morpholinyl thiocarbamate | 936-64-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 恶嗪烷类
• 英文名称: morpholinyl thiocarbamate
• 英文别名: morpholine-4-carbothioic acid O-ethyl ester；Morpholin-4-thiocarbonsaeure-O-aethylester；Morpholino-thiocarbonsaeureethylester；ethyl morpholinocarbothionate；O-ethyl morpholine-4-carbothioate
• CAS: 936-64-1
• 化学式: C₇H₁₃NO₂S
• 分子量: 175.252
• InChiKey: RFQPGWZYSRHBTC-UHFFFAOYSA-N

物化性质

• 熔点：
  58-59 °C
• 沸点：
  236.6±50.0 °C(Predicted)
• 密度：
  1.164±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  53.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  morpholinyl thiocarbamate 、 丙二腈 在 氯胺 、 sodium hydride 作用下， 生成 3-amino-5-(4-morpholinyl)isothiazole-4-carbonitrile
  参考文献：
  名称：

  Shishoo, C. J.; Devani, M. B.; Ananthan, S., Journal of Heterocyclic Chemistry, 1988, vol. 25, # 2, p. 759 - 765

  摘要：

  DOI：
• 作为产物：
  描述：

  吗啉 、 alkaline earth salt of/the/ methylsulfuric acid 在 乙醇 作用下， 生成 morpholinyl thiocarbamate
  参考文献：
  名称：

  Mameli et al., Annali di Chimica, 1956, vol. 46, p. 211,222

  摘要：

  DOI：

文献信息

• 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.
• Kinetics and Mechanism of the Aminolysis of Phenyl and 4-Nitrophenyl Ethyl Thionocarbonates
  作者：Enrique A. Castro、María Cubillos、José G. Santos

  DOI：10.1021/jo951726u

  日期：1996.1.1

  The reactions of the title substrates (PTOC and NPTOC, respectively) with secondary alicyclic amines are subjected to a kinetic study in aqueous solution at 25.0 degrees C, ionic strength 0.2 M (KCI). Under amine excess, pseudo-first-order rate coefficients (k(obsd)) are found throughout. The order in amine is one for the reactions of piperidine but is of intermediate order between 1 and 2 for the reactions of the other amines. The kinetic results can be accommodated by a reaction scheme with two hypothetical tetrahedral intermediates: a zwitterionic (T-+/-) and an anionic (T-) one, whereby amine catalysis (deprotonation of T-+/- to give T-) is kinetically important. Both the pK(a) of T-+/- and the rate coefficient for proton transfer (k(3) ca. 10(10) s(-1) M(-1)) are estimated. The values of the other rate microcoefficients of the scheme are found by a nonlinear least-squares fitting, and these values are compared with those exhibited in the aminolysis of phenyl thionoacetate (PTOA), and S-phenyl and S-(4-nitrophenyl) O-ethyl dithiocarbonates (PDTC and NPDTC, respectively). The Bronsted type plots for amine basicity have slopes beta(N) ca, 0.2 for rate-determining amine attack (k(1)) and beta(N) ca. 0.8 for amine expulsion from T-+/- (k(-1)), in accord with the beta(N) values found in similar aminolyses. The general base catalysis by amine found in the aminolysis of NPTOC, in contrast with the lack of such catalysis in the aminolysis of 4-nitrophenyl methyl carbonate, is explained by a smaller rate coefficient for expulsion of 4-nitrophenoxide (k(2)) from T-+/- (which competes with amine deprotonation of T-+/-) relative to the same expulsion from the analogous oxy intermediate.
• 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：——
• Kinetics and mechanism of the aminolysis of O-ethyl S-aryl dithiocarbonates
  作者：Mauricio Cabrera、Enrique A. Castro、Mirtha Salas、Jose G. Santos、Patricia Sepulveda

  DOI：10.1021/jo00018a022

  日期：1991.8

  The reactions of O-ethyl S-phenyl dithiocarbonate (1) and O-ethyl S-(p-nitrophenyl) dithiocarbonate (2) with a series of secondary alicyclic amines, namely, piperidine, piperazine, 1-(beta-hydroxyethyl)piperazine, morpholine, 1-formylpiperazine, and (with 2 only) piperazinium ion, are subject to a kinetic study at several pH values. The reaction leads to the corresponding thiocarbamates and thiophenols (measured as thiophenoxide ion by UV-vis spectrophotometry). Pseudo-first-order rate coefficients (k(obsd)) are found throughout (amine excess). The kinetics are first order in amine for the reactions of 2. The plots of k(obsd) vs [amine] for the reactions of 1, except with 1-formylpiperazine, are linear, but near the origin they are curved, showing a more complex rate equation. The reaction of 1 with 1-formylpiperazine shows a second-order dependence on the amine. No dependence on pH of the second-order rate constant values is observed. The findings are well-accommodated by a mechanistic model involving reversible nucleophilic attack on the thiocarbonyl group, two tetrahedral intermediates, 3 and 4, and a deprotonation step. The Bronsted-type plots obtained are linear (beta-1 = 0.22) for the reaction of 1 and curved for 2 (beta-1 = 0.2 and beta-2 = 0.8). The Bronsted-type plot obtained with the rate constants for amine expulsion from 3 is linear with beta-1 = -0.67 and -0.54 for the reactions of 1 and 2, respectively.