) 1997 John Wiley & Sons, Inc.
• Castro, Enrique A.; Alvarado, Noemi E.; Pena, Sergio A., Journal of the Chemical Society. Perkin transactions II, 1989, p. 635 - 642
  作者：Castro, Enrique A.、Alvarado, Noemi E.、Pena, Sergio A.、Santos, Jose G.

  DOI：——

  日期：——