1,6-Bis(diazo)-1,6-diphenylhexane | 21266-01-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 1,6-Bis(diazo)-1,6-diphenylhexane
• 英文别名: (1,6-Didiazo-6-phenylhexyl)benzene
• CAS: 21266-01-3
• 化学式: C₁₈H₁₈N₄
• 分子量: 290.368
• InChiKey: VNPDCKCSKJFKSP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,6-Bis(diazo)-1,6-diphenylhexane 在 copper(II) perchlorate 作用下， 以 乙腈 为溶剂， 以84%的产率得到(2-苯基环己烯-1-基)苯
  参考文献：
  名称：

  重氮甲烷自由基阳离子作为重氮化合物二聚烯烃形成中的亲偶极体

  摘要：

  提出了一种涉及重氮甲烷自由基阳离子的新型环加成机制，用于通过重氮化合物的单电子氧化形成二聚烯烃。通过苯基在环加成步骤中的次级轨道相互作用来理解从苯基重氮甲烷形成顺式二苯乙烯的优选性。

  DOI：

  10.1246/cl.1987.1853
• 作为产物：
  描述：

  1,6-二苯基-1,6-己二酮二腙 在 氢氧化钾 、 sodium sulfate 、 mercury(II) oxide 作用下， 以 乙醚 为溶剂， 反应 6.0h， 生成 1,6-Bis(diazo)-1,6-diphenylhexane
  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