N-methoxyamide

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: N-methoxyamide
• 英文别名: methoxylamide；methoxyamide；Methoxyazanide；methoxyazanide
• 化学式: CH₄NO
• 分子量: 46.0489
• InChiKey: NOPVNWCIHNOJKG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  10.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  3-氯苯甲酰乙腈 在 NH2 radical 作用下， 生成 methanolate 、 N-methoxyamide
  参考文献：
  名称：

  Base-induced imine-forming 1,2-elimination reactions in the gas phase

  摘要：

  The gas-phase reactivity of CH3NHOCH3 (N,O-dimethylhydroxylamine, DHA) and NH2OCH3 (O-methylhydroxylamine, MHA) toward a series of anionic bases has been studied using the method of Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Both DHA and MHA undergo a competing proton abstraction from and nucleophilic substitution reaction on the nitrogen atom. The competition between these processes is governed by the strength of the base used. Unexpectedly, the nucleophilic attack on the nitrogen atom leading to the substitution of the methoxy group is found to be a relatively facile process. This is especially evident in the substitution reactions with O-methylhydroxylamine, NH2OCH3, where the formation of methoxide ions is much more efficient than in the highly inefficient substitution reactions of dimethyl ether, CH3OCH3. Apparently, substitution reactions on the nitrogen atom do not suffer from a very unfavorable activation barrier which is assumed to hamper nucleophilic substitution reactions on carbon atoms in the gas phase. This seems to be supported by high-level density-functional (DF) calculations which indicate that the nucleophilic substitution reactions on the nitrogen atom proceed via an entropically favored less tight, S(N)1-like transition state. However, in the reactions of N,O-dimethylhydroxylamine, Ch3NHOCH3, the proton abstraction and substitution processes unfavorably compete with a base-induced imine-forming 1,2-elimination. The efficiency of the imine-forming elimination reactions of CH3NHOCH3 can be compared favorably with the efficiency of base-induced alkene-forming 1,2-elimination reactions of corresponding simple ethers such as CH3CH2OC2H5.

  DOI：

  10.1021/jo00061a016

文献信息

• Base-induced imine-forming 1,2-elimination reactions in the gas phase
  作者：F. Matthias Bickelhaupt、Leo J. de Koning、Nico M. M. Nibbering

  DOI：10.1021/jo00061a016

  日期：1993.4

  The gas-phase reactivity of CH3NHOCH3 (N,O-dimethylhydroxylamine, DHA) and NH2OCH3 (O-methylhydroxylamine, MHA) toward a series of anionic bases has been studied using the method of Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Both DHA and MHA undergo a competing proton abstraction from and nucleophilic substitution reaction on the nitrogen atom. The competition between these processes is governed by the strength of the base used. Unexpectedly, the nucleophilic attack on the nitrogen atom leading to the substitution of the methoxy group is found to be a relatively facile process. This is especially evident in the substitution reactions with O-methylhydroxylamine, NH2OCH3, where the formation of methoxide ions is much more efficient than in the highly inefficient substitution reactions of dimethyl ether, CH3OCH3. Apparently, substitution reactions on the nitrogen atom do not suffer from a very unfavorable activation barrier which is assumed to hamper nucleophilic substitution reactions on carbon atoms in the gas phase. This seems to be supported by high-level density-functional (DF) calculations which indicate that the nucleophilic substitution reactions on the nitrogen atom proceed via an entropically favored less tight, S(N)1-like transition state. However, in the reactions of N,O-dimethylhydroxylamine, Ch3NHOCH3, the proton abstraction and substitution processes unfavorably compete with a base-induced imine-forming 1,2-elimination. The efficiency of the imine-forming elimination reactions of CH3NHOCH3 can be compared favorably with the efficiency of base-induced alkene-forming 1,2-elimination reactions of corresponding simple ethers such as CH3CH2OC2H5.