3,5-dinitrophenylchlorodiazirine | 153621-95-5

• 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: 3,5-dinitrophenylchlorodiazirine
• 英文别名: 3-Chloro-3-(3,5-dinitrophenyl)diazirine
• CAS: 153621-95-5
• 化学式: C₇H₃ClN₄O₄
• 分子量: 242.578
• InChiKey: PMMDBIOOCJYNEP-UHFFFAOYSA-N

物化性质

• 沸点：
  351.5±52.0 °C(Predicted)
• 密度：
  1.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  116
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  乙烯,四甲氧基- 、 3,5-dinitrophenylchlorodiazirine 以 正戊烷 为溶剂， 反应 3.0h， 以64%的产率得到1-chloro-1-(3,5-dinitrophenyl)-2,2,3,3-tetramethoxycyclopropane
  参考文献：
  名称：

  卡宾加成四甲氧基乙烯的负活化能

  摘要：

  确定了在戊烷和癸烷中向四甲氧基乙烯（TMeOE）和四甲基乙烯（TME）中添加三种芳基卤代卡宾的活化能。对于在癸烷中的TMeOE中添加3,5-二硝基苯基氯卡宾，E a  = -10.4±0.7 kcal / mol，这是卡宾-烯烃加成反应中遇到的最负的活化能。计算研究平行并阐明了实验结果。

  DOI：

  10.1016/j.tetlet.2016.08.001
• 作为产物：
  描述：

  3,5-二硝基苯甲腈 在 sodium hypochlorite 、 sodium methylate 、 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 31.83h， 生成 3,5-dinitrophenylchlorodiazirine
  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

• Activation Parameters for Additions to Alkenes of Arylchlorocarbenes with Enhanced Electrophilicity
  作者：Lei Wang、Karsten Krogh-Jespersen、Robert A. Moss

  DOI：10.1021/acs.joc.5b01210

  日期：2015.8.7

  Activation parameters are reported for additions of phenylchlorocarbene (PhCCl), pentafluorophenylchlorocarbene (F5-PhCCl), and 3,5-dinitrophenyl-chlorocarbene (3,5-DN-PhCCl) to tetramethylethylene (TME), cyclohexene, and 1-hexene. The order of activation enthalpies is F5-PhCCl > PhCCl > 3,5-DN-PhCCl. Activation enthalpies also increase as the degree of alkene alkylation decreases. In general, the

  报道了向四甲基乙烯（TME），环己烯和1-己烯中添加苯基氯卡宾（PhCCl），五氟苯基氯卡宾（F 5 -PhCCl）和3,5-二硝基苯基-氯卡宾（3,5-DN-PhCCl）的活化参数。活化焓的顺序为F 5 -PhCCl> PhCCl> 3,5-DN-PhCCl。活化焓也随着烯烃烷基化程度的降低而增加。通常，激活熵随激活焓的增加而增加。
• Negative activation energies for carbene additions to tetramethoxyethylene
  作者：Lei Wang、Robert A. Moss、Karsten Krogh-Jespersen

  DOI：10.1016/j.tetlet.2016.08.001

  日期：2016.9

  Activation energies were determined for the additions of three arylhalocarbenes to tetramethoxyethylene (TMeOE) and tetramethylethylene (TME) in pentane and decane. For addition of 3,5-dinitrophenylchlorocarbene to TMeOE in decane, Ea = −10.4 ± 0.7 kcal/mol, the most negative activation energy yet encountered in a carbene–alkene addition reaction. Computational studies parallel and elucidate the experimental

  确定了在戊烷和癸烷中向四甲氧基乙烯（TMeOE）和四甲基乙烯（TME）中添加三种芳基卤代卡宾的活化能。对于在癸烷中的TMeOE中添加3,5-二硝基苯基氯卡宾，E a  = -10.4±0.7 kcal / mol，这是卡宾-烯烃加成反应中遇到的最负的活化能。计算研究平行并阐明了实验结果。
• 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).