1-ethynyl-9-fluorenone | 221458-73-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 1-ethynyl-9-fluorenone
• 英文别名: 1-Ethynylfluoren-9-one
• CAS: 221458-73-7
• 化学式: C₁₅H₈O
• 分子量: 204.228
• InChiKey: MQQSOHYSDGQSOL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-ethynyl-9-fluorenone 在 copper(l) iodide 、 四(三苯基膦)钯 、 叔丁基锂 、 N,N-二异丙基乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 12.5h， 生成
  参考文献：
  名称：

  Thermolysis of Benzoenyne−Allenes To Form Biradicals and Subsequent Intramolecular Trapping with a Tetraarylallene To Generate Two Triarylmethyl Radical Centers

  摘要：

  Thermolysis of the benzoenyne-allene 20 in 1,4-cyclohexadiene (1,4-CHD) at 75 degrees C produced the cycloaromatized adduct 23 in 22% yield. The reaction presumably proceeds through a cascade sequence involving an initial Myers cyclization reaction to form the biradical 21. The subsequent trapping of the aryl radical center in 21 with the tetraarylallenic moiety intramolecularly affords 22, having two stabilized triarylmethyl radical centers. Hydrogen-atom abstraction from 1,4-CHD by 22, manifesting its radical character, then produces 23. Similarly, thermolysis of benzoenyne-allenes 25 in 1,4-CHD furnished fluoranthenes 27 in essentially quantitative yields. The presence of the fused five-membered ring in 20 and 25 is necessary to direct the initial biradical-forming step toward the Myers cyclization reaction. Without the five-membered ring as in the cases of 31, the C2-C6 cyclization reaction became the preferred pathway, leading to benzofluorenes 34.

  DOI：

  10.1021/jo982326k
• 作为产物：
  描述：

  1-iodo-9-fluorenone 在 sodium hydroxide 、 copper(l) iodide 、 四(三苯基膦)钯 、 N,N-二异丙基乙胺 作用下， 以 甲醇 、 乙醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 12.5h， 生成 1-ethynyl-9-fluorenone
  参考文献：
  名称：

  Thermolysis of Benzoenyne−Allenes To Form Biradicals and Subsequent Intramolecular Trapping with a Tetraarylallene To Generate Two Triarylmethyl Radical Centers

  摘要：

  Thermolysis of the benzoenyne-allene 20 in 1,4-cyclohexadiene (1,4-CHD) at 75 degrees C produced the cycloaromatized adduct 23 in 22% yield. The reaction presumably proceeds through a cascade sequence involving an initial Myers cyclization reaction to form the biradical 21. The subsequent trapping of the aryl radical center in 21 with the tetraarylallenic moiety intramolecularly affords 22, having two stabilized triarylmethyl radical centers. Hydrogen-atom abstraction from 1,4-CHD by 22, manifesting its radical character, then produces 23. Similarly, thermolysis of benzoenyne-allenes 25 in 1,4-CHD furnished fluoranthenes 27 in essentially quantitative yields. The presence of the fused five-membered ring in 20 and 25 is necessary to direct the initial biradical-forming step toward the Myers cyclization reaction. Without the five-membered ring as in the cases of 31, the C2-C6 cyclization reaction became the preferred pathway, leading to benzofluorenes 34.

  DOI：

  10.1021/jo982326k

文献信息

• Thermolysis of Benzoenyne−Allenes To Form Biradicals and Subsequent Intramolecular Trapping with a Tetraarylallene To Generate Two Triarylmethyl Radical Centers
  作者：Kung K. Wang、Hai-Ren Zhang、Jeffrey L. Petersen

  DOI：10.1021/jo982326k

  日期：1999.3.1

  Thermolysis of the benzoenyne-allene 20 in 1,4-cyclohexadiene (1,4-CHD) at 75 degrees C produced the cycloaromatized adduct 23 in 22% yield. The reaction presumably proceeds through a cascade sequence involving an initial Myers cyclization reaction to form the biradical 21. The subsequent trapping of the aryl radical center in 21 with the tetraarylallenic moiety intramolecularly affords 22, having two stabilized triarylmethyl radical centers. Hydrogen-atom abstraction from 1,4-CHD by 22, manifesting its radical character, then produces 23. Similarly, thermolysis of benzoenyne-allenes 25 in 1,4-CHD furnished fluoranthenes 27 in essentially quantitative yields. The presence of the fused five-membered ring in 20 and 25 is necessary to direct the initial biradical-forming step toward the Myers cyclization reaction. Without the five-membered ring as in the cases of 31, the C2-C6 cyclization reaction became the preferred pathway, leading to benzofluorenes 34.