6-methoxybenzofluoranthene | 100516-27-6

• 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: 6-methoxybenzofluoranthene
• 英文别名: 18-Methoxypentacyclo[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: 100516-27-6
• 化学式: C₂₁H₁₄O
• 分子量: 282.342
• InChiKey: FLRVNEAJQIUQFG-UHFFFAOYSA-N

物化性质

• 熔点：
  145-146 °C
• 沸点：
  498.6±14.0 °C(Predicted)
• 密度：
  1.282±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  22
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  6-methoxybenzofluoranthene 在 三溴化硼 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以74%的产率得到6-hydroxybenzofluoranthene
  参考文献：
  名称：

  Chemical carcinogenesis. 93. Synthesis of potential phenolic metabolites of benzo[b]fluoranthene

  摘要：

  DOI：

  10.1021/jo00358a009
• 作为产物：
  描述：

  9-溴菲 在 bis(triphenylphosphine)palladium(II)-chloride 2,6-二甲基吡啶 、 盐酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三苯基膦 、 lithium chloride 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 14.0h， 生成 6-methoxybenzofluoranthene
  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

• Regioselective Activation of a Sterically More Hindered C−C Bond of Biphenylenes Using an Alkene as Both a Directing Group and a Reaction Moiety
  作者：Hideaki Takano、Takeharu Ito、Kyalo Stephen Kanyiva、Takanori Shibata

  DOI：10.1002/chem.201804044

  日期：2018.10.12

  The Rh‐catalyzed intramolecular reaction of 1‐(2‐vinylaryl)‐substituted biphenylenes was used to construct a dihydrobenzo[b]fluoranthene skeleton. This transformation was achieved by regioselective C−C bond cleavage of a sterically more hindered biphenylene site by using alkene as both a directing group and a reaction moiety. Furthermore, we measured and analyzed the photophysical properties of the

  1-（2-乙烯基芳基）取代的联苯的Rh催化的分子内反应被用来构建二氢苯并[ b ]荧蒽骨架。通过使用烯烃作为导向基团和反应部分，通过在空间上更受阻的联苯部位的区域选择性C-C键断裂实现了该转化。此外，我们测量并分析了新型多环稠合化合物的光物理性质。
• Rice, Joseph E.; Cai, Zhen-Wei, Tetrahedron Letters, 1992, vol. 33, # 13, p. 1663 - 1678
  作者：Rice, Joseph E.、Cai, Zhen-Wei

  DOI：——

  日期：——
• AMIN, SHANTU;HUIE, KEITH;HUSSAIN, NALBAND;BALANIKAS, G.;CARMELLA, S. G.;H+, J. ORG. CHEM., 1986, 51, N 8, 1206-1211
  作者：AMIN, SHANTU、HUIE, KEITH、HUSSAIN, NALBAND、BALANIKAS, G.、CARMELLA, S. G.、H+

  DOI：——

  日期：——
• Chemical carcinogenesis. 93. Synthesis of potential phenolic metabolites of benzo[b]fluoranthene
  作者：Shantu Amin、Keith Huie、Nalband Hussain、George Balanikas、Steven G. Carmella、Stephen S. Hecht

  DOI：10.1021/jo00358a009

  日期：1986.4
• 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.