9,10-Bis(trifluorovinyl)phenanthrene | 131759-26-7

• 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: 9,10-Bis(trifluorovinyl)phenanthrene
• 英文别名: 9,10-Bis(trifluoroethenyl)phenanthrene；9,10-bis(1,2,2-trifluoroethenyl)phenanthrene
• CAS: 131759-26-7
• 化学式: C₁₈H₈F₆
• 分子量: 338.252
• InChiKey: WKCVAUPOYPNEHP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  3.0
• 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：
  6

反应信息

• 作为反应物：
  描述：

  9,10-Bis(trifluorovinyl)phenanthrene 以16%的产率得到
  参考文献：
  名称：

  DOLBIER, WILLIAM R. (JR);PALMER, KEITH;KORONIAK, HENRYK;ZHANG, HUA-QI;GOE+, J. AMER. CHEM. SOC., 113,(1991) N, C. 1059-1060

  摘要：

  DOI：
• 作为产物：
  描述：

  9-溴菲 在 四(三苯基膦)钯 硝酸 、 sodium iodide 作用下， 以 乙酸酐 、 溶剂黄146 、 N,N-二甲基甲酰胺 为溶剂， 反应 30.5h， 生成 9,10-Bis(trifluorovinyl)phenanthrene
  参考文献：
  名称：

  Thermal rearrangements of 9,10-bis(trifluorovinyl)phenanthrene

  摘要：

  Results from a study of the thermal unimolecular rearrangement of 9,10-bis(trifluorovinyl)-phenanthrene are reported. Kinetic and product studies indicate that it is unexpectedly resistant to rearrangement, that its expected 6pi electrocyclic rearrangement plays but a minor role, and that the major rearrangement process was a virtually unprecedented thermal reaction for 1,3,5-trienes, that of conversion to a bicyclo[3.1.0]hex-2-ene system (7). Activation parameters are provided for the minor electrocyclic process (DELTAH(double dagger) = 29.9 kcal/mol; DELTAS(double dagger) = -19.6 eu) and for the conversion to 7 (DELTAH(double dagger) = 34.4 kcal/mol; DELTAS(double dagger) = -6.6 eu) as well as for the secondary conversions of 7 to 4-(difluoromethylidene)-3,3,5,5-tetrafluoro-1,2-(9,10-phenanthro)cyclopent-1-ene (8) (DELTAH(double dagger) = 31.3 kcal/mol; DELTAS(double dagger) = -12.7 eu) and to 1,2-(9,10-phenanthro)-3,5,5-trifluoro-4-(trifluoromethyl)-1,3-cyclopentadiene (9) (DLETAH(double dagger) = 31.4 kcal/mol; DELTAS(double dagger) = -13.4 eu). A rarely encountered fluorine steric effect deriving from the stringent steric demands of the reaction's boat-like transition state is invoked to explain the inhibition of 1's electrocyclic process, while equally rare thermal 1,2-fluorine atom shifts are proposed to explain the rearrangement of 7.

  DOI：

  10.1021/jo00077a027

文献信息

• Modular Construction of Fluoroarenes from a New Difluorinated Building Block by Cross-Coupling/Electrocyclisation/Dehydrofluorination Reactions
  作者：Jonathan M. Percy、Helena Emerson、James W. B. Fyfe、Alan R. Kennedy、Sergej Maciuk、David Orr、Lucie Rathouská、Joanna M. Redmond、Peter G. Wilson

  DOI：10.1002/chem.201601584

  日期：2016.8.16

  were used to assemble precursors to 6π‐electrocyclisations of three different types. Electrocyclisations took place at temperatures between 90 and 240 °C, depending on the central component of the π‐system; nonaromatic trienes were most reactive, but even systems that required the temporary dearomatisation of two arenyl subunits underwent electrocyclisation, albeit at elevated temperatures. Photochemical

  基于新颖且易于合成的二氟化有机三氟硼酸盐的钯催化偶联反应被用于组装前体，以形成三种不同类型的6π电环化反应。电环化发生在90到240°C的温度之间，具体取决于π系统的中心组成。非芳族三烯具有最高的反应活性，但是即使需要将两个戊基亚基暂时脱芳香化的系统也要进行电环化，尽管温度较高。光化学条件对于这些更苛刻的反应是有效的。该方法包通过灵活的途径提供了结构上多样化的氟化芳烃组，其跨越20kcal mol -1的反应性范围。
• Fluorine substituent effects on thermal isomerizations: a new thermal reaction of 1,3,5-hexatrienes
  作者：William R. Dolbier、Keith Palmer、Henryk Koroniak、Hua Qi Zhang、Virgil L. Goedkin

  DOI：10.1021/ja00003a059

  日期：1991.1

  Fluorine substituents have been observed to have a remarkable effect upon the rate and stereochemical outcome of the butadiene-cyclobutene thermal conrotatory 4π-electron electrocyclic interconversion. The substituent effects observed in this system and in other pericyclic systems have enhanced one's understanding of the mechanisms of such reactions, such that only a small probable effect of fluorine

  已经观察到氟取代基对丁二烯-环丁烯热旋转 4π-电子电环互变的速率和立体化学结果有显着影响。在该系统和其他周环系统中观察到的取代基效应增强了人们对此类反应机制的理解，因此对于相关的 6π-电子系统，即偏旋 1,3 ,5-己三烯-1,3-环己二烯转化。为了探索该系统，设计了一种利用 1,2-双（三氟乙烯基）萘的热解的策略
• DOLBIER, WILLIAM R. (JR);PALMER, KEITH;KORONIAK, HENRYK;ZHANG, HUA-QI;GOE+, J. AMER. CHEM. SOC., 113,(1991) N, C. 1059-1060
  作者：DOLBIER, WILLIAM R. (JR)、PALMER, KEITH、KORONIAK, HENRYK、ZHANG, HUA-QI、GOE+

  DOI：——

  日期：——
• Dolbier William R., (Jr), Palmer Keith W., J. Org. Chem, 58 (1993) N 25, S 7064- 7069
  作者：Dolbier William R., (Jr), Palmer Keith W.

  DOI：——

  日期：——
• Thermal rearrangements of 9,10-bis(trifluorovinyl)phenanthrene
  作者：William R. Dolbier、Keith W. Palmer

  DOI：10.1021/jo00077a027

  日期：1993.12

  Results from a study of the thermal unimolecular rearrangement of 9,10-bis(trifluorovinyl)-phenanthrene are reported. Kinetic and product studies indicate that it is unexpectedly resistant to rearrangement, that its expected 6pi electrocyclic rearrangement plays but a minor role, and that the major rearrangement process was a virtually unprecedented thermal reaction for 1,3,5-trienes, that of conversion to a bicyclo[3.1.0]hex-2-ene system (7). Activation parameters are provided for the minor electrocyclic process (DELTAH(double dagger) = 29.9 kcal/mol; DELTAS(double dagger) = -19.6 eu) and for the conversion to 7 (DELTAH(double dagger) = 34.4 kcal/mol; DELTAS(double dagger) = -6.6 eu) as well as for the secondary conversions of 7 to 4-(difluoromethylidene)-3,3,5,5-tetrafluoro-1,2-(9,10-phenanthro)cyclopent-1-ene (8) (DELTAH(double dagger) = 31.3 kcal/mol; DELTAS(double dagger) = -12.7 eu) and to 1,2-(9,10-phenanthro)-3,5,5-trifluoro-4-(trifluoromethyl)-1,3-cyclopentadiene (9) (DLETAH(double dagger) = 31.4 kcal/mol; DELTAS(double dagger) = -13.4 eu). A rarely encountered fluorine steric effect deriving from the stringent steric demands of the reaction's boat-like transition state is invoked to explain the inhibition of 1's electrocyclic process, while equally rare thermal 1,2-fluorine atom shifts are proposed to explain the rearrangement of 7.