2-chloro-1-methylpyrimidinium triflate | 143859-73-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 2-chloro-1-methylpyrimidinium triflate
• 英文别名: 2-Chloro-1-methylpyrimidin-1-ium;trifluoromethanesulfonate
• CAS: 143859-73-8
• 化学式: CF₃O₃S*C₅H₆ClN₂
• 分子量: 278.639
• InChiKey: YROPJYZLADFCPF-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  0.61
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  82.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-chloro-1-methylpyrimidinium triflate 在 硫酸 、 sodium chloride 作用下， 生成
  参考文献：
  名称：

  Hydrolyses of 2- and 4-fluoro N-heterocycles. 4. Proton inventories of the hydrolyses of 2-fluoro-1-methylpyridinium iodide, 4-fluoroquinaldine, and 2-chloro-1-methylpyrimidinium triflate

  摘要：

  Rate constants for the hydrolyses of 2-fluoro-1-methylpyridinium iodide (3), 4-fluoroquinaldine (4), and 2-chloro-1-methylpyrimidinium triflate (5) in 2 X 10(-3) M aqueous sulfuric acid, in D2O/D2SO4, and in mixed H2O/H2SO4-D2O/D2SO4 media are reported. Significant solvent deuterium kinetic isotope effects are evident, with k(H)/k(D) = 2.07 for 3, 1.62 for 4, and 2.12 for 5. The results of the proton inventories for the hydrolyses of 3 and 5 are best fit by a form of the Gross-Butler equation for three nearly equivalent sites with fractionation factors of 0.78. The proton inventory of 4 does not yield a unique solution to the Gross-Butler equation, but the results are also consistent with three transition state sites with nearly equal fractionation factors of 0.72-0.78, as well as an additional transition-state site with phi > 1 and a reactant site with phi less-than-or-equal-to 1. These proton inventories are consistent with mechanisms in which nucleophilic addition of water in the rate-determining step is assisted by proton-transfer to a second water molecule, with development of an "immature hydronium ion" in the transition state. Mechanism with cyclic proton transfer are also consistent, but are less satisfactory as hydrolysis routes.

  DOI：

  10.1021/jo00050a017
• 作为产物：
  描述：

  2-氯嘧啶 、 三氟甲烷磺酸甲酯 以 二氯甲烷 为溶剂， 以68%的产率得到2-chloro-1-methylpyrimidinium triflate
  参考文献：
  名称：

  Hydrolyses of 2- and 4-fluoro N-heterocycles. 4. Proton inventories of the hydrolyses of 2-fluoro-1-methylpyridinium iodide, 4-fluoroquinaldine, and 2-chloro-1-methylpyrimidinium triflate

  摘要：

  Rate constants for the hydrolyses of 2-fluoro-1-methylpyridinium iodide (3), 4-fluoroquinaldine (4), and 2-chloro-1-methylpyrimidinium triflate (5) in 2 X 10(-3) M aqueous sulfuric acid, in D2O/D2SO4, and in mixed H2O/H2SO4-D2O/D2SO4 media are reported. Significant solvent deuterium kinetic isotope effects are evident, with k(H)/k(D) = 2.07 for 3, 1.62 for 4, and 2.12 for 5. The results of the proton inventories for the hydrolyses of 3 and 5 are best fit by a form of the Gross-Butler equation for three nearly equivalent sites with fractionation factors of 0.78. The proton inventory of 4 does not yield a unique solution to the Gross-Butler equation, but the results are also consistent with three transition state sites with nearly equal fractionation factors of 0.72-0.78, as well as an additional transition-state site with phi > 1 and a reactant site with phi less-than-or-equal-to 1. These proton inventories are consistent with mechanisms in which nucleophilic addition of water in the rate-determining step is assisted by proton-transfer to a second water molecule, with development of an "immature hydronium ion" in the transition state. Mechanism with cyclic proton transfer are also consistent, but are less satisfactory as hydrolysis routes.

  DOI：

  10.1021/jo00050a017

文献信息

• Hydrolyses of 2- and 4-fluoro N-heterocycles. 4. Proton inventories of the hydrolyses of 2-fluoro-1-methylpyridinium iodide, 4-fluoroquinaldine, and 2-chloro-1-methylpyrimidinium triflate
  作者：Oliver J. Muscio、Jialun Meng、Haisheng Wang、Songyuan Shi

  DOI：10.1021/jo00050a017

  日期：1992.11

  Rate constants for the hydrolyses of 2-fluoro-1-methylpyridinium iodide (3), 4-fluoroquinaldine (4), and 2-chloro-1-methylpyrimidinium triflate (5) in 2 X 10(-3) M aqueous sulfuric acid, in D2O/D2SO4, and in mixed H2O/H2SO4-D2O/D2SO4 media are reported. Significant solvent deuterium kinetic isotope effects are evident, with k(H)/k(D) = 2.07 for 3, 1.62 for 4, and 2.12 for 5. The results of the proton inventories for the hydrolyses of 3 and 5 are best fit by a form of the Gross-Butler equation for three nearly equivalent sites with fractionation factors of 0.78. The proton inventory of 4 does not yield a unique solution to the Gross-Butler equation, but the results are also consistent with three transition state sites with nearly equal fractionation factors of 0.72-0.78, as well as an additional transition-state site with phi > 1 and a reactant site with phi less-than-or-equal-to 1. These proton inventories are consistent with mechanisms in which nucleophilic addition of water in the rate-determining step is assisted by proton-transfer to a second water molecule, with development of an "immature hydronium ion" in the transition state. Mechanism with cyclic proton transfer are also consistent, but are less satisfactory as hydrolysis routes.