1-Dimethylamino-ethenol anion | 136569-08-9

• 英文名称: 1-Dimethylamino-ethenol anion
• 英文别名: 1-(Dimethylamino)ethenolate
• CAS: 136569-08-9
• 化学式: C₄H₈NO
• 分子量: 86.1136
• InChiKey: NVLNZFLRJJQWMO-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  6
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-Dimethylamino-ethenol anion 在 水 作用下， 生成 N,N-二甲基乙酰胺
  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：

  N,N-二甲基乙酰胺 在 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 1-Dimethylamino-ethenol anion
  参考文献：
  名称：

  邻近基团对含 Si-O-Si 化合物裂解速率的影响

  摘要：

  附近束缚官能团（G，G = 叔酰胺或胺）的存在会显着影响 Si-O 键的断裂速率。我们在这里报告了对含有两种不同 Si-O 子结构（即烷氧基二硅氧烷 [GRO-Si(Me 2 )-O-SiMe 3 ] 和碳二硅氧烷 [GR-Si (Me 2 )–O–SiMe 3 ]。通过计算探讨了烷氧基二硅氧烷水解的相对速率的趋势（随着链长度的增加而减慢，但有明显的例外）。结果与实验数据吻合良好。与烷氧基二硅氧烷的水解相反，碳二硅氧烷没有完全水解，而是形成起始不对称二硅氧烷、两种硅烷醇和新的对称二硅氧烷的平衡混合物。我们还发现了引入的硅烷醇与碳二硅氧烷底物的容易的甲硅烷氧基复分解反应[例如，Me 2 NR–Si(Me 2 )–O–SiMe 3 + HOSiEt 3 ⇋ Me 2 NR–Si(Me 2 )–O– SiEt 3 + HOSiMe 3 ]由侧二甲氨基促进，这一过程也通过计算进行了探讨。

  DOI：

  10.1021/acs.joc.2c02126

文献信息

• Gas-phase Broensted versus Lewis acid-base reactions of 6,6-dimethylfulvene. A sensitive probe of the electronic structures of organic anions
  作者：Mark D. Brickhouse、Robert R. Squires

  DOI：10.1021/ja00217a002

  日期：1988.4