N-carbethoxymethylene-2-phenylthiazolidine | 145224-22-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: N-carbethoxymethylene-2-phenylthiazolidine
• 英文别名: 3-<(ethoxycarbonyl)methyl>-2-phenylthiazolidine；Ethyl 2-(2-phenyl-1,3-thiazolidin-3-yl)acetate
• CAS: 145224-22-2
• 化学式: C₁₃H₁₇NO₂S
• 分子量: 251.349
• InChiKey: GAQXFOZQXGLYQE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  54.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  一氧化碳 、 N-carbethoxymethylene-2-phenylthiazolidine 在 甲醇 、 chloro(1,5-cyclooctadiene)rhodium(I) dimer 、 potassium iodide 作用下， 以 苯 为溶剂， 180.0 ℃ 、6.59 MPa 条件下， 反应 48.0h， 以72%的产率得到3-<(ethoxycarbonyl)methyl>thiazolidin-2-one
  参考文献：
  名称：

  Sequential Ring Expansion and Ketene Elimination Reactions in the Novel Rhodium(I)-Catalyzed Carbonylation of Thiazolidines

  摘要：

  1,3-Thiazolidines react with carbon monoxide, in the presence of catalytic quantities of chloro(1,5-cyclooctadiene)rhodium(I) dimer and potassium iodide, to give thiazolidinones in 56-88% yields. Reaction in the absence of KI afforded the six-membered ring thiazin-3-one, The rhodium(I) complex can catalyze the quantitative conversion of the thiazin-3-one to the thiazolidinone under carbon monoxide, with ketene as the reaction by-product. The conversion of thiazolidines to thiazolidinones involves a novel regiospecific insertion of carbon monoxide into one of two ring carbon-nitrogen bonds, as well as a metal-catalyzed ketene elimination process.

  DOI：

  10.1021/ja00092a016
• 作为产物：
  描述：

  2-苯基-1,3-噻唑烷 、 溴乙酸乙酯 在 potassium carbonate 作用下， 以 乙醇 为溶剂， 以57%的产率得到N-carbethoxymethylene-2-phenylthiazolidine
  参考文献：
  名称：

  Sequential Ring Expansion and Ketene Elimination Reactions in the Novel Rhodium(I)-Catalyzed Carbonylation of Thiazolidines

  摘要：

  1,3-Thiazolidines react with carbon monoxide, in the presence of catalytic quantities of chloro(1,5-cyclooctadiene)rhodium(I) dimer and potassium iodide, to give thiazolidinones in 56-88% yields. Reaction in the absence of KI afforded the six-membered ring thiazin-3-one, The rhodium(I) complex can catalyze the quantitative conversion of the thiazin-3-one to the thiazolidinone under carbon monoxide, with ketene as the reaction by-product. The conversion of thiazolidines to thiazolidinones involves a novel regiospecific insertion of carbon monoxide into one of two ring carbon-nitrogen bonds, as well as a metal-catalyzed ketene elimination process.

  DOI：

  10.1021/ja00092a016

文献信息

• Structure–reactivity correlations of substituted 2-phenylthiazolidines
  作者：R. Umarani、G. Radhakrishnan

  DOI：10.1139/v92-252

  日期：1992.7.1

  Systematic investigations of the kinetics of the reactions of ethyl bromoacetate (EBA) and of picryl bromide (PB) with 2-phenylthiazolidines (PT) in 100% ethanol were undertaken at 30, 35, 40, and 45 °C. The most incisive information concerning the Hammett equation comes from the extensive studies on the substituted 2-phenylthiazolidines, establishing linear Hammett plots with negative ρ values. The kinetic data, plotted in a Brønsted fashion against pK_a of the corresponding thiazolidinium ions, yield linear relationships. The activation parameters were computed. The linear relationships between ΔH^≠ and ΔS^≠ signify a consistent mechanism throughout the series.

  在100%乙醇中，对乙基溴乙酸酯（EBA）和硝基溴苯（PB）与2-苯基噻唑啉（PT）的反应动力学进行了系统研究，温度分别为30、35、40和45°C。对取代2-苯基噻唑啉的广泛研究提供了关于Hammett方程最具洞察力的信息，建立了具有负ρ值的线性Hammett图。以对应噻唑啉阳离子的pKa为横坐标，以Brønsted方式绘制的动力学数据呈线性关系。计算了活化参数。ΔH≠与ΔS≠之间的线性关系表明整个系列中存在一致的机理。
• Sequential Ring Expansion and Ketene Elimination Reactions in the Novel Rhodium(I)-Catalyzed Carbonylation of Thiazolidines
  作者：Kanjai Khumtaveeporn、Howard Alper

  DOI：10.1021/ja00092a016

  日期：1994.6

  1,3-Thiazolidines react with carbon monoxide, in the presence of catalytic quantities of chloro(1,5-cyclooctadiene)rhodium(I) dimer and potassium iodide, to give thiazolidinones in 56-88% yields. Reaction in the absence of KI afforded the six-membered ring thiazin-3-one, The rhodium(I) complex can catalyze the quantitative conversion of the thiazin-3-one to the thiazolidinone under carbon monoxide, with ketene as the reaction by-product. The conversion of thiazolidines to thiazolidinones involves a novel regiospecific insertion of carbon monoxide into one of two ring carbon-nitrogen bonds, as well as a metal-catalyzed ketene elimination process.

表征谱图