diphenyldiazomethane radical cation | 64401-31-6

• 英文名称: diphenyldiazomethane radical cation
• CAS: 64401-31-6
• 化学式: C₁₃H₁₀N₂
• 分子量: 194.236
• InChiKey: XKAWCRUFSHGCHZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  甲醇 、 diphenyldiazomethane radical cation 在 吡啶 、 sodium perchlorate 作用下， 生成 二苯甲酮 、 (甲氧基-苯基甲基)苯 、 1,1,2,2-四苯乙烯
  参考文献：
  名称：

  Carbene cation radicals: the kinetics of their formation from diazoalkane cation radicals and their reactions

  摘要：

  DOI：

  10.1021/ja00251a002
• 作为产物：
  描述：

  二苯基重氮甲烷 在 tetrabutylammonium tetrafluoroborate 作用下， 以 二氯甲烷 为溶剂， 生成 diphenyldiazomethane radical cation
  参考文献：
  名称：

  Formation and reactivity of .sigma.-radical cation intermediates in the carbon-carbon coupling reaction of phenyldiazomethanes by one-electron oxidation

  摘要：

  One-electron oxidation of phenyldiazomethanes afforded cis-stilbene predominantly. The reaction was independent of the oxidation methods, e.g., electrolysis, copper(II), triarylaminium salts, or photosensitized one-electron oxidations. The C-C coupling reaction was retarded by introducing alpha-substituents on phenyldiazomethane. The ESR spectra of diazoalkane radical cations could be obtained during the electrolysis at low temperature and the resulting spectra revealed their unique electronic structure as sigma-radicals for most cases. When a bulky tert-butyl group was substituted, the corresponding pi-radical cation was observed, but the C-C coupling reaction did not occur. The novel HOMO-LUMO switching by one-electron removal from the HOMO pi-orbital of diazomethane is explained by the interaction of phenyl group with the C-N-N sigma-radical moiety. The C-C coupling reaction proceeds via facile [4 + 2] cycloaddition between the diazomethane and sigma-radical cation, and the preferential formation of cis-olefins is based on the secondary orbital interaction between the two phenyl groups. The structure and the stability of radical cation intermediates are rationalized on the basis of ab initio calculations.

  DOI：

  10.1021/jo00037a021