(p-Methylphenyl)tert-butyldiazomethane | 133861-35-5

• 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: (p-Methylphenyl)tert-butyldiazomethane
• 英文别名: 1-(1-Diazo-2,2-dimethylpropyl)-4-methylbenzene；1-(1-diazo-2,2-dimethylpropyl)-4-methylbenzene
• CAS: 133861-35-5
• 化学式: C₁₂H₁₆N₂
• 分子量: 188.272
• InChiKey: NSNODQAJZTXBJN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (p-Methylphenyl)tert-butyldiazomethane 在 tetrabutylammonium tetrafluoroborate 作用下， 以 二氯甲烷 为溶剂， 生成
  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
• 作为产物：
  描述：

  2,2-二甲基-1-(4-甲基苯基)丙-1-酮 在 氢氧化钾 、 一水合肼 、 mercury(II) oxide 作用下， 以 乙醚 、 乙醇 为溶剂， 反应 10.0h， 生成 (p-Methylphenyl)tert-butyldiazomethane
  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

文献信息

• Formation and reactivity of .sigma.-radical cation intermediates in the carbon-carbon coupling reaction of phenyldiazomethanes by one-electron oxidation
  作者：Katsuya Ishiguro、Masatoshi Ikeda、Yasuhiko Sawaki

  DOI：10.1021/jo00037a021

  日期：1992.5

  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.