7-Fluorobenzofluoranthene | 89883-22-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 7-Fluorobenzofluoranthene
• 英文别名: 7-F-benzofluoroanthene；Benz(e)acephenanthrylene, 7-fluoro-；17-fluoropentacyclo[10.7.1.02,7.08,20.013,18]icosa-1(19),2(7),3,5,8(20),9,11,13,15,17-decaene
• CAS: 89883-22-7
• 化学式: C₂₀H₁₁F
• 分子量: 270.306
• InChiKey: HXFZQKJCQNOMBF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  9-溴菲 在 bis(triphenylphosphine)palladium(II)-chloride 2,6-二甲基吡啶 、 三溴化硼 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 lithium chloride 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 19.0h， 生成 7-Fluorobenzofluoranthene
  参考文献：
  名称：

  An intramolecular arene-triflate coupling reaction for the regiospecific synthesis of substituted benzofluoranthenes

  摘要：

  An intramolecular triflate-arene coupling reaction mediated by bis(triphenylphosphine)palladium(II) chloride has been developed for the synthesis of each of the isomeric benzofluoranthenes. This reaction, which results in formation of a new five-membered ring, proceeds in highest yield when performed using 0.1 equiv of the palladium catalyst, 3 equiv of lithium chloride, and 1.2 equiv of 1,8-diazabicyclo[5.4.0]undec-7-ene in N,N-dimethylformamide at 140-degrees-C. The biaryl precursors needed for the coupling reaction can be prepared by [1,2-bis(diphenylphosphino)ethane]nickel(II) chloride catalyzed coupling of an aryl bromide with an [o-(methoxymethoxy)aryl]magnesium bromide (prepared by ortho-lithiation of an aryl methoxymethyl ether followed by transmetalation with magnesium bromide). Using this procedure benzo[a]fluoranthene, benzo[b]fluoranthene, benzo[j]fluoranthene, and benzo[k]fluoranthene were prepared in yields of 84%, 85%, 93%, and 64%, respectively. The reaction to prepare benzo[j]fluoranthene was regiospecific and afforded none of the six-membered ring product, perylene. The method was extended to the preparation of benzo[b]fluoranthene (BbF) derivatives with fluoro or methoxy groups on the benzo ring. The cyclization of compounds possessing a methoxy group on the same ring as the triflate required the addition of 0.4 equiv of triphenylphosphine to the reaction mixture. Strategies are reported for the regiospecific preparation of 4-, 5-, 6-, and 7-substituted benzo[b]fluoranthenes. Evidence is presented which suggests the intermediacy of radicals in the oxidative-addition of aryl triflates to the palladium catalyst.

  DOI：

  10.1021/jo00058a023

文献信息

• Synthesis and 1H and 13C NMR spectra of 7-fluoro-, 9-fluoro- and 11-fluoro-benzo[b]fluoranthenes
  作者：D.J. Sardella、P.K. Ghoshal、E. Boger

  DOI：10.1016/s0022-1139(00)85208-2

  日期：1984.2

  We have synthesized 7-fluoro-, 9-fluoro- and 11-fluoro- benzo[b]fluoranthene as part of a study designed to locate the molecular sites involved in the metabolic activation of the carcinogenic parent hydrocarbon. Analysis of the proton NMR spectra reveals the effect of fluorine substitution to be almost entirely localized in the substituted ring, the principal exception being a strong deshielding of

  我们合成了7-氟-，9-氟-和11-氟-苯并[b]荧蒽，作为旨在定位与致癌母体烃代谢活化有关的分子位点的研究的一部分。质子NMR谱的分析表明，氟取代的作用几乎完全位于取代的环中，主要的例外是在空间拥挤的位点（即周向或伪湾区）中相对质子的强屏蔽作用。
• An intramolecular arene-triflate coupling reaction for the regiospecific synthesis of substituted benzofluoranthenes
  作者：Joseph E. Rice、Zhen Wei Cai

  DOI：10.1021/jo00058a023

  日期：1993.3

  An intramolecular triflate-arene coupling reaction mediated by bis(triphenylphosphine)palladium(II) chloride has been developed for the synthesis of each of the isomeric benzofluoranthenes. This reaction, which results in formation of a new five-membered ring, proceeds in highest yield when performed using 0.1 equiv of the palladium catalyst, 3 equiv of lithium chloride, and 1.2 equiv of 1,8-diazabicyclo[5.4.0]undec-7-ene in N,N-dimethylformamide at 140-degrees-C. The biaryl precursors needed for the coupling reaction can be prepared by [1,2-bis(diphenylphosphino)ethane]nickel(II) chloride catalyzed coupling of an aryl bromide with an [o-(methoxymethoxy)aryl]magnesium bromide (prepared by ortho-lithiation of an aryl methoxymethyl ether followed by transmetalation with magnesium bromide). Using this procedure benzo[a]fluoranthene, benzo[b]fluoranthene, benzo[j]fluoranthene, and benzo[k]fluoranthene were prepared in yields of 84%, 85%, 93%, and 64%, respectively. The reaction to prepare benzo[j]fluoranthene was regiospecific and afforded none of the six-membered ring product, perylene. The method was extended to the preparation of benzo[b]fluoranthene (BbF) derivatives with fluoro or methoxy groups on the benzo ring. The cyclization of compounds possessing a methoxy group on the same ring as the triflate required the addition of 0.4 equiv of triphenylphosphine to the reaction mixture. Strategies are reported for the regiospecific preparation of 4-, 5-, 6-, and 7-substituted benzo[b]fluoranthenes. Evidence is presented which suggests the intermediacy of radicals in the oxidative-addition of aryl triflates to the palladium catalyst.