9-甲基-9-苯基芴 | 56849-83-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 中文名称: 9-甲基-9-苯基芴
• 英文名称: 9-methyl-9-phenylfluorene
• 英文别名: 9-Methyl-9-phenyl-fluoren
• CAS: 56849-83-3
• 化学式: C₂₀H₁₆
• 分子量: 256.347
• InChiKey: ZNGOZTGLIVGMQC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  9-chloro-9-phenyl-9H-fluorene 在 二叔丁基过氧化物 、 苄硫醇 作用下， 生成 9-甲基-9-苯基芴
  参考文献：
  名称：

  Substituent effects at the origin of a free-radical 1,2-aryl migration and in the related disproportionation reaction of 10-hydro-9-p-X-phenyl-9-phenanthryl radicals

  摘要：

  DOI：

  10.1021/jo00421a004

文献信息

• Direct C–H bond arylation of fluorenes with aryl chlorides catalyzed by N-heterocyclic carbene–palladium(<scp>ii</scp>)–1-methylimidazole complex and further transformation of the products in a one-pot procedure
  作者：Ya-Yun Ji、Li-Li Lu、Yu-Chun Shi、Li-Xiong Shao

  DOI：10.1039/c4ob01594k

  日期：——

  We report here the NHC–Pd(II)–Im complex 1-catalyzed direct C–H bond functionalization of the C9 position of fluorenes with aryl chlorides and further transformation of the resulting products in a one-pot procedure. Under the optimal conditions, arylated fluorenes can be obtained in moderate to almost quantitative yields using various activated and unactivated (hetero)aryl chlorides as the arylating reagents. Furthermore, if the mixture from the arylation reaction is exposed to air, the C9-oxidized products can be obtained in acceptable to good yields in a one-pot procedure. In addition, alkyl groups can also be efficiently introduced to the above mixture from the arylation reaction, producing further C9-alkylated products in good to almost quantitative yields in a one-pot procedure, thus providing an expedient, inexpensive and practical strategy for the mono- and di-functionalization of fluorenes.

  我们在这里报道了NHC–Pd(II)–Im配合物1催化下，通过一步法直接对芴类化合物C9位进行C–H键官能团化，使用芳基氯化物作为芳基化试剂，并进一步转化所得产物。在最佳条件下，可以通过使用各种活化和未活化的（杂）芳基氯化物作为芳基化试剂，以中等至几乎定量的产率获得芳基化芴类化合物。此外，如果将来自芳基化反应的混合物暴露于空气中，可以在一步法中以可接受的至良好产率获得C9氧化产物。此外，还可以有效地将烷基引入上述来自芳基化反应的混合物中，通过一步法以良好至几乎定量的产率产生进一步的C9烷基化产物，从而为芴类化合物的单功能化和二功能化提供了一种便捷、经济且实用的策略。
• Metal-free cycloisomerizations of <i>o</i>-alkynylbiaryls
  作者：Jingyi Zhang、Siqi Li、Yan Qiao、Cheng Peng、Xiao-Na Wang、Junbiao Chang

  DOI：10.1039/c8cc05484c

  日期：——

  We describe a novel and highly efficient metal-free strategy to construct 9,9-disubstituted fluorenes and phenanthrenes via the TfOH-catalyzed cycloisomerizations of o-alkynylbiaryls. Notably, the significant effects of the electronic properties and steric hindrance of the alkyne terminus on the reaction selectivity have been observed.

  我们描述了一种新型且高效的无金属策略，可通过T-OH催化的邻炔基联芳基的环异构化反应来构建9,9-二取代的芴和菲。值得注意的是，已经观察到炔烃末端的电子性质和位阻对反应选择性的显着影响。
• ALIPHATIC CHEMISTRY OF FLUORENE: PART II. AN UNUSUAL GRIGNARD REACTION
  作者：P. M. G. Bavin

  DOI：10.1139/v60-125

  日期：1960.6.1

  The reaction between methyl 9-methylfluorene-9-carboxylate and phenyl magnesium iodide gave 9,9′-dimethyl-9,9′-difluorenyl in almost quantitative yield. Evidence is presented which shows that 9-methylfluorene anion is an intermediate. The probable intervention of elemental iodine is discussed.9-Methyl-9,9′-difluorenyl and 9,9′-dimethyl-9,9′-difluorenyl have been synthesized. A convenient preparation

  9-甲基芴-9-羧酸甲酯和苯基碘化镁之间的反应以几乎定量的产率得到9,9'-二甲基-9,9'-二芴基。提供的证据表明 9-甲基芴阴离子是中间体。讨论了元素碘的可能干预作用。已经合成了9-甲基-9,9'-二芴基和9,9'-二甲基-9,9'-二芴基。描述了 9,9'-二芴基的方便制备。
• The one-electron oxidation of biphenyl-2-ylethylenes. Subsequent chemical reactivity controlled by electron return or proton transfer
  作者：Ren� Lapouyade、Patrice Villeneuve、Aziz Nourmamode、Jean-Pierre Morand

  DOI：10.1039/c39870000776

  日期：——

  Biphenyl-2-ylethylenes react with (4-BrC6H4)3N˙+SbCl6– to give the radical cation of the electrocyclization product which initiates a protic catalysis to the related fluorenes or, in presence of 2,6-di-t-butylpyridine or water, lead stoicheiometrically to phenanthrenes; with photochemical oxidants only phenanthrenes or 9,10-dihydrophenanthrenes are obtained, with an efficiency related to the polarity

  联苯-2- ylethylenes与反应（4- BRC 6 ħ 4）3 Ñ +的SbCl 6 - ，得到发起质子催化现有芴，或在2,6-二存在下electrocyclization产物的自由基阳离子-叔丁基吡啶或水，从化学计量学上导致菲；用光化学氧化剂只能得到菲或9，10-二氢菲，其效率与溶剂的极性以及三重态供体和自由基离子对的相对能量有关。
• Iridium-Catalyzed Formal [4 + 1] Cycloaddition of Biphenylenes with Alkenes Initiated by C–C Bond Cleavage for the Synthesis of 9,9-Disubstituted Fluorenes
  作者：Hideaki Takano、Kyalo Stephen Kanyiva、Takanori Shibata

  DOI：10.1021/acs.orglett.6b00619

  日期：2016.4.15

  An Ir-catalyzed intermolecular reaction of biphenylenes as a C4 unit with various alkenes as a C1 unit gave 9,9-disubstituted fluorenes in moderate to high yields. Preliminary mechanistic studies revealed that this formal [4 + 1] cycloaddition probably proceeds via C–C bond cleavage, alkene insertion, β-hydrogen elimination, intramolecular alkene insertion, and then reductive elimination. An example

  Ir催化的联苯作为C4单元与各种烯烃作为C1单元的分子间反应以中等至高收率得到9,9-二取代的芴。初步的机理研究表明，这种正式的[4 +1]环加成反应可能是通过C–C键断裂，烯烃插入，β-氢消除，分子内烯烃插入，然后是还原消除进行的。还公开了对映选择性反应的实例。