methoxy(3,5-dinitrophenyl)methanimine | 86475-51-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methoxy(3,5-dinitrophenyl)methanimine
• 英文别名: Methyl 3,5-dinitrobenzimidate；methyl 3,5-dinitrobenzenecarboximidate
• CAS: 86475-51-6
• 化学式: C₈H₇N₃O₅
• 分子量: 225.161
• InChiKey: NYBPSDAHZWJNCJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  125
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methoxy(3,5-dinitrophenyl)methanimine 在 sodium hypochlorite 、 sodium azide 、 2-硝基丙烷钠盐 、 氯化铵 、 sodium chloride 作用下， 以 甲醇 、 乙醚 、 正己烷 、 二甲基亚砜 为溶剂， 反应 13.51h， 生成 3,5-二硝基苯甲腈
  参考文献：
  名称：

  C-Azidodiazirines in the SRN1 reaction of azide ion with arylchlorodiazirines. Further insights into reaction mechanism

  摘要：

  Mixtures of arylchlorodiazirines and sodium azide in DMSO form visible charge transfer complexes. Irradiation of these solutions with fluorescent room light leads to S(RN)1 displacement of chloride and the transient formation of C-azidodiazirines. Relative reactivity studies (using competition experiments) show that nitro-substituted arylchlorodiazirines are substantially more reactive than other arylchlorodiazirines. This is attributed to facile electron transfer in the propagation cycle, involving the nitro-substituted aromatic ring. C-Azidodiazirines can be isolated in solution and spectroscopically characterized when the S(RN)1 reaction is initiated by addition of catalytic amounts of the sodium salt of 2-nitropropane. These azidodiazirines readily decompose at room temperature by first order processes to give molecular nitrogen and benzonitriles. Solvent and substituent effects on decomposition rates are minimal. Computational studies on potential intermediate carbenes in the decomposition of azidodiazirines have been carried out at the HF/6-31G* level. Singlet alpha-azidocarbenes RCN3, where R = NH2, OH, F, vinyl, phenyl, and CH3, are energy minima at this computational level. Isodesmic calculations show that the azido group is comparable to OH in its carbene stabilizing ability. Subsequent loss of N2 from alpha-azidocarbenes, leading to nitriles, is a highly exothermic process (126 kcal when R = vinyl and 128 kcal when R = phenyl).

  DOI：

  10.1021/jo00079a014
• 作为产物：
  描述：

  3,5-二硝基苯甲腈 、 sodium methylate 以 甲醇 为溶剂， 反应 48.0h， 以0.6867 g的产率得到methoxy(3,5-dinitrophenyl)methanimine
  参考文献：
  名称：

  3,5-二硝基苯甲腈与甲醇钠在甲醇中的反应机理

  摘要：

  已经重新研究了 3,5-二硝基苯甲腈在含有低浓度甲醇钠的甲醇溶液中的反应。已发现最终产物是甲氧基（3,5-二硝基苯基）甲胺，它是通过催化反应产生的。介绍了在反应体系中形成迈森海默配合物和最终产物的反应机理。已经根据 3,5-二硝基苄腈的 LUMO 系数和它们形成的相对势能分别讨论了它们形成的速率和热力学稳定性，还考虑了溶剂效应。

  DOI：

  10.1246/bcsj.56.1206

文献信息

• C-Azidodiazirines in the SRN1 reaction of azide ion with arylchlorodiazirines. Further insights into reaction mechanism
  作者：Xavier Creary

  DOI：10.1021/jo00079a014

  日期：1993.12

  Mixtures of arylchlorodiazirines and sodium azide in DMSO form visible charge transfer complexes. Irradiation of these solutions with fluorescent room light leads to S(RN)1 displacement of chloride and the transient formation of C-azidodiazirines. Relative reactivity studies (using competition experiments) show that nitro-substituted arylchlorodiazirines are substantially more reactive than other arylchlorodiazirines. This is attributed to facile electron transfer in the propagation cycle, involving the nitro-substituted aromatic ring. C-Azidodiazirines can be isolated in solution and spectroscopically characterized when the S(RN)1 reaction is initiated by addition of catalytic amounts of the sodium salt of 2-nitropropane. These azidodiazirines readily decompose at room temperature by first order processes to give molecular nitrogen and benzonitriles. Solvent and substituent effects on decomposition rates are minimal. Computational studies on potential intermediate carbenes in the decomposition of azidodiazirines have been carried out at the HF/6-31G* level. Singlet alpha-azidocarbenes RCN3, where R = NH2, OH, F, vinyl, phenyl, and CH3, are energy minima at this computational level. Isodesmic calculations show that the azido group is comparable to OH in its carbene stabilizing ability. Subsequent loss of N2 from alpha-azidocarbenes, leading to nitriles, is a highly exothermic process (126 kcal when R = vinyl and 128 kcal when R = phenyl).
• The Mechanism of the Reaction of 3,5-Dinitrobenzonitrile with Sodium Methoxide in Methanol
  作者：Takehiro Abe

  DOI：10.1246/bcsj.56.1206

  日期：1983.4

  mechanism has been presented for the formation of the Meisenheimer complexes and the final product in the reaction system. The rate and thermodynamic stabilities for their formation have been discussed on the basis of the LUMO coefficients of 3,5-dinitrobenzonitrile and from the relative potential energies of their formation respectively, considering also the solvent effects.

  已经重新研究了 3,5-二硝基苯甲腈在含有低浓度甲醇钠的甲醇溶液中的反应。已发现最终产物是甲氧基（3,5-二硝基苯基）甲胺，它是通过催化反应产生的。介绍了在反应体系中形成迈森海默配合物和最终产物的反应机理。已经根据 3,5-二硝基苄腈的 LUMO 系数和它们形成的相对势能分别讨论了它们形成的速率和热力学稳定性，还考虑了溶剂效应。