1-Aminoethen-1-olate | 31108-39-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-Aminoethen-1-olate
• 英文别名: 1-aminoethenolate
• CAS: 31108-39-1
• 化学式: C₂H₄NO
• 分子量: 58.0599
• InChiKey: UEFNHFCSZBRPPV-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  4
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  49.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-Aminoethen-1-olate 在 水 作用下， 生成 乙酰胺
  参考文献：
  名称：

  Formation and Stability of Enolates of Acetamide and Acetate Anion:  An Eigen Plot for Proton Transfer at α-Carbonyl Carbon

  摘要：

  Second-order rate constants were determined in D2O for deprotonation of acetamide, N,N-dimethylacetamide, and acetate anion by deuterioxide ion and for deprotonation of acetamide by quinuclidine. The values of k(B) = 4.8 x 10(-8) m(-1) s(-1) for deprotonation of acetamide by quinuclidine (pK(BH) = 11.5) and k(BH) = 2-5 x 10(9) M-1 s(-1) for the encounter-limited reverse protonation of the enolate by protonated quinucildine give pK(a)(C) = 28.4 for ionization of acetamide as a carbon acid. The limiting value of k(HOH) = 1 x 10(11) s(-1) for protonation of the enolate of acetate anion by solvent water and k(HO) = 3.5 x 10(-9) M-1 s(-1) for deprotonation of acetate anion by HO- give pK(a)(C) approximate to 33.5 for acetate anion, The change in the rate-limiting step from chemical proton transfer to solvent reorganization results in a downward break in the slope of the plot of log k(HO) against carbon acid pK(a) for deprotonation of a wide range of neutral a-carbonyl carbon acids by hydroxide ion, from -0.40 to -1.0. Good estimates are reported for the stabilization of the carbonyl group relative to the enol tautomer by electron donation from alpha-SEt, alpha-OMe, alpha-NH2, and alpha-O- substituents. The alpha-NH2 and alpha-OMe groups show similar stabilizing interactions with the carbonyl group, while the interaction of alpha-O- is only 3.4 kcal/mol more stabilizing than for alpha-OH, We propose that destabilization of the enolate intermediates of enzymatic reactions results in an increasing recruitment of metal ions by the enzyme to provide electrophilic catalysis of enolate formation.

  DOI：

  10.1021/ja0125321
• 作为产物：
  描述：

  乙酰胺 在 氘氧化钾 、 重水 作用下， 生成 1-Aminoethen-1-olate
  参考文献：
  名称：

  Formation and Stability of Enolates of Acetamide and Acetate Anion:  An Eigen Plot for Proton Transfer at α-Carbonyl Carbon

  摘要：

  Second-order rate constants were determined in D2O for deprotonation of acetamide, N,N-dimethylacetamide, and acetate anion by deuterioxide ion and for deprotonation of acetamide by quinuclidine. The values of k(B) = 4.8 x 10(-8) m(-1) s(-1) for deprotonation of acetamide by quinuclidine (pK(BH) = 11.5) and k(BH) = 2-5 x 10(9) M-1 s(-1) for the encounter-limited reverse protonation of the enolate by protonated quinucildine give pK(a)(C) = 28.4 for ionization of acetamide as a carbon acid. The limiting value of k(HOH) = 1 x 10(11) s(-1) for protonation of the enolate of acetate anion by solvent water and k(HO) = 3.5 x 10(-9) M-1 s(-1) for deprotonation of acetate anion by HO- give pK(a)(C) approximate to 33.5 for acetate anion, The change in the rate-limiting step from chemical proton transfer to solvent reorganization results in a downward break in the slope of the plot of log k(HO) against carbon acid pK(a) for deprotonation of a wide range of neutral a-carbonyl carbon acids by hydroxide ion, from -0.40 to -1.0. Good estimates are reported for the stabilization of the carbonyl group relative to the enol tautomer by electron donation from alpha-SEt, alpha-OMe, alpha-NH2, and alpha-O- substituents. The alpha-NH2 and alpha-OMe groups show similar stabilizing interactions with the carbonyl group, while the interaction of alpha-O- is only 3.4 kcal/mol more stabilizing than for alpha-OH, We propose that destabilization of the enolate intermediates of enzymatic reactions results in an increasing recruitment of metal ions by the enzyme to provide electrophilic catalysis of enolate formation.

  DOI：

  10.1021/ja0125321