3-Azido-3-(4-methyl-3-nitrophenyl)diazirine | 153622-00-5

• 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: 3-Azido-3-(4-methyl-3-nitrophenyl)diazirine
• CAS: 153622-00-5
• 化学式: C₈H₆N₆O₂
• 分子量: 218.175
• InChiKey: MJMHJEVPWQCKIH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  84.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3-Azido-3-(4-methyl-3-nitrophenyl)diazirine 以 甲醇 为溶剂， 生成 4-甲基-3-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：

  4-methyl-3-nitro-benzimidic acid methyl ester 在 sodium hypochlorite 、 sodium azide 、 2-硝基丙烷钠盐 、 氯化铵 、 sodium chloride 作用下， 以 甲醇 、 正己烷 、 二甲基亚砜 为溶剂， 反应 75.03h， 生成 3-Azido-3-(4-methyl-3-nitrophenyl)diazirine
  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

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).